CN101514533B - Flaky calcium carbonate, preparation method and application thereof - Google Patents
Flaky calcium carbonate, preparation method and application thereof Download PDFInfo
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- CN101514533B CN101514533B CN2008102049799A CN200810204979A CN101514533B CN 101514533 B CN101514533 B CN 101514533B CN 2008102049799 A CN2008102049799 A CN 2008102049799A CN 200810204979 A CN200810204979 A CN 200810204979A CN 101514533 B CN101514533 B CN 101514533B
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Abstract
The invention discloses flaky calcium carbonate, a preparation method and application thereof. The preparation method comprises the following steps: adding fibrous light calcium carbonate into water, and adding a composite grinding aid into the water to prepare fibrous light calcium pulp with weight content of between 65 and 75 percent; and grinding the pulp to prepare the flaky calcium carbonate. The prepared flaky calcium carbonate has low price and size of between 0.2 and 0.6 mu m, approaches to half wavelength of visible light, and has even particles and narrow particle size distribution; the appearance of the particle is similar to square figure; and when the flaky calcium carbonate is applied to paper coating, lustrousness and smoothness are higher.
Description
Technical field
The present invention relates to a kind of flaky calcium carbonate and its production and application, specifically, is a kind of precipitated calcium carbonate that can be used for papermaking paint.
Background technology
Calcium carbonate can be divided into powdered whiting and precipitated calcium carbonate.Powdered whiting is directly pulverized natural calcite, lime stone, Bai Jian, shell etc. with mechanical means and is made; Precipitated calcium carbonate then is through Chemical Manufacture, and raw material calcination such as lime stone are become quick lime and carbon dioxide, adds water again and is digested to milk of lime, feeds carbon dioxide reaction then and generates precipitation of calcium carbonate, after dehydration, dry and pulverize and make.Because the limitation of mechanical crushing method, it is limited to pulverize the fine degree of grain diameter that is produced, so the granularity of powdered whiting particle can only reach micron order.Precipitated calcium carbonate then is to generate calcium carbonate crystal from the Chemical Manufacture synthetic reaction, makes the calcium carbonate product of various different-shapes and particle diameter by control synthetic reaction condition, crystal formation control additive.
Calcium carbonate is widely used in industries such as rubber, plastics, coating, printing ink, papermaking, medicine, food, feed as a kind of main inorganic chemical product.Owing to the non-transparency of precipitated calcium carbonate with to the scattering of light performance, make paper plant can produce the light tight paper of higher level, PCC also has than the high glossiness of conventional china clay pigment, uses it can make the paper product glossiness higher.Glossiness height, opacity for paper, on aesthetic standard, have very strong attraction to the consumer by force.Flaky calcium carbonate is mainly used in the paper coating, can increase the glossiness and the flatness of paper, is the kaolinic ideal substitute of paper grade (stock).
Common precipitated calcium carbonate is raw material usually with the lime stone, makes quick lime through calcining, and quick lime adds water digestion and absorbing carbon dioxide carries out carbonization then, and dehydration, drying obtain product at last.The preparation method of flaky calcium carbonate mainly is divided into two-step method and one-step method.Two-step method is meant under liquid-phase condition, at first with carbon dioxide the milk of lime carbonization is arrived to a certain degree, and controlled condition obtains the intermediate product of sheet, separate, do not changing under the prerequisite that forms crystalline form, continue carbonization, finish the carburizing reagent of second half section, finally obtain flaky calcium carbonate.The clear 63-50316 of Japan Patent, clear 61-219717 adopt two-step method exactly.The weak point of two-step method is: the one, and course of reaction is carried out in two steps, and is more loaded down with trivial details, and the second step carbonization technique energy consumption is more; The 2nd, in carbonisation, obtain the sheet intermediate and crystalline form be destroyed in the second stage carbonization, condition is difficult to control, the unstable product quality that obtains.One-step method is meant that as the common winnofil of preparation, carbonization technique one step finishes, and adds crystal control agent between being characterized in carbonisation in due course to obtain flaky calcium carbonate.Japanese patent laid-open 5-116936 disclose in carbonisation add organic phosphoric compound as crystal control agent in, add water miscible alkali salt and play synergy, the flaky calcium carbonate that this method obtains is used for papermaking, make paper performance that bigger improvement be arranged, but because the organic phosphoric compound toxicity of adding is bigger, and cost an arm and a leg, so this method is restricted aspect industrialization.Yuan Wei, gold stupidly reported among the No.2 in " fine chemistry industry " in 1998, and the boride that adopts inexpensive, low toxicity also can obtain flaky calcium carbonate as crystal control agent.But yield is lower, poor stability, and radius-thickness ratio is little.Chinese patent CN1986413 is with sheet Zr (HPO
4)
2Joining weight concentration is 2～20%Ca (OH)
2In the slurry, sheet Zr (HPO
4)
2Addition be Ca (OH)
20.5～5% (over dry/over dry) of weight feeds and contains CO
2The gas carbonization, carburizing temperature is 10～90 ℃, CO
2The volumetric concentration of gas be 10～100%, carbonization carbonization when the pH of slurry is 6.5-7.5 finishes, and obtains flake light calcium carbonate.The used zirconates of this method prepares crystal seed, and the costing an arm and a leg of zirconates is so the flake light calcium price of preparation is also more expensive; The flake light calcium size of this method preparation is bigger than normal in addition, and particle size distribution is wide, and its effect is reduced.
Summary of the invention
The purpose of this invention is to provide a kind of flaky calcium carbonate and its production and application, to overcome the above-mentioned defective that prior art exists.
Method of the present invention, comprise the steps: fibrous light cakium carbonate is added in the entry, and Xiang Shuizhong adds composite grinding aids, be made into weight content and be 65～75% fiber fine particle calcium carbonate slurry, then slurry is ground, make the flaky calcium carbonate slurry, wherein grain diameter is less than the weight content 90～100% of the flaky calcium carbonate of 1 μ m;
Described preparing fiber lightweight calcium can adopt the method for Chinese patent CN1935657, and this method is preparation polygon particulate calcium carbonate crystal seed earlier, the preparation method of crystal seed: at Ca (OH)
2In the water slurry, add MgCl
26H
2O adds lactic acid simultaneously, feeds that to contain volumetric concentration be 10～100% CO
2The gas carbonization, carbonization is 6.5～7.5 o'clock to pH, the polygon particulate calcium carbonate crystal seed in the collecting reaction product.Then crystal seed and the crystal face growth control agent boric acid that obtains is joined Ca (OH)
2In the water slurry, feed CO
2The gas carbonization, carbonization is 6.5～7.5 o'clock to pH, obtains fibrous light cakium carbonate, the draw ratio of described fibrous light cakium carbonate is: 20: 1～80: 1;
Described composite grinding aids is the mixture of Sodium Polyacrylate (weight content is 42%), calgon and triethanolamine, and the parts by weight proportioning is:
25～35 parts of Sodium Polyacrylates
20～30 parts of calgons
3～7 parts of triethanolamines
In the described Sodium Polyacrylate, the Sodium Polyacrylate weight content is 30～55%.
It is 0.3～3.0% with respect to fiber fine particle calcium carbonate oven dry weight that described composite grinding aids adds weight, and described oven dry weight refers to water-free weight;
In the slurry that contains flaky calcium carbonate that is obtained, the diameter of flaky calcium carbonate is 0.2～0.6 μ m, and radius-thickness ratio is 10: 1～30: 1, and the weight solid content is 65～75%.
Adopt the flaky calcium carbonate of method for preparing, be suitable for doing coating for paper, with described flaky calcium carbonate part substituting import one china clay and calcined kaolin, the page of making has good glossiness, smoothness, opacity and printing adaptability.
The characteristics of present technique are to adopt fibrous light cakium carbonate to grind to prepare the flaky calcium carbonate low price that makes.The flaky calcium carbonate of this method preparation is of a size of 0.2～0.6 μ m micron in addition, near the half-wavelength of visible light, and uniform particles, narrow diameter distribution, granule-morphology is a squarish, and it is used coating, glossiness and smoothness are higher.
The specific embodiment
Among the embodiment, the ultra-fine machine of delaminating of wet type is the universal product, and the trade mark that for example can adopt company of double leaf fine chemistry industry machinery Co., Ltd to produce is the ultra-fine machine of delaminating of wet type of BP series.
Embodiment 1
The allotment of composite grinding aids: with 21 kilograms of Sodium Polyacrylate (Shanghai dongsheng New Materials Co., Ltd, the trade mark is the product of DS-FS 531, weight content is 42%, join in 50 liters of reactors down together), open and stir, then 7.5 kilograms of calgons and 1.5 kilograms of triethanolamines are joined in the reactor, fully stir and make its dissolving, obtain 30 kilograms of composite grinding aids;
1000 kilograms of fiber fine particle calcium carbonates are joined in 303 kg of water, in water, add 30 kilograms of composite grinding aids simultaneously, stirring makes the composite grinding aids dissolving, be made into weight content and be 75% fiber fine particle calcium carbonate slurry, stir, adopt the ultra-fine machine of delaminating of wet type of 80 liters of two series connection then, the fiber fine particle calcium carbonate is ground, make the flaky calcium carbonate slurry, wherein grain diameter is less than the weight content 99% of the fiber fine particle calcium carbonate of 1 μ m.
Adopt the method for ISO 2884-2-2003 standard code, recording slurry viscosity with NDJ-1 type rotation viscometer is 230 centipoises.With sem observation flake light calcium diameter is 0.24 μ m, and radius-thickness ratio is 18: 1.
Embodiment 2
The allotment of composite grinding aids: 14 kilograms of Sodium Polyacrylates (weight content is 42%) are joined in 50 liters of reactors, open and stir, then 5 kilograms of calgons and 1 kilogram of triethanolamine are joined in the reactor, fully stir and make its dissolving, obtain 20 kilograms of composite grinding aids.
2000 kilograms of fiber fine particle calcium carbonates are joined in 758 kg of water, in water, add 20 kilograms of composite grinding aids simultaneously, stirring makes the composite grinding aids dissolving, be made into weight content and be 72% fiber fine particle calcium carbonate slurry, stir, adopt 300 liters the ultra-fine machine of delaminating of wet type then, the fiber fine particle calcium carbonate is ground, make the flaky calcium carbonate slurry, wherein grain diameter is 90% less than the weight content of the flaky calcium carbonate of 1 μ m.
Adopt the method for ISO 2884-2-2003 standard code, recording slurry viscosity with NDJ-1 type rotation viscometer is 250 centipoises.With sem observation flake light calcium diameter is 0.32 μ m, and radius-thickness ratio is 12: 1.
Embodiment 3
The allotment of composite grinding aids: 11.2 kilograms of Sodium Polyacrylates (weight content is 42%) are joined in 50 liters of reactors, open and stir, then 4 kilograms of calgons and 0.8 kilogram of triethanolamine are joined in the reactor, fully stir and make its dissolving, obtain 16 kilograms of composite grinding aids.
5000 kilograms of fiber fine particle calcium carbonates are joined in 2337 kg of water, in water, add 16 kilograms of composite grinding aids simultaneously, stirring makes the composite grinding aids dissolving, be made into weight content and be 68% fiber fine particle calcium carbonate slurry, stir, adopt 3000 liters the ultra-fine machine of delaminating of wet type then, the fiber fine particle calcium carbonate is ground, make the flaky calcium carbonate slurry, wherein grain diameter is 100% less than the weight content of the flaky calcium carbonate of 1 μ m.
Adopt the method for ISO 2884-2-2003 standard code, recording slurry viscosity with NDJ-1 type rotation viscometer is 348 centipoises.With sem observation flake light calcium diameter is 0.22 μ m, and radius-thickness ratio is 29: 1.
Embodiment 4
The allotment of composite grinding aids: 22.4 kilograms of Sodium Polyacrylates (weight content is 42%) are joined in 50 liters of reactors, open and stir, then 8 kilograms of calgons and 1.6 kilograms of triethanolamines are joined in the reactor, fully stir and make its dissolving, obtain 32 kilograms of composite grinding aids.
2500 kilograms of fiber fine particle calcium carbonates are joined in 1314 kg of water, in water, add 32 kilograms of composite grinding aids simultaneously, stirring makes the composite grinding aids dissolving, be made into weight content and be 65% fiber fine particle calcium carbonate slurry, stir, adopt the ultra-fine machine of delaminating of wet type of 300 liters of two series connection then, the fiber fine particle calcium carbonate is ground, make the flaky calcium carbonate slurry, wherein grain diameter is 97% less than the weight content of the flaky calcium carbonate of 1 μ m.
Adopt the method for ISO 2884-2-2003 standard code, recording slurry viscosity with NDJ-1 type rotation viscometer is 218 centipoises.With sem observation flake light calcium diameter is 0.34 μ m, and radius-thickness ratio is 22: 1.
Embodiment 5
The allotment of composite grinding aids: 7 kilograms of Sodium Polyacrylates (weight content is 42%) are joined in 30 liters of reactors, open and stir, then 2.5 kilograms of calgons and 0.5 kilogram of triethanolamine are joined in the reactor, fully stir and make its dissolving, obtain 10 kilograms of composite grinding aids.
1500 kilograms of fiber fine particle calcium carbonates are joined in 545 kg of water, in water, add 32 kilograms of composite grinding aids simultaneously, stirring makes the composite grinding aids dissolving, be made into weight content and be 73% fiber fine particle calcium carbonate slurry, stir, adopt the ultra-fine machine of delaminating of wet type of 80 liters of three series connection then, the fiber fine particle calcium carbonate is ground, make the flaky calcium carbonate slurry, wherein grain diameter is 95% less than the flaky calcium carbonate weight content of 1 μ m.
Adopt the method for ISO 2884-2-2003 standard code, recording slurry viscosity with NDJ-1 type rotation viscometer is 233 centipoises.With sem observation flake light calcium diameter is 0.38 μ m, and radius-thickness ratio is 21: 1.
Embodiment 6
Be coated with in the prescription at white card face, use the import china clay and the calcined kaolin of the foregoing description flake light calcium sample instead of part, performance variation situations such as the physical index of investigation coating pattern and printability.Face is coated with the art post paperboard that the band precoating is adopted in experiment, uses linear spreading rod to carry out face and is coated with coating weight 10g/m
2Compare with the coating pattern of original formulation.Coating rolling condition: get above-mentioned coating pattern respectively with twice of the hard press polish of small-sized calender (0.3Mpa, 90 ℃).Adopt the GB/T1033-1995 standard to detect.
Table 1 face is coated with face and is coated with prescription
Plastic pigments adopts the disclosed hollow polymer emulsion particle of Chinese patent CN1896110A.
Table 2 coating pattern detects data
From the result, similarity condition is compared with original formulation down, the foregoing description flake light calcium part substituting import one china clay and calcined kaolin, pattern level and smooth, to be coated with glossiness, surface strength, ink absorption and other difference little.
Claims (6)
1. the preparation method of flaky calcium carbonate slurry, it is characterized in that, comprise the steps: fibrous light cakium carbonate is added in the entry, and Xiang Shuizhong adds composite grinding aids, be made into weight content and be 65～75% fibrous light cakium carbonate slurry, then slurry is ground, make the flaky calcium carbonate slurry;
Described composite grinding aids is the mixture of the mixture, calgon and the triethanolamine that contain Sodium Polyacrylate, and the parts by weight proportioning is:
25～35 parts in the mixture that contains Sodium Polyacrylate
20～30 parts of calgons
3～7 parts of triethanolamines
In the described mixture that contains Sodium Polyacrylate, the Sodium Polyacrylate weight content is 30～55%.
2. method according to claim 1 is characterized in that, the draw ratio of described fibrous light cakium carbonate is: 20: 1～80: 1.
3. method according to claim 1 is characterized in that, it is 0.3～3.0% with respect to the fibrous light cakium carbonate oven dry weight that described composite grinding aids adds weight.
4. according to the flaky calcium carbonate slurry of each described method preparation of claim 1～3.
5. according to the flaky calcium carbonate slurry of the described method preparation of claim 4, it is characterized in that the diameter of flaky calcium carbonate is 0.2～0.6 μ m, radius-thickness ratio is 10: 1～30: 1.
6. according to the application of the flaky calcium carbonate slurry of the described method of claim 5 preparation, it is characterized in that, be used as coating for paper.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102049799A CN101514533B (en) | 2008-12-30 | 2008-12-30 | Flaky calcium carbonate, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102049799A CN101514533B (en) | 2008-12-30 | 2008-12-30 | Flaky calcium carbonate, preparation method and application thereof |
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| CN101514533A CN101514533A (en) | 2009-08-26 |
| CN101514533B true CN101514533B (en) | 2011-06-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107034726A (en) * | 2017-04-17 | 2017-08-11 | 华东理工大学 | A kind of preparation method of dumb light paper coating calcium carbonate |
| CN107055585B (en) * | 2017-06-21 | 2019-11-15 | 杭州杭钢三江矿业有限公司 | A kind of preparation method of flame retardant type major diameter flaky calcium carbonate |
| CN107244686A (en) * | 2017-06-21 | 2017-10-13 | 长兴大地新型材料有限公司 | A kind of preparation method of major diameter flaky calcium carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359986A (en) * | 2001-12-29 | 2002-07-24 | 中国地质大学（武汉） | Process for preparing flaky heavy calcium carbonate |
| CN1526642A (en) * | 2003-03-05 | 2004-09-08 | 上海东升新材料有限公司 | Prepn of superfine light precipited calcium carbonate |
| CN1935657A (en) * | 2006-10-11 | 2007-03-28 | 上海东升新材料有限公司 | Method for preparing length and diameter controllable fibrous light calcium carbonate |
| CN1986413A (en) * | 2006-12-25 | 2007-06-27 | 上海东升新材料有限公司 | Flake light calcium carbonate and its preparing method and application |
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- 2008-12-30 CN CN2008102049799A patent/CN101514533B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359986A (en) * | 2001-12-29 | 2002-07-24 | 中国地质大学（武汉） | Process for preparing flaky heavy calcium carbonate |
| CN1526642A (en) * | 2003-03-05 | 2004-09-08 | 上海东升新材料有限公司 | Prepn of superfine light precipited calcium carbonate |
| CN1935657A (en) * | 2006-10-11 | 2007-03-28 | 上海东升新材料有限公司 | Method for preparing length and diameter controllable fibrous light calcium carbonate |
| CN1986413A (en) * | 2006-12-25 | 2007-06-27 | 上海东升新材料有限公司 | Flake light calcium carbonate and its preparing method and application |
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