CN101302025A - Porous calcium carbonate, and preparation and application thereof - Google Patents
Porous calcium carbonate, and preparation and application thereof Download PDFInfo
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- CN101302025A CN101302025A CNA2008100398102A CN200810039810A CN101302025A CN 101302025 A CN101302025 A CN 101302025A CN A2008100398102 A CNA2008100398102 A CN A2008100398102A CN 200810039810 A CN200810039810 A CN 200810039810A CN 101302025 A CN101302025 A CN 101302025A
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Abstract
The invention provides a porous calcium carbonate, a method for preparing the same and an application of the porous calcium carbonate. The preparation method comprises the following steps that: (1) carbon dioxide is led to a calvital sizing agent for carbonization; in the carbonization process, an ammonium persulfate solution and a hydrazine hydrate solution are respectively and separately added till the PH value of the sizing agent is between 9.0 and 11.0, then the addition of the ammonium persulfate solution and the hydrazine hydrate solution is stopped; the sizing agent is continuously carbonized till the PH value is between 6.5 and 7.5; (2) the acquired calcium carbonate sizing agent is filtered, washed and made into a filter cake, then the filter cake is dispersed into a sizing agent by water; and the sizing agent is added with a sodium polyacrylate dispersant containing 1.0 to 2.0 percent of calcium carbonate dry weight and subject to spraying and drying, thereby obtaining alveolate calcium carbonate dry powder. The porous calcium carbonate has large amount of porosity and can markedly increase the loose depth of paper and the bonding force between fillers and fibres, thereby improving the porocity and the loose depth of the paper without reducing the strength of the paper.
Description
Technical field
The present invention relates to a kind of preparation method and application of porous calcium carbonate.
Background technology
Lime carbonate is important inorganic chemical product, and particle diameter is generally less than 2 μ m, often makes filler.Be widely used in operations such as rubber, plastics, coating, papermaking and printing ink, ordinary calcium carbonate is raw material usually with the Wingdale, makes unslaked lime through calcining, and unslaked lime adds water digestion and absorbing carbon dioxide carries out carbonization then, and dehydration, drying obtain product at last.
Owing to the non-transparency of PCC with to the scattering of light performance, make paper plant can produce the light tight paper of higher category, PCC also has than the high whiteness of conventional china clay pigment, uses it can make the paper product whiteness higher.Whiteness height, opaqueness for paper, on aesthetic standard, have very strong magnetism to the human consumer by force.Usually the paper product that has this performance also is a high value-added product, and the high bulking power of PCC can make the paper mill use more filler in the processing paper process, thereby saves the paper pulp consumption, reduces cost.PCC has following advantage as the paper grade (stock) filler: have higher opaqueness and whiteness; As filler, bulking power is strong; Particle diameter keeps evenly; The color confining force is strong.
Chinese patent CN1951230 discloses calcium carbonate powder composition and preparation method thereof, and this invention provides and can make lime carbonate be dispersed in calcium carbonate powder composition in the liquid long-term and stably with the form of primary particle or the particulate close with it.This powder composition is that the BET specific surface area is 10-40m
2The scope of/g, total micropore volume are the lime carbonate primary particle aggregation of 0.10-0.28mL/g scope, contain the porous calcium carbonate particle, and this porous calcium carbonate particulate surface is the emulsifying agent covering of 3-20 quality % scope by the containing ratio with respect to total amount.
Calcium alginate gel beads that it is shell that Chinese patent CN1985995 discloses a kind of porous calcium carbonate microballoon and preparation method thereof.It is the preparation method of the calcium alginate gel beads of shell that this method provides a kind of porous calcium carbonate microballoon, is that the sodium alginate water is distributed to the oil phase that contains the porous calcium carbonate microballoon, forms water-in-oil emulsion through emulsification; The porous calcium carbonate microballoon is adsorbed onto the emulsion droplet surface, forms shell, stablizes emulsion droplet; Add the gluconic acid lactone aqueous solution and carry out the sodium alginate gel reaction.The present invention can be simply, to prepare with the porous calcium carbonate microballoon in a large number be that shell is the microballon of nuclear with the calcium alginate gel.
Chinese patent CN1919445 discloses a kind of method of utilizing doping porous calcium carbonate mould plates to prepare microcapsule.This disclosure of the Invention a kind of method of utilizing doping porous calcium carbonate mould plates to prepare microcapsule.Having in the presence of the polyelectrolyte of negative charge, preparing negative charge polyelectrolyte doped porous lime carbonate colloidal particle by calcic inorganic salt and the reaction that contains the carbonate inorganic salt; The polyelectrolyte that will have positive charge is adsorbed on this colloidal particle surface, decomposes by diluted acid or EDTA complex removal calcium carbonate microparticle again, and by the ionic linkage effect between positive and negative electric charge polyelectrolyte, original position forms hollow microcapsule.Preparation method of the present invention is simple and efficient, and material source is extensive, is suitable for the large-scale commercial production hollow microcapsule, has excellent industrial application foreground.
Chinese patent CN1528468 discloses porous calcium carbonate-hydroxy-apatite gradient material and preparation method.The basis that this invention is reacted with the hydrothermal exchange that lime carbonate is converted into hydroxyapatite, by change to lime carbonate and phosphate content, obtain the different biomaterials that transform ratio, material surface of the present invention is the thin clothing layer of hydroxyapatite, and central authorities are 4.5%～33.8% for the concentration gradients of Calcium phosphate hydroxyapatite.Have good biocompatibility, highly porous, the controllable characteristics of biodegradation rate have good bone defect repair effect.
The raising of paper bulk helps paper " lightweight ", can reduce the wood pulp consumption.The technology of existing raising paper bulk mainly is: reduce the line pressure of squeezing and rolling press, but can cause smoothness of paper to reduce like this; Select suitable filler, talcum powder, kaolin, water-ground limestone etc. all can make bulk increase, and common light calcium carbonate has effect to improving the paper bulk, but effect is not remarkable; High bulky chemical additives can significantly improve the paper bulk, but can bring the remarkable reduction of paper strength, so can only use on a small quantity, consumption is not obvious to the raising of bulk very little.Because high bulky chemical all is a cats product, after tensio-active agent adds, positively charged ion one end that tensio-active agent polarity is very strong and the negatively charged ion generation effect on wood pulp cellulose surface, SURFACTANT ADSORPTION is to the wood pulp cellulose surface, the long-chain hydrocarbon that the other end polarity is very weak covers the wood pulp cellulose surface, makes the wood pulp cellulose surface become low-pole.Make wood pulp cellulose reaction force attenuation each other like this, it is very near that wood pulp cellulose can not lean on each other, and wood pulp cellulose produces certain space each other, thereby improved the paper bulk.
Summary of the invention
An object of the present invention is for a kind of porous calcium carbonate and its production and application is provided, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) will leading to carbon dioxide, to feed weight content be 5～20% calcium hydroxide slurry, carry out carbonization, the solution that adds ammonium persulfate solution and hydrazine hydrate in the process of carbonization simultaneously respectively independently, when carbonization when the pH of slurry is 9.0～11.0, stop in slurry, to add ammonium persulfate solution and hydrazine hydrate solution, continuing logical carbon dioxide and carry out carbonization, is end carbonization in 6.5～7.5 o'clock until pH;
The mass percentage concentration of described ammonium persulfate solution is 15%～25%;
The mass percentage concentration of described hydrazine hydrate solution is 15%～60%;
The add-on of described ammonium persulphate is 1.0～5.0% of a calcium hydroxide dry weight;
The add-on of described hydrazine hydrate is 1.0～10.0% of a calcium hydroxide dry weight;
Described carbonic acid gas can be the mixed gas of pure carbon dioxide or carbonated 10～35%;
(2) calcium carbonate slurry that obtains is filtered, washs, make filter cake, again the filter cake water is dispersed into slurry, the weight solid content of slurry is 40～60%, add lime carbonate oven dry weight 1.0～2.0% sodium polyacrylate dispersion agents in the slurry, slurry carries out spraying drying, obtains cellular calcium carbonate dry powder.
Described sodium polyacrylate dispersion agent is selected conventional commercially available prod for use, and for example Shanghai dongsheng New Materials Co., Ltd's trade mark is the product of FS-531.
Described spraying drying can be centrifugal spraying or press atomization.
Porous calcium carbonate with this patent preparation is used as papermaking filler, can improve the Gas permeability and the bulk of paper.
The porous calcium carbonate of the present invention preparation has bigger porosity, and tap density is little, can significantly increase the paper bulk so add in the paper as filler.Simultaneously, the internal surface of the hole of porous calcium carbonate has higher surface energy, can attract wood pulp cellulose tiny after pulling an oar to enter porous calcium carbonate hole inside, has increased the bonding force of filler and fiber greatly, the negative impact that does not have high bulky chemical to be brought.Porous calcium carbonate has bigger porosity in addition, also helps the raising of paper permeability.So porous calcium carbonate, can improve the Gas permeability and the bulk of paper as filler, do not reduce paper strength again.
Description of drawings
Fig. 1 is the electromicroscopic photograph of embodiment 1.
Embodiment
Among the embodiment, if no special instructions, components contents is weight content.
Embodiment 1
Take by weighing the 40kg ammonium persulphate, add 200kg water in the reactor that 0.5 cubic metre of band stirs, the 40kg ammonium persulphate is joined in the reactor, stirring and dissolving is made ammonium persulfate aqueous solution.
It is stand-by to take by weighing the 50kg weight concentration and be 60% hydrazine hydrate aqueous solution;
With the 8000kg solid content is that 20% calcium hydroxide slurry joins in the carbonating tower that 12 cubic metres band stirs, feeding carbonic acid gas volume content is 10% mixed gas in carbonating tower, add above-mentioned ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution with two volume pumps in carbonating tower simultaneously, the flow of ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution is respectively 4.0kg/min and 0.8kg/min.When carbonization was carried out 55 minutes, pH was 9.3, stopped to add ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution, continued to feed carbon dioxide gas mixture 11 minutes in carbonating tower, and pH is 7.2, stops carbonization.The plate-and-frame filter press of calcium carbonate slurry with 100 square metres filtered, washs, and obtaining the lime carbonate solid content is 50% filter cake 4020kg.Filter cake is joined in the reactor of 5 cubic metres of band stirrings, add 30kg sodium polyacrylate dispersion agent (FS-531 of Shanghai dongsheng New Materials Co., Ltd dispersion agent), it is 50% slurry that dispersed with stirring is made solid content.With spiral pump slurry is sent in the centrifugal spray dryer drying system that water evaporation quantity is 600kg/hr and to be carried out drying, centrifugal spray dryer drying system inlet temperature is 340 ℃, and air outlet temperature is 94 ℃, obtains cellular calcium carbonate dry powder 1976kg.Electromicroscopic photograph is seen Fig. 1.
Embodiment 2
Take by weighing the 16kg ammonium persulphate, add 100kg water in the reactor that 0.3 cubic metre of band stirs, the 16kg ammonium persulphate is joined in the reactor, stirring and dissolving is made ammonium persulfate aqueous solution.
It is stand-by to take by weighing 120kg concentration and be 25% hydrazine hydrate aqueous solution.
With the 8000kg solid content is that 5% calcium hydroxide slurry joins in the carbonating tower that 12 cubic metres band stirs, feeding carbonic acid gas volume content is 35% mixed gas in carbonating tower, add above-mentioned ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution with two volume pumps in carbonating tower simultaneously, the flow of ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution is respectively 2.0kg/min and 1.8kgmin.When carbonization was carried out 50 minutes, pH was 9.8, stopped to add ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution, continued to feed carbon dioxide gas mixture 9 minutes in carbonating tower, and pH is 7.1, stops carbonization.The plate-and-frame filter press of calcium carbonate slurry with 60 square metres filtered, washs, and obtaining the lime carbonate solid content is 53% filter cake 955kg.Filter cake is joined in the reactor that 2 cubic metres of bands stir, add 21kg sodium polyacrylate dispersion agent (FS-531 of Shanghai dongsheng New Materials Co., Ltd dispersion agent), adding the water dispersed with stirring again, to make the weight solid content be 40% slurry.With spiral pump slurry is sent in the centrifugal spray dryer drying system that water evaporation quantity is 200kg/hr and to be carried out drying, centrifugal spray dryer drying system inlet temperature is 325 ℃, and air outlet temperature is 95 ℃, obtains cellular calcium carbonate dry powder 486kg.
Embodiment 3
Take by weighing the 12kg ammonium persulphate, add 50kg water in the reactor that 0.1 cubic metre of band stirs, the 12kg ammonium persulphate is joined in the reactor, stirring and dissolving is made ammonium persulfate aqueous solution.
It is stand-by to take by weighing the 62kg weight concentration and be 45% hydrazine hydrate aqueous solution.
With the 8000kg solid content is that 15% calcium hydroxide slurry joins in the carbonating tower that 12 cubic metres band stirs, feeding carbonic acid gas volume content is 19% mixed gas in carbonating tower, add above-mentioned ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution with two volume pumps in carbonating tower simultaneously, the flow of ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution is respectively 1.0kg/min and 0.9kgmin.When carbonization was carried out 52 minutes, pH was 10, stopped to add ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution, continued to feed carbon dioxide gas mixture 12 minutes in carbonating tower, and pH is 6.8, stops carbonization.The plate-and-frame filter press of calcium carbonate slurry with 60 square metres filtered, washs, and obtaining the lime carbonate solid content is 51% filter cake 2945kg.Filter cake is joined in the reactor of 5 cubic metres of band stirrings, add 16kg sodium polyacrylate dispersion agent (FS-531 of Shanghai dongsheng New Materials Co., Ltd dispersion agent), it is 51% slurry that dispersed with stirring is made solid content.With spiral pump slurry is sent in the pressure spray dryer system that water evaporation quantity is 500kg/hr and to be carried out drying, pressure spray dryer system inlet temperature is 310 ℃, and air outlet temperature is 91 ℃, obtains cellular calcium carbonate dry powder 1456kg.
Embodiment 4
Take by weighing the 32kg ammonium persulphate, add 100kg water in the reactor that 0.3 cubic metre of band stirs, the 32kg ammonium persulphate is joined in the reactor, stirring and dissolving is made ammonium persulfate aqueous solution.
It is stand-by to take by weighing the 125kg weight concentration and be 35% hydrazine hydrate aqueous solution.
With 8000kg weight solid content is that 10% calcium hydroxide slurry joins in the carbonating tower that 12 cubic metres band stirs, feeding carbonic acid gas volume content is 23% mixed gas in carbonating tower, add above-mentioned ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution with two volume pumps in carbonating tower simultaneously, the flow of ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution is respectively 2.0kg/min and 1.8kgmin.When carbonization was carried out 49 minutes, pH was 11, stopped to add ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution, continued to feed carbon dioxide gas mixture 11 minutes in carbonating tower, and pH is 6.5, stops carbonization.The plate-and-frame filter press of calcium carbonate slurry with 100 square metres filtered, washs, and obtaining the lime carbonate solid content is 52% filter cake 2010kg.Filter cake is joined in the reactor of 3 cubic metres of band stirrings, add 21kg sodium polyacrylate dispersion agent (FS-531 of Shanghai dongsheng New Materials Co., Ltd dispersion agent), it is 52% slurry that dispersed with stirring is made solid content.With spiral pump slurry is sent in the centrifugal spray dryer drying system that water evaporation quantity is 500kg/hr and to be carried out drying, centrifugal spray dryer drying system inlet temperature is 335 ℃, and air outlet temperature is 95 ℃, obtains cellular calcium carbonate dry powder 975kg.
Embodiment 5
Take by weighing the 45kg ammonium persulphate, add 200kg water in the reactor that 0.5 cubic metre of band stirs, the 45kg ammonium persulphate is joined in the reactor, stirring and dissolving is made ammonium persulfate aqueous solution.
It is stand-by to take by weighing the 42kg weight concentration and be 15% hydrazine hydrate aqueous solution.
With the 8000kg solid content is that 8% calcium hydroxide slurry joins in the carbonating tower that 12 cubic metres band stirs, in carbonating tower, feed the mixed gas of carbonic acid gas volume content 26%, add above-mentioned ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution with two volume pumps in carbonating tower simultaneously, the flow of ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution is respectively 4.0kg/min and 0.7kgmin.When carbonization was carried out 56 minutes, pH was 10.8, stopped to add ammonium persulfate aqueous solution and hydrazine hydrate aqueous solution, continued to feed carbon dioxide gas mixture 10 minutes in carbonating tower, and pH is 6.9, stops carbonization.The plate-and-frame filter press of calcium carbonate slurry with 100 square metres filtered, washs, and obtaining the lime carbonate solid content is 55% filter cake 1469kg.Filter cake is joined in the reactor of 2 cubic metres of band stirrings, add 17kg sodium polyacrylate dispersion agent (FS-531 of Shanghai dongsheng New Materials Co., Ltd dispersion agent), it is 55% slurry that dispersed with stirring is made solid content.With spiral pump slurry is sent in the pressure spray dryer system that water evaporation quantity is 200kg/hr and to be carried out drying, pressure spray dryer system inlet temperature is 340 ℃, and air outlet temperature is 92 ℃, obtains cellular calcium carbonate dry powder 766kg.
Application Example
With 1880 fourdrinier wire multi-cylinder culture papers, replace common fine particle calcium carbonate to be used for double gummed paper production with porous calcium carbonate, investigate EFFECT OF HEMI-CELLULOSE CONTENT.Paper bulk measuring method reference: GB/T451.2-2002 " the quantitative assay method of paper and cardboard ", GB/T451.3-2002 " assay method of paper and cal(l)iper ", bulk be paper thickness divided by paper quantitatively; Press GB/T 453-2002 and detect pattern intensity.Experiment condition: paper machine type, 1880 fourdrinier wire multi-cylinder culture papers; Produce the paper kind, 80g/m
2Double gummed paper, filler, porous calcium carbonate; Common fine particle calcium carbonate
Contrast sample 1 is common fine particle calcium carbonate, and contrast sample 2 is the paper quality improver of patent CN1668812 preparation.Compare with contrast sample 1, porous calcium carbonate bulk of the present invention and opaqueness comparison are than sample 1 height, and tensile strength is basic identical with contrast sample 1; Compare with contrast sample 2, porous calcium carbonate bulk comparison of the present invention is lower than sample 2, and opaqueness is basic identical with contrast sample 2, and tensile strength is compared than sample 2 height.
Claims (10)
1. the porous calcium carbonate preparation method is characterized in that, comprises the steps:
(1) will lead to carbon dioxide feeding calcium hydroxide slurry and carry out carbonization, the solution that adds ammonium persulfate solution and hydrazine hydrate in the process of carbonization simultaneously respectively independently, carbonization is 9.0～11.0 o'clock to the pH of slurry, stop in slurry, to add ammonium persulfate solution and hydrazine hydrate solution, continuing logical carbon dioxide and carry out carbonization, is end carbonization in 6.5～7.5 o'clock until pH;
(2) calcium carbonate slurry that obtains is filtered, washs, make filter cake, again the filter cake water is dispersed into slurry, add lime carbonate oven dry weight 1.0～2.0% sodium polyacrylate dispersion agents in the slurry, slurry carries out spraying drying, obtains cellular calcium carbonate dry powder.
2. method according to claim 1 is characterized in that, the weight content of calcium hydroxide slurry is 5～20%.
3. method according to claim 1 is characterized in that, the mass percentage concentration of described ammonium persulfate solution is 15%～25%.
4. method according to claim 1 is characterized in that, the mass percentage concentration of described hydrazine hydrate solution is 15%～60%.
5. method according to claim 1 is characterized in that, the add-on of described ammonium persulphate is 1.0～5.0% of a calcium hydroxide dry weight.
6. method according to claim 1 is characterized in that, the add-on of described hydrazine hydrate is 1.0～10.0% of a calcium hydroxide dry weight.
7. method according to claim 1 is characterized in that, described spraying drying is centrifugal spray drying or pressure spray dryer.
8. according to each described method of claim 1～7, it is characterized in that described carbonic acid gas is the mixed gas of pure carbon dioxide or carbonated 10～35%.
9. according to the porous calcium carbonate of each described method preparation of claim 1～8.
10. the application of porous calcium carbonate according to claim 9 is characterized in that, as papermaking filler.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103099777A (en) * | 2011-11-15 | 2013-05-15 | 上海高科生物工程有限公司 | Bio-enzyme hydrogel taking porous calcium carbonate as carrier and preparation method of bio-enzyme hydrogel |
| CN108928875A (en) * | 2018-07-20 | 2018-12-04 | 张莉敏 | A kind of dedicated improver of water quality in fish pond and preparation method thereof |
-
2008
- 2008-06-30 CN CNB2008100398102A patent/CN100562495C/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103099777A (en) * | 2011-11-15 | 2013-05-15 | 上海高科生物工程有限公司 | Bio-enzyme hydrogel taking porous calcium carbonate as carrier and preparation method of bio-enzyme hydrogel |
| CN108928875A (en) * | 2018-07-20 | 2018-12-04 | 张莉敏 | A kind of dedicated improver of water quality in fish pond and preparation method thereof |
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