CN101514265A - Mixed calcium carbonate, preparation method and application thereof - Google Patents
Mixed calcium carbonate, preparation method and application thereof Download PDFInfo
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- CN101514265A CN101514265A CNA2008102049549A CN200810204954A CN101514265A CN 101514265 A CN101514265 A CN 101514265A CN A2008102049549 A CNA2008102049549 A CN A2008102049549A CN 200810204954 A CN200810204954 A CN 200810204954A CN 101514265 A CN101514265 A CN 101514265A
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Abstract
The invention provides mixed calcium carbonate, a preparation method and application thereof. The preparation method comprises the following steps: adding ground whiting powder into water to prepare a ground whiting pulp; carrying out superfine grinding on the ground whiting to prepare the ground whiting pulp; adding an anionic polyelectrolyte solution equivalent to the weight of the ground whiting dry powder into the pulp; and adding precipitated calcium carbonate into the pulp and stirring the mixed solution to prepare mixed calcium carbonate pulp. The mixed calcium carbonate has advantages of both the ground whiting and the precipitated calcium carbonate, and can be used for packing of paper making.
Description
Technical field
The present invention relates to the preparation method of lime carbonate.
Background technology
The adding filler can improve paper in the papermaking opaqueness and brightness improve smoothness of paper and uniform state, increase the flexibility of paper, reduce the water absorbability and the deformation extent of paper, also help simultaneously to reduce production costs.Titanium dioxide has high refractive index and scattering coefficient, is good papermaking filler, but because it costs an arm and a leg, generally only is used for high-grade thin page or leaf printing paper, to improve the opaqueness of paper; And lime carbonate is cheap owing to it, and can improve the opaqueness of paper, the oil suction performance of ink of increase paper equally, has certain cost advantage as papermaking filler.
Along with acid papermaking changes to neutral papermaking, lime carbonate becomes the important raw and processed materials that Chinese paper industry improves paper quality, reduces the papermaking cost day by day.Coarse whiting and the fine particle calcium carbonate effect in paper has bigger difference: fine particle calcium carbonate and coarse whiting are copied the pattern whiteness and are more or less the same, and both whiteness are all higher; But aspect opaqueness, the opaqueness of pattern that fine particle calcium carbonate is copied is higher, can improve the opaqueness of page behind the adding fine particle calcium carbonate.With its bulk of pattern that fine particle calcium carbonate is copied apparently higher than coarse whiting; The median size of fine particle calcium carbonate is little than coarse whiting, correspondingly has bigger specific surface area, and is stronger than coarse whiting to the adsorption of AKD sizing agent, thereby the amount ratio coarse whiting of AKD sizing agent is big.When identical amount of filler, fine particle calcium carbonate mainly is because the particle diameter of coarse whiting is little than the ash content height of coarse whiting, and when the page dehydration was shaped, it is poor that fiber is held back fine particle; Though and the particle diameter of fine particle calcium carbonate is also very little, fine particle calcium carbonate is agglomerated into bigger particle easily, and paper fibre is had good bridging action, so be better than coarse whiting at fine particle calcium carbonate aspect the ash content reservation; In addition, the water-ground limestone particle diameter is little and be the cubic structure mostly, and light calcium carbonate is more serious than light calcium carbonate to the wearing and tearing of net relatively.But the stability of the pH value of water-ground limestone is than light calcium carbonate height; The water-ground limestone low price, in the course of processing energy consumption low, and light calcium carbonate price height, in the course of processing energy consumption big, consume a large amount of hard coals in the production process.So the application in papermaking of water-ground limestone and light calcium carbonate respectively has relative merits, how the advantages with the two is the key of dealing with problems together.
Pigment particles of Chinese patent CN 1217007 coated with precipitated calcium carbonate and preparation method thereof, introduced kaolin, natural whiting or titanium dioxide water have been made slurry, pH value of slurry is transferred to 6-11 then, adding grain diameter in slurry is the light calcium carbonate slurry of 30-100nm, make the light calcium carbonate particle be coated in kaolin, natural whiting or titanium dioxide surface by absorption, obtain coated with precipitated calcium carbonate pigment, can be used for papermaking filler and papermaking pigment.New type of paper filler that Chinese patent CN 1335874 is treated or pigment or mineral substance, particularly contain pigment, its manufacture method and the composition and the application of natural whiting, introduced marble, calcite, chalk or the carbonate that contains rhombspar have been prepared into aqeous suspension, in aqeous suspension, add sulfuric acid, hydrochloric acid, phosphoric acid or oxalic acid, in aqeous suspension, feed carbonic acid gas then, obtain containing the pigment of natural whiting, this pigment can reduce the paper weight of constant surface area.
Chinese patent CN101209569 provide a kind of composite calcium carbonate and preparation method thereof, comprise the steps: that (1) mixes heavy calcium carbonate and water, the content that is made into water-ground limestone is 35～75% heavy calcium carbonate slurry, adopt the ultra-fine machine of delaminating of wet type that water-ground limestone is carried out ultra-fine mill then, make heavy calcium carbonate slurry; Add when in the acid solution of ground whiting dry powder weight 0.2～2.0% in slurry then, stirred 0.5～1.0 hour, filter dehydration is made filter cake, adds water and makes slurry, adds ammonium salt solution in slurry, stirs, and obtains activatory coarse whiting slurry; (2) add calcium hydroxide slurry in the coarse whiting slurry after the activation, lead to carbon dioxide again in the coarse whiting slurry, when carbonization is 6-7 to the pH value, obtain coarse whiting and fine particle calcium carbonate compound calcium carbonate slurry.
The method that Chinese patent CN101209569 provides has had bigger improvement than method in the past, but its used ammonium salt activator ion intensity is high not enough, and water-ground limestone combines jail not enough with light calcium carbonate; In addition, this method will add calcium hydroxide slurry in the coarse whiting slurry after the activation, and it is cumbersome that logical again carbon dioxide carries out carbonization, so also existing the improvement.
Summary of the invention
The purpose of this invention is to provide a kind of mixed calcium carbonate and its production and application, to overcome the above-mentioned defective that prior art exists.
The preparation method of mixed calcium carbonate of the present invention comprises the steps:
100～600 order heavy calcium carbonates are added in the entry, be made into the weight solid content and be 15～25% heavy calcium carbonate slurry; Adopt the ultra-fine machine of delaminating of wet type that water-ground limestone is carried out ultra-fine mill, make particle diameter and be 50～90% slurry less than the water-ground limestone weight content of 2 μ m;
In slurry, add the cationic polyelectrolyte solution that is equivalent to ground whiting dry powder weight 0.2～2.0% then, stirred 0.5～1.0 hour;
Add the light calcium carbonate that is equivalent to ground whiting dry powder amount 60～120% again in slurry, restir 20～30 minutes obtains the mixed calcium carbonate slurry;
The preparation method of described cationic polyelectrolyte solution is as follows:
With weight content is that 60～70% the dimethyl diallyl ammonium chloride aqueous solution is heated to 80～90 ℃, adds lauryl mercaptan then, adds the persulphate aqueous solution again, obtains cationic polyelectrolyte solution;
The add-on of described lauryl mercaptan is 0.1～0.5% of a dimethyl diallyl ammonium chloride oven dry weight;
Described persulphate can be more than one in ammonium persulphate, Sodium Persulfate or the Potassium Persulphate, the weight concentration of the persulphate aqueous solution is 5～15%, and the adding weight of the persulphate aqueous solution is 8～20% of dimethyl diallyl ammonium chloride oven dry weight;
Preferably, between 3～5 hours, the described persulphate aqueous solution is joined in the dimethyl diallyl ammonium chloride aqueous solution;
The mixed calcium carbonate slurry that adopts aforesaid method to obtain can directly be used as papermaking filler, also can further dewater and make filter cake, and filter cake can be used as papermaking filler; Also filtration cakes torrefaction, pulverizing can be made the compound calcium carbonate powders, as papermaking filler.
The present invention adds cationic polyelectrolyte in heavy calcium carbonate slurry, the positively charged ion in the cationic polyelectrolyte solution has positive charge, is easy to be adsorbed onto electronegative water-ground limestone particle surface, makes the water-ground limestone particle surface lotus that becomes positively charged.In heavy calcium carbonate slurry, add light calcium carbonate then, electronegative because of tiny calcium carbonate granule, be easy to be adsorbed onto the positively charged water-ground limestone particle surface in surface, thereby make the water-ground limestone particle surface coat light calcium carbonate.So the mixed calcium carbonate of present technique preparation has water-ground limestone and light calcium carbonate advantage separately.
Embodiment
Among the embodiment, if no special instructions, all be weight percentage.
Embodiment 1
The dimethyl diallyl ammonium chloride aqueous solution of 30kg65% (weight) joined in 100 liters the reactor, be heated to 80 ℃, add the 90g lauryl mercaptan, adding 4kg concentration again within 5 hours is 15% (weight) sodium persulfate aqueous solution, obtains cationic polyelectrolyte solution 33.2kg;
2.0 ton of 200 order heavy calcium carbonate joined in 8.0 tons of deionized waters, slurry is made in stirring, with pump slurry is sent into 300 liters of machines of delaminating then, with the machine of delaminating water-ground limestone is ground, making heavy calcium carbonate slurry, is that the weight content of 2 μ m is 50% less than grain diameter wherein.
Then 33.2kg cationic polyelectrolyte solution is joined in the above-mentioned heavy calcium carbonate slurry, again 2.0 tons of light calcium carbonate powder are joined in the heavy calcium carbonate slurry, obtain 12.1 tons in mixed calcium carbonate slurry.
Embodiment 2
The dimethyl diallyl ammonium chloride aqueous solution of 45kg65% (weight) joined in 100 liters the reactor, be heated to 90 ℃, add the 140g lauryl mercaptan then, adding 7kg concentration again within 4 hours is 10% (weight) ammonium persulfate aqueous solution, obtains cationic polyelectrolyte solution 51.3kg;
3.0 ton of 300 order heavy calcium carbonate joined in 10.0 tons of deionized waters, stir and make slurry, fully stir, make slurry obtain good flowability.With pump slurry is sent into 300 liters of machines of delaminating then, with the machine of delaminating water-ground limestone is ground, make heavy calcium carbonate slurry, wherein the weight content less than grain diameter 2 μ m is 90%.Then 51.3kg cationic polyelectrolyte solution is joined in the heavy calcium carbonate slurry, again 2.0 tons of light calcium carbonate powder are joined in the heavy calcium carbonate slurry, obtain 14.9 tons in mixed calcium carbonate slurry.
Embodiment 3
The dimethyl diallyl ammonium chloride aqueous solution of 40kg65% (weight) joined in 100 liters the reactor, be heated to 82 ℃, add the 100g lauryl mercaptan, within 3 hours, add the 6kg weight concentration again and be 12% persulfate aqueous solution, obtain cationic polyelectrolyte solution 45.2kg.
3.0 ton of 500 order heavy calcium carbonate joined in 12.0 tons of deionized waters, slurry is made in stirring, with pump slurry is sent into 300 liters of machines of delaminating then, with the machine of delaminating water-ground limestone is ground, make heavy calcium carbonate slurry, wherein the weight content less than grain diameter 2 μ m is 80%.Then 45.2kg cationic polyelectrolyte solution is joined in the heavy calcium carbonate slurry, again 4.0 tons of light calcium carbonate powder are joined in the heavy calcium carbonate slurry, obtain 18.8 tons in mixed calcium carbonate slurry.
Embodiment 4
The dimethyl diallyl ammonium chloride aqueous solution of 10kg65% (weight) joined in 50 liters the reactor, be heated to 85 ℃, add the 30g lauryl mercaptan then, in 3.5 hours, add the 1kg weight concentration again and be 5% ammonium persulfate aqueous solution, obtain cationic polyelectrolyte solution 10.4kg.
3.0 ton of 100 order heavy calcium carbonate joined in 15.0 tons of deionized waters, slurry is made in stirring, with pump slurry is sent into 300 liters of machines of delaminating then, with the machine of delaminating water-ground limestone is ground, make heavy calcium carbonate slurry, wherein the weight content less than grain diameter 2 μ m is 70%.Then 10.4kg cationic polyelectrolyte solution is joined in the heavy calcium carbonate slurry, again 3.8 tons of light calcium carbonate powder are joined in the heavy calcium carbonate slurry, obtain 21.4 tons in mixed calcium carbonate slurry.
Embodiment 5
The dimethyl diallyl ammonium chloride aqueous solution of 6kg65% (weight) joined in 20 liters the reactor, be heated to 75 ℃, add the 20g lauryl mercaptan, within 4.5 hours, add the 0.8kg weight concentration again and be 9% persulfate aqueous solution, obtain cationic polyelectrolyte solution 6.5kg.
3.0 ton of 300 order heavy calcium carbonate joined in 17.0 tons of deionized waters, stir and make slurry, fully stir, make slurry obtain good flowability.With pump slurry is sent into 300 liters of machines of delaminating then, with the machine of delaminating water-ground limestone is ground, make heavy calcium carbonate slurry, wherein grain diameter is % less than the weight content 75 of 2 μ m.Then 6.5kg cationic polyelectrolyte solution is joined in the heavy calcium carbonate slurry, again 3.0 tons of light calcium carbonate powder are joined in the heavy calcium carbonate slurry, obtain 22.8 tons in mixed calcium carbonate slurry.
Embodiment 6
With 1880 fourdrinier wire multi-cylinder culture papers, replace common coarse whiting and common fine particle calcium carbonate to be used for double gummed paper production with composite calcium carbonate, investigate the manufacture paper with pulp influence of process of papermaking, the variation of white water consistency, machine water concentration, initial journey retention rate, bulk, opaqueness.
Experiment condition:
Paper machine type, 1880 fourdrinier wire multi-cylinder culture papers;
Produce the paper kind, 70g/m
2Double gummed paper;
Filler, mixed calcium carbonate; Common coarse whiting; Common fine particle calcium carbonate.
Result such as table 1
Table 1
| White water consistency (%) | Initial journey retention (%) | Machine water concentration (%) | Filler retention (%) | Quantitative (g/m 2) | Bulk (cm 3/g) | Opaqueness (%) | |
| 50%40 grades of coarse whitings and 50%30 grades of fine particle calcium carbonate mixtures | 0.33 | 63.8 | 0.19 | 74.7 | 70.7 | 1.49 | 91.2 |
| Embodiment 1 | 0.21 | 74.9 | 0.11 | 84.3 | 70.3 | 1.88 | 92.9 |
| 60%40 grades of coarse whitings and 40%30 grades of fine particle calcium carbonate mixtures | 0.26 | 66.9 | 0.13 | 75.9 | 69.9 | 1.54 | 91.2 |
| Embodiment 2 | 0.21 | 74.8 | 0.11 | 84.5 | 71.4 | 1.89 | 92.7 |
| 38%40 grades of coarse whitings and 62%30 grades of fine particle calcium carbonate mixtures | 0.32 | 61.8 | 0.19 | 71.5 | 70.8 | 1.50 | 91.3 |
| Embodiment 3 | 0.22 | 75.1 | 0.09 | 85.3 | 71.2 | 1.94 | 93.1 |
| 65%40 grades of coarse whitings and 35%30 grades of fine particle calcium carbonate mixtures | 0.29 | 66.8 | 0.11 | 79.0 | 69.4 | 1.61 | 91.2 |
| Embodiment 4 | 0.22 | 75.2 | 0.10 | 84.6 | 70.9 | 1.87 | 92.8 |
| 50 grades of common coarse whitings | 0.31 | 65.7 | 0.18 | 68.8 | 69.4 | 1.50 | 92.2 |
| Embodiment 5 | 0.21 | 75.5 | 0.10 | 84.8 | 71.2 | 1.92 | 92.9 |
| 60 grades of common fine particle calcium carbonates | 0.30 | 63.8 | 0.19 | 72.4 | 68.1 | 1.49 | 90.9 |
By above simultaneous test as can be seen: under quantitatively identical situation, products obtained therefrom of the present invention is compared with the fine particle calcium carbonate mixture with the coarse whiting of common coarse whiting, common fine particle calcium carbonate and different ratios, and initial journey retention, filler retention, bulk, opaqueness obviously increase; And white water consistency, machine water concentration obviously reduce.So products obtained therefrom of the present invention has overcome the shortcoming of fine particle calcium carbonate, coarse whiting and coarse whiting and fine particle calcium carbonate simple mixtures, have the advantage of fine particle calcium carbonate and coarse whiting concurrently, reach good result of use.
Claims (9)
1. the preparation method of mixed calcium carbonate is characterized in that, comprises the steps:
Heavy calcium carbonate is added in the entry, be made into heavy calcium carbonate slurry; Water-ground limestone is carried out ultra-fine mill, make heavy calcium carbonate slurry;
In slurry, add the cationic polyelectrolyte solution that is equivalent to ground whiting dry powder weight then;
In slurry, add light calcium carbonate again, stir, obtain the mixed calcium carbonate slurry.
2. method according to claim 1 is characterized in that, 100～600 order heavy calcium carbonates are added in the entry, is made into the weight solid content and is 15～25% heavy calcium carbonate slurry; Adopt the ultra-fine machine of delaminating of wet type that water-ground limestone is carried out ultra-fine mill, make particle diameter and be 50～90% slurry less than the water-ground limestone weight content of 2 μ m;
In slurry, add the cationic polyelectrolyte solution that is equivalent to ground whiting dry powder weight 0.2～2.0% then, stirred 0.5～1.0 hour;
In slurry, add the light calcium carbonate that is equivalent to ground whiting dry powder amount 60～120% again, stirred 20～30 minutes.
3. method according to claim 1 and 2 is characterized in that, the preparation method of described cationic polyelectrolyte solution is as follows:
The dimethyl diallyl ammonium chloride aqueous solution is heated to 80～90 ℃, adds lauryl mercaptan then, add the persulphate aqueous solution again, obtain cationic polyelectrolyte solution.
4. method according to claim 3 is characterized in that, the add-on of described lauryl mercaptan is 0.1～0.5% of a dimethyl diallyl ammonium chloride oven dry weight.
5. method according to claim 3 is characterized in that, the weight content of the dimethyl diallyl ammonium chloride aqueous solution is 60～70%.
6. method according to claim 3, it is characterized in that, described persulphate is more than one in ammonium persulphate, Sodium Persulfate or the Potassium Persulphate, the weight concentration of the persulphate aqueous solution is 5～15%, and the adding weight of the persulphate aqueous solution is 8～20% of dimethyl diallyl ammonium chloride oven dry weight.
7. method according to claim 3 is characterized in that, between 3～5 hours, the described persulphate aqueous solution is joined in the dimethyl diallyl ammonium chloride aqueous solution.
8. according to the mixed calcium carbonate of each described method preparation of claim 1～7.
9. the application of mixed calcium carbonate according to claim 8 is characterized in that, as papermaking filler.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106830041A (en) * | 2017-01-19 | 2017-06-13 | 井陉县华北碳酸钙有限公司 | A kind of preparation method of functional calcium carbonate |
| CN106906693A (en) * | 2017-04-17 | 2017-06-30 | 华东理工大学 | A kind of preparation method of papermaking filler heavy calcium carbonate slurry |
| CN106948215A (en) * | 2017-04-17 | 2017-07-14 | 华东理工大学 | A kind of preparation method and application of papermaking filler calcium carbonate slurry |
| CN106968129A (en) * | 2017-04-17 | 2017-07-21 | 华东理工大学 | A kind of preparation method and application of low abrasion calcium carbonate slurry |
| CN107012723A (en) * | 2017-04-17 | 2017-08-04 | 华东理工大学 | A kind of preparation method of low abrasion calcium carbonate slurry |
| CN114621605A (en) * | 2022-02-28 | 2022-06-14 | 上海东升新材料有限公司 | Mixed calcium carbonate filler and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100441507C (en) * | 2006-12-25 | 2008-12-10 | 上海东升新材料有限公司 | Preparation method of high retention heavy calcium carbonate |
| CN100567635C (en) * | 2007-06-28 | 2009-12-09 | 上海东升新材料有限公司 | A kind of dispersant and its production and application |
| CN100572662C (en) * | 2007-12-24 | 2009-12-23 | 上海东升新材料有限公司 | A kind of composite calcium carbonate and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830041A (en) * | 2017-01-19 | 2017-06-13 | 井陉县华北碳酸钙有限公司 | A kind of preparation method of functional calcium carbonate |
| CN106830041B (en) * | 2017-01-19 | 2018-11-06 | 井陉县华北碳酸钙有限公司 | A kind of preparation method of functional calcium carbonate |
| CN106906693A (en) * | 2017-04-17 | 2017-06-30 | 华东理工大学 | A kind of preparation method of papermaking filler heavy calcium carbonate slurry |
| CN106948215A (en) * | 2017-04-17 | 2017-07-14 | 华东理工大学 | A kind of preparation method and application of papermaking filler calcium carbonate slurry |
| CN106968129A (en) * | 2017-04-17 | 2017-07-21 | 华东理工大学 | A kind of preparation method and application of low abrasion calcium carbonate slurry |
| CN107012723A (en) * | 2017-04-17 | 2017-08-04 | 华东理工大学 | A kind of preparation method of low abrasion calcium carbonate slurry |
| CN114621605A (en) * | 2022-02-28 | 2022-06-14 | 上海东升新材料有限公司 | Mixed calcium carbonate filler and preparation method thereof |
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