CN1253373C - Method for manufacturing super fine calcium carbonate dispersing particles - Google Patents
Method for manufacturing super fine calcium carbonate dispersing particles Download PDFInfo
- Publication number
- CN1253373C CN1253373C CNB2004100251557A CN200410025155A CN1253373C CN 1253373 C CN1253373 C CN 1253373C CN B2004100251557 A CNB2004100251557 A CN B2004100251557A CN 200410025155 A CN200410025155 A CN 200410025155A CN 1253373 C CN1253373 C CN 1253373C
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- suspension
- lime
- calcium hydroxide
- seed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a method for producing dispersive superfine grains of calcium carbonate. The method comprises the following steps: firstly preparing uniform cubical precipitated calcium carbonate as precursors under the condition of exceeding critical supersaturation degree (K<**>), then adding control agents of reaction speed to adjust the reaction conditions and make the supersaturation degree K smaller than K<**> and larger than K<*>, preparing crystals on the surfaces of the calcium carbonate precursors, and thereby obtaining the dispersive superfine grains of calcium carbonate with controllable granularity and uniform granularity distribution. The method is suitable for various kinds of existing reacting equipment, and has no need of increasing equipment, and the use quantity of additives in the process is a little. The obtained dispersive grains have the characteristics of controllable granularity and distribution, good dispersancy, high whiteness, high luster and low viscosity, and is not only used as paper filling materials, paper coating pigment but also used as semi-reinforcing agent and high-grade filling materials for paint, plastic, etc.
Description
Technical field
The present invention relates to a kind of method of producing lime carbonate, relate to a kind of method of producing the calcium carbonate superfine powder particle dispersion specifically.
Technical background
Along with the development of paper-making technique, precipitated chalk has become the indispensable important source material of paper-making industry.The fine precipitated chalk need possess apparent characteristics such as high whiteness, high covering power, printing ink anchorage and excellent in optical properties.
From powdered material physical chemistry angle, require precipitated chalk: 1) thus the low high whiteness of high purity that embodies of contained foreign pigment content such as ferrimanganic; 2) have the particle scale and the homogeneous granules degree thereof that are complementary with the pigment requirement and distribute, under the single particle dispersion state, embody excellent pigment optical characteristics and filling intensity; 3) have regular granule-morphology, be easy to during use disperse, minimum apparent hardness embodies excellent coating rheological properties such as highly filled low viscosity; 4) lower manufacturing cost.
Difference according to the technical scheme that adopts, the way of contact of milk of lime and carbon dioxide containing gas mainly contains the bubbling hybrid mode, the mechanical stirring hybrid mode, and gas phase is the milk of lime spraying way of contact of external phase, and wherein the specific energy consumption of first kind of mode is saved the most.But, in the tradition bubble tower, if do not add the crystal formation control agent, the product that obtains mostly is spindle-type, two-dimensional projection's maximum length of primary particle is 2 μ m～6 μ m, normally with 10 sticking coacervates that are associated in together more than the particle, the yardstick of coacervate is generally 15 μ m～40 μ m between the primary particle, and oil-absorption(number) is at 55gDOP/100gCaCO
3More than.Produce the dispersiveness of precipitated chalk and satisfy of the requirement of different application field in order to improve traditional technology, proposed various Technological improvement plans particle scale.
For example, the open CN1330039A of Chinese patent application, in order to obtain certain products granularity and size-grade distribution thereof, adding under carbohydrate and the cold condition, adopt the mechanical stirring hybrid mode, synthetic size is at the cube calcium carbonate superfine powder of 0.02 μ m～0.09 μ m, deals with cohesion between the nano level primary particle by soap or titanate coupling agent., the nano level precipitated chalk after handling like this is not suitable for being used as the pigment of paper grade (stock) weighting agent or coating paper but having hydrophobic surface.
The open CN1348428A of Chinese patent application has announced the preparation method who is suitable for as the precipitated chalk of paper weighting agent and coating paper colors.Adding under 0.5～3% and 30～80 ℃ of temperature of sugar, adopt the mechanical stirring hybrid mode, by control reaction temperature and carbohydrate additive add-on, the discrete particle precipitated chalk of synthetic 0.1 μ m～3 μ m.
U.S. Pat P5811070 has announced the method for the precipitated chalk of preparation granularity 0.1 μ m～1 μ m.This method adopts lower lime milk concentration, multistep operation repeatedly, and the technology controlling and process complexity, the unit volume productive rate is not high.
The technical issues that need to address of the present invention are to disclose a kind of method of producing the calcium carbonate superfine powder particle dispersion, to overcome the above-mentioned defective that prior art exists, satisfy the needs of relevant field development.
Principle of the present invention and technical conceive:
Greater than the thermodynamic principles of crystal growth free energy, the ratio (Ng/Ns) of crystalline growth velocity and nucleus formation speed is proportional to and can supplies the growth total surface area in the rapid reaction crystallisation process, as reactant degree of supersaturation (K according to nucleus free energy of formation in the crystallisation process
*) the critical degree of supersaturation (K that generates less than nucleus
*) time Ng/Ns trend infinitely great.As long as in whole measured response zone, the crystal surface of keeping enough Gong growths amasss, that is in the unit's of keeping reaction volume the area A of crystalline growth greater than threshold value A
*, can prevent the generation of secondary nucleus effectively, thereby the granularity that realizes precipitated chalk trends towards controllability and homogenizing.The present invention's imagination is at first surpassing critical degree of supersaturation (K by the reaction of two steps
*) condition under the uniform cube precipitated chalk of preparation as seed, in second step, the condition of adding speed of response control agent adjustment reaction makes degree of supersaturation K less than K then
*And greater than K
*, carry out the crystalline growth on the surface of seed lime carbonate.Thereby obtain the controlled and uniform calcium carbonate superfine powder particle dispersion of distribution of particle sizes of granularity.
Method of the present invention comprises the steps:
(1) carbonated gas is fed a calcium hydroxide aqeous suspension that contains the crystal shape control agent and carry out carbonization, carbonization to the pH value of aqeous suspension is 6～6.9, obtain the suspension that contains the nano-calcium carbonate seed of favorable dispersity, the median size L of this nano-calcium carbonate seed of sampling analysis is 0.045 μ m, σ is 0.000807, specific surface area 31m
2/ g.
Said crystal shape control agent is selected from a kind of or its mixture in sucrose, glucose or the sodium sulfate, and the gross weight of crystal shape control agent is 0.7%～7% of a gained lime carbonate seed.Crystal shape control agent consumption is less than 0.7%, non-cube particle appears, cause the distribution of particle sizes of lime carbonate seed to broaden, perhaps require milk of lime is cooled to lower temperature of reaction to obtain desirable shape and granularity, so not only waste energy, and the coalescence of gained lime carbonate seed primary particle will become very serious.The total consumption of crystal shape control agent surpasses 7%, will become uneconomical in the scope of other conditions that the present invention requires.
During carbonization, one time calcium hydroxide aqeous suspension starting temperature is 20～40 ℃, and lower starting temperature needs more cooling energy and uneconomical, and too high starting temperature needs more crystal shape control agent, and distribution of particle sizes will broaden, and best initial reaction temperature is 24～36 ℃.
Said carbon dioxide containing gas comprises a kind of in the mixture of the mixture of pure carbon dioxide, air and carbonic acid gas and nitrogen and carbonic acid gas or the kiln gas that the Wingdale thermolysis produces, the preferably kiln gas of Wingdale thermolysis generation, and the carbonated concentration of handling through water washing cleaning at least is 10%～40% clean kiln gas.
The initial calcium hydroxide content of a calcium hydroxide aqeous suspension is between 5%～13%, and the calcium hydroxide content of a calcium hydroxide aqeous suspension is lower than 5%, and is uneconomical.One time milk of lime calcium hydroxide content surpasses 10%, and the cube lime carbonate seed demand that obtain uniform granularity improves the consumption of crystal shape control agent, and its result also is uneconomic.The initial calcium hydroxide content of a preferred milk of lime is 6～11%.
The flow of carbon dioxide containing gas is 2～50m during carbonization
3/ (h.m
3Milk of lime).The flow of carbon dioxide containing gas is also relevant with the whipped form of reactor, when the mechanical type of the Forced Mixing that adopts applied power stirs, can adopt lower flow; When adopting the bubbling column reactor of no mechanical type stirring, can use bigger flow;
(2) be that 10～16% secondary milk of lime adds the suspension that contains speed of response control agent and nano-calcium carbonate seed with the calcium hydroxide weight concentration, the ratio of lime carbonate seed suspension and secondary milk of lime accounts for 0.5～15% of secondary milk of lime lime carbonate quality meter according to lime carbonate seed in the lime carbonate seed suspension, is preferably 1～7%.Feed carbonated gas, carburizing reagent, carbonization to the pH of suspension be 6.0～7, adopt conventional method to collect calcium carbonate granule this then from reactant, this calcium carbonate granule is that prism and cube are main, and main size distribution is at 0.4-1.0 μ m, L=0.71 μ m, σ=0.047, BET is 5.6m
2/ g.
Said speed of response control agent is selected from a kind of or its mixture in sucrose, alkali-metal carbonate or supercarbonate, polyacrylic acid and the sodium salt thereof;
Said speed of response control gross weight is 0.5～5% of a gained calcium carbonate calcium carbonate gross weight, preferably 0.8～4%;
The polyacrylic acid preferred molecular weight of being addressed be in 400～2000 the polyacrylic acid low-molecular-weight resin any one.This resin can be polymerized by emulsion polymerization by one or two or more kinds the monomer in vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, the styrene monomer.
Starting temperature is 35～60 ℃, and most economical initial reaction temperature is that the first step reaction finishes back lime carbonate seed suspension and the mixed temperature of secondary milk of lime, need not additional heat may or cooling, and this mixing temperature is between 38～55 ℃ usually.
The flow of carbonated gas is 1～50m
3/ (h.m
3Milk of lime).
The granularity size of indication of the present invention is to observe the arithmetical av L=∑ (Li/50) of the size on 50 particulate projection limits according to particle with the suspension method sample preparation under transmission electron microscope, and the degree of uniformity of particle size calculates σ=(∑ (L-Li) according to 50 particulate variances
2)/50.
By the detailed description of technique scheme as can be seen, the method of production calcium carbonate superfine powder particle dispersion provided by the invention, be suitable for existing all kinds of conversion unit, need not increase equipment, just can implement in various intermittent type precipitator method lime carbonate factory, and used additive amount is few in the process, the product that obtains has granular size and distributes controlled, the characteristics that good dispersity and whiteness are high, not only be suitable as the paper stopping composition and paper coating pigment has gloss height and low viscosity characteristics, and be suitable for coating, application scenarios such as plastics are as semi-reinforcing agent and senior filler.
Description of drawings
The transmission electron microscope photo of Fig. 1 embodiment 1 and embodiment 6 seeds, scale are 0.05 micron.
The transmission electron microscope photo of Fig. 2 embodiment 3 and embodiment 7 seeds, scale are 0.05 micron.
The transmission electron microscope photo of Fig. 3 embodiment 1 product calcium carbonate powders, scale is 0.2 micron.
The transmission electron microscope photo of Fig. 4 embodiment 4 product calcium carbonate powderss, scale is 0.2 micron.
The transmission electron microscope photo of Fig. 5 embodiment 5 product calcium carbonate powderss, scale is 0.2 micron.
The transmission electron microscope photo of Fig. 6 embodiment 6 product calcium carbonate powderss, scale is 0.1 micron.
Embodiment:
By the following examples the concrete embodiment of the present invention is narrated, but embodiment does not limit protection scope of the present invention.
Embodiment 1
5 liters of purified calcium hydroxide concentrations of adding are a calcium hydroxide emulsion of 7% in 7 liters stirred autoclave, add again after 23.6g sucrose stirs, make its starting temperature remain on 28 ℃, the kiln gas that begins to feed carbonated 40% then begins carburizing reagent, its initial flow is 250L/h, when carbonation rate reaches 30%, reducing the kiln gas flow is 150L/h, reach at 6.7 o'clock up to the pH of aqeous suspension value, stop ventilation, carburizing reagent finishes, obtain the nano-calcium carbonate seed suspension B of favorable dispersity, the median size of this nano-calcium carbonate seed of sampling analysis is 0.021 μ m, and σ is 0.0000452, specific surface area 65m
2/ g, its transmission electron microscope photo is seen accompanying drawing 1.
In calcium hydroxide concentration is 14% two calcium hydroxide emulsions, adds and contain 198.45gCaCO
3Behind the suspension and 30g sodium polyacrylate mixing of the first step reaction gained of seed, the 15L suspension that obtains like this placed aspect ratio 8: 1, in the bubble tower of internal diameter 140mm, keeping the slurries starting temperature is 50 ℃, and begins to feed the kiln gas of carbonated 15%, the beginning carburizing reagent, its initial flow is 200L/h, reaches 25% to carbonation rate, and augmented flow is 600L/h, pH to suspension is 6.7 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, pulverizing obtains the cube of good dispersion property and the class sphere is main, and main size distribution is at 0.11-0.41 μ m, L=0.28 μ m, σ=0.0066, BET is 14m
2The calcium carbonate granule of/g.The transmission electron microscope photo is seen Fig. 3.
Embodiment 2
5 liters of purified calcium hydroxide concentrations of adding are a calcium hydroxide emulsion of 10% in 7 liters stirred autoclave, add again after 27g sodium sulfate stirs, make its starting temperature remain on 35 ℃, the kiln gas that begins to feed carbonated 15% then begins carburizing reagent, and its initial flow is 150L/h, when carbonation rate reaches 15%, reducing the kiln gas flow is 100L/h, reach at 6.9 o'clock up to the pH of aqeous suspension value, stop ventilation, obtain the nanometer CaCO of favorable dispersity
3Seed suspension C, this nanometer of sampling analysis CaCO
3The particle diameter of seed is 0.075 μ m, and σ is 0.000499, specific surface area 18.5m
2/ g.
Calcium hydroxide concentration is in 16% the secondary calcium hydroxide emulsion, adds and contains 160gCaCO
3The suspension and the 17.8g sodium bicarbonate of the first step reaction gained of seed, behind the mixing, this 15L mixing suspension was placed aspect ratio 8: 1, in the bubble tower of internal diameter 140mm, the slurries starting temperature is 55 ℃, and begin to feed the kiln gas of carbonated 30%, and the beginning carburizing reagent, its initial flow is 200L/h, reach 30% to carbonation rate, augmented flow is 750L/h, to the pH of suspension be 6.7 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, it is main pulverizing the prism and the cube that obtain good dispersion property, main size distribution is at 0.4-1.0 μ m, L=0.71 μ m, σ=0.047, BET is 5.6m
2The calcium carbonate granule of/g.
Embodiment 3
Blistering reaction still (aspect ratio 8: 1 to 20 liters, internal diameter 140mm) 15 liters of purified calcium hydroxide concentrations of adding are a calcium hydroxide emulsion of 8% in, add again after 30g sucrose and 18.6g sodium sulfate stirs, make its starting temperature remain on 30 ℃, the kiln gas that begins to feed carbonated 25% then begins carburizing reagent, its initial flow is 600L/h, when carbonation rate reaches 20%, reducing the kiln gas flow is 400L/h, reach at 6.7 o'clock up to the pH of aqeous suspension value, stop ventilation, obtain the nano-calcium carbonate seed suspension of favorable dispersity, the median size of this nano-calcium carbonate seed of sampling analysis is 0.050 μ m, and σ is 0.000147, specific surface area 28m
2/ g, its transmission electron microscope photo is seen accompanying drawing 2.
In the secondary calcium hydroxide emulsion of calcium hydroxide 12%, add and contain 24.3gCaCO
3Behind the suspension and 52g sodium bicarbonate mixing of the first step reaction gained of seed, then this 15L mixing suspension was placed aspect ratio 8: 1, in the bubble tower of internal diameter 140mm, keeping the slurries starting temperature is 45 ℃, and begins to feed the kiln gas of carbonated 25%, the beginning carburizing reagent, its initial flow is 300L/h, reaching 15% augmented flow to carbonation rate is 700L/h, to the pH of suspension be 6.8 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, it is main pulverizing the prism and the cube that obtain good dispersion property, main size distribution is at 0.3-1.1 μ m, L=0.96 μ m, σ=0.049, BET is 4.2m
2The calcium carbonate granule of/g.
Embodiment 4
5 liters of purified calcium hydroxide weight concentrations of adding are a calcium hydroxide aqeous suspension of 6% in 7 liters of stirred autoclaves, add again after 1.3g glucose stirs, make its starting temperature remain on 24 ℃, the kiln gas that begins to feed carbonated 33% then begins carburizing reagent, its initial flow is 175L/h, when carbonation rate reaches 20%, reducing the kiln gas flow is 100L/h, reach at 6.8 o'clock up to the pH of aqeous suspension value, stop ventilation, obtain the nano-calcium carbonate seed suspending liquid A of favorable dispersity, the median size L of this nano-calcium carbonate seed of sampling analysis is 0.045 μ m, σ is 0.000807, specific surface area 31m
2/ g.
In calcium hydroxide concentration is 14% secondary calcium hydroxide emulsion, adds and contain 198.45gCaCO
3After the suspending liquid A and 5.5g sodium bicarbonate and 15g sodium polyacrylate mixing of the first step reaction gained of seed, the 15L suspension that obtains like this placed aspect ratio 8: 1, in the bubble tower of internal diameter 140mm, keeping the slurries starting temperature is 48 ℃, and begins to feed the kiln gas of carbonated 22%, the beginning carburizing reagent, its initial flow is 100L/h, reaches 20% to carbonation rate, and augmented flow is 500L/h, pH to suspension is 6.9 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, cube edge cylindricality and a small amount of class sphere that pulverizing obtains good dispersion property are main, and main size distribution is at 0.16-0.56 μ m, L=0.36, σ=0.015, BET is 11m
2The calcium carbonate granule of/g.Its transmission electron microscope photo is seen accompanying drawing 4.
Embodiment 5
5 liters of purified calcium hydroxide concentrations of adding are a calcium hydroxide emulsion of 10% in 7 liters stirred autoclave, add again after 27g sodium sulfate stirs, make its starting temperature remain on 35 ℃, the kiln gas that begins to feed carbonated 15% then begins carburizing reagent, and its initial flow is 150L/h, when carbonation rate reaches 15%, reducing the kiln gas flow is 100L/h, reach at 6.9 o'clock up to the pH of aqeous suspension value, stop ventilation, obtain the nanometer CaCO of favorable dispersity
3Seed suspension C, this nanometer of sampling analysis CaCO
3The particle diameter of seed is 0.075 μ m, and σ is 0.000499, specific surface area 18.5m
2/ g.
At calcium hydroxide concentration is to add in 16% the secondary calcium hydroxide emulsion to contain 56.5gCaCO
3Behind the suspension and 5.6g sodium bicarbonate and 10g sucrose mixing of the first step reaction gained of seed, the 5L suspended emulsion that obtains like this adds in the stirred autoclave of 7L, keeping the starting temperature of slurries is 35 ℃, and to begin to feed carbonated be 40% kiln gas, the beginning carburizing reagent, and its initial flow is 30L/h, reach 30% to carbonation rate, augmented flow is 75L/h, to the pH of suspended emulsion be 6.8 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, pulverize obtain favorable dispersity based on cube and prismatic, main size distribution is at 0.3-0.7 μ m, L=0.57 μ m, σ=0.0419, BET is 6.5m
2The calcium carbonate granule of/g.Its transmission electron microscope photo is seen accompanying drawing 5.
Embodiment 6
5 liters of purified calcium hydroxide concentrations of adding are a calcium hydroxide emulsion of 7% in 7 liters stirred autoclave, add again after 23.6g sucrose stirs, make its starting temperature remain on 28 ℃, the kiln gas that begins to feed carbonated 40% then begins carburizing reagent, its initial flow is 250L/h, when carbonation rate reaches 30%, reducing the kiln gas flow is 150L/h, reach at 6.7 o'clock up to the pH of aqeous suspension value, stop ventilation, carburizing reagent finishes, obtain the nano-calcium carbonate seed suspension B of favorable dispersity, the median size of this nano-calcium carbonate seed of sampling analysis is 0.021 μ m, and σ is 0.0000452, specific surface area 65m
2/ g, its transmission electron microscope photo is seen accompanying drawing 1.
At calcium hydroxide concentration is to add in 12% the secondary oxidation calcium emulsion to contain 24.5gCaCO
3Behind the suspension and 10g sucrose and 8.1g yellow soda ash mixing of the first step reaction gained of seed, the 5L suspended emulsion that obtains like this adds in the stirred autoclave of 7L, keeping the starting temperature of slurries is 40 ℃, and to begin to feed carbonated be 25% kiln gas, the beginning carburizing reagent, and its initial flow is 40L/h, reach 25% to carbonation rate, augmented flow is 90L/h, to the pH of suspended emulsion be 6.6 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, pulverize obtain favorable dispersity based on rhombus and class sphere, main size distribution is at 0.08-0.26 μ m, L=0.14, σ=0.00050, BET is 16m
2The calcium carbonate granule of/g.Its transmission electron microscope photo is seen accompanying drawing 6.
Embodiment 7
Blistering reaction still (aspect ratio 8: 1 to 20 liters, internal diameter 140mm) 15 liters of purified calcium hydroxide concentrations of adding are a calcium hydroxide emulsion of 8% in, add again after 30g sucrose and 18.6g sodium sulfate stirs, make its starting temperature remain on 30 ℃, the kiln gas that begins to feed carbonated 25% then begins carburizing reagent, its initial flow is 600L/h, when carbonation rate reaches 20%, reducing the kiln gas flow is 400L/h, reach at 6.7 o'clock up to the pH of aqeous suspension value, stop ventilation, obtain the nano-calcium carbonate seed suspension of favorable dispersity, the median size of this nano-calcium carbonate seed of sampling analysis is 0.050 μ m, and σ is 0.000147, specific surface area 28m
2/ g, its transmission electron microscope photo is seen accompanying drawing 2.
At calcium hydroxide concentration is to add in 13% the secondary oxidation calcium emulsion to contain 64.5gCaCO
3Behind the suspension and 5g sodium bicarbonate and 5g sodium polyacrylate mixing of the first step reaction gained of seed, the 5L suspended emulsion that obtains like this adds in the stirred autoclave of 7L, keeping the starting temperature of slurries is 50 ℃, and to begin to feed carbonated be 15% kiln gas, the beginning carburizing reagent, and its initial flow is 40L/h, reach 20% to carbonation rate, augmented flow is 80L/h, continue carbonization to the pH of suspended emulsion be 6.8 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, pulverize obtain favorable dispersity based on prismatic and cube, main size distribution is at 0.09-0.40 μ m, L=0.22, σ=0.0014, BET is 13m
2The calcium carbonate granule of/g.
Embodiment 8
5 liters of purified calcium hydroxide weight concentrations of adding are a calcium hydroxide aqeous suspension of 6% in 7 liters of stirred autoclaves, add again after 1.3g glucose stirs, make its starting temperature remain on 24 ℃, the kiln gas that begins to feed carbonated 33% then begins carburizing reagent, its initial flow is 175L/h, when carbonation rate reaches 20%, reducing the kiln gas flow is 100L/h, reach at 6.8 o'clock up to the pH of aqeous suspension value, stop ventilation, obtain the nano-calcium carbonate seed suspending liquid A of favorable dispersity, the median size L of this nano-calcium carbonate seed of sampling analysis is 0.045 μ m, σ is 0.000807, specific surface area 31m
2/ g.
After calcium hydroxide concentration is to add the suspending liquid A and 11g sodium bicarbonate mixing of the first step reaction gained that contains the 11gCaCO3 seed in 15% the secondary oxidation calcium emulsion, the 5L suspended emulsion that obtains like this adds in the stirred autoclave of 7L, keeping the starting temperature of slurries is 45 ℃, and to begin to feed carbonated be 25% kiln gas, the beginning carburizing reagent, its initial flow is 36L/h, reach 25% to carbonation rate, augmented flow is 70L/h, continue carbonization to the pH of suspended emulsion be 6.7 o'clock, stop ventilation, carburizing reagent finishes, after filtration, oven dry, pulverize obtain favorable dispersity based on prismatic and cube, main size distribution is at 0.10-0.60 μ m, L=0.41 μ m, σ=0.0014, BET is the calcium carbonate granule of 7.8m2/g.
Claims (3)
1. a method of making the calcium carbonate superfine powder particle dispersion is characterized in that, comprises the steps:
(1) carbonated gas is fed a calcium hydroxide aqeous suspension that contains the crystal shape control agent and carry out carbonization, carbonization to the pH value of aqeous suspension is 6～6.9, acquisition contains the suspension of nano-calcium carbonate seed, during carbonization, one time calcium hydroxide aqeous suspension starting temperature is 20～40 ℃, the initial calcium hydroxide weight content of a calcium hydroxide aqeous suspension is 5%～13%, and the flow of carbon dioxide containing gas is 2～50m during carbonization
3/ (h.m
3Milk of lime);
Said crystal shape control agent is selected from a kind of or its mixture in sucrose, glucose or the sodium sulfate, and the gross weight of crystal shape control agent is 0.7%～7% of a gained lime carbonate seed;
(2) be that 10～16% secondary milk of lime adds the suspension that contains speed of response control agent and nano-calcium carbonate seed with the calcium hydroxide weight concentration, feed carbonated gas, carburizing reagent, starting temperature is 35～60 ℃, carbonization to the pH of suspension be 6.0～7, adopt conventional method to collect calcium carbonate granule then from reactant, wherein, the flow of carbon dioxide containing gas is 1～50m during carbonization
3/ (h.m
3Milk of lime), the ratio of lime carbonate seed suspension and secondary milk of lime accounts for 0.5～15% of secondary milk of lime lime carbonate quality meter according to lime carbonate seed in the lime carbonate seed suspension;
Said speed of response control agent is selected from a kind of or its mixture in sucrose, alkali-metal carbonate or supercarbonate, polyacrylic acid and the sodium salt thereof, and the gross weight of speed of response control agent is 0.5～5% of a gained weight of calcium carbonate.
2. method according to claim 1 is characterized in that, the polyacrylic acid of being addressed is that molecular weight is 400～2000 polyacrylic acid low-molecular-weight resin.
3. method according to claim 1 is characterized in that, said carbon dioxide containing gas is selected from a kind of in the mixture of mixture, nitrogen and carbonic acid gas of pure carbon dioxide, air and carbonic acid gas or the kiln gas that the Wingdale thermolysis produces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100251557A CN1253373C (en) | 2004-06-14 | 2004-06-14 | Method for manufacturing super fine calcium carbonate dispersing particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100251557A CN1253373C (en) | 2004-06-14 | 2004-06-14 | Method for manufacturing super fine calcium carbonate dispersing particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583570A CN1583570A (en) | 2005-02-23 |
| CN1253373C true CN1253373C (en) | 2006-04-26 |
Family
ID=34601168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100251557A Expired - Fee Related CN1253373C (en) | 2004-06-14 | 2004-06-14 | Method for manufacturing super fine calcium carbonate dispersing particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253373C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9902652B2 (en) | 2014-04-23 | 2018-02-27 | Calera Corporation | Methods and systems for utilizing carbide lime or slag |
| US11377363B2 (en) | 2020-06-30 | 2022-07-05 | Arelac, Inc. | Methods and systems for forming vaterite from calcined limestone using electric kiln |
| US11577965B2 (en) | 2020-02-25 | 2023-02-14 | Arelac, Inc. | Methods and systems for treatment of lime to form vaterite |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323947C (en) * | 2005-12-29 | 2007-07-04 | 上海耀华纳米科技有限公司 | Tech. for preparing super fine actived calcium carbonate with low oil absorpsion value |
| CN101531391B (en) * | 2009-04-16 | 2011-05-18 | 芜湖卓越纳米新材料有限公司 | Method for industrially preparing nanometer calcium carbonate for solvent type ink addition agent |
| CN103950965B (en) * | 2014-04-29 | 2016-07-13 | 东华大学 | A kind of method using kind of crystallization to prepare different size nano-calcium carbonate |
| CN106517285B (en) * | 2016-11-21 | 2017-11-14 | 广西华纳新材料科技有限公司 | A kind of preparation method of rod-like nano calcium carbonate |
| CN108928844B (en) * | 2018-08-01 | 2021-01-05 | 建德华明科技有限公司 | Preparation method of regular cubic calcium carbonate |
| CN110813059A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Method for reducing regeneration energy consumption of carbon dioxide capture solvent |
| CN111003722B (en) * | 2019-08-28 | 2022-10-28 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive |
| CN111874933A (en) * | 2020-08-14 | 2020-11-03 | 王权广 | Quick preparation process of rice-grain light calcium carbonate |
| JP6948086B1 (en) * | 2020-12-22 | 2021-10-13 | 株式会社白石中央研究所 | Calcium carbonate production method and its crystal growth method |
| CN112811456A (en) * | 2021-01-26 | 2021-05-18 | 江西势通钙业有限公司 | Nano calcium carbonate with high specific surface area and preparation method thereof |
-
2004
- 2004-06-14 CN CNB2004100251557A patent/CN1253373C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9902652B2 (en) | 2014-04-23 | 2018-02-27 | Calera Corporation | Methods and systems for utilizing carbide lime or slag |
| US11577965B2 (en) | 2020-02-25 | 2023-02-14 | Arelac, Inc. | Methods and systems for treatment of lime to form vaterite |
| US11377363B2 (en) | 2020-06-30 | 2022-07-05 | Arelac, Inc. | Methods and systems for forming vaterite from calcined limestone using electric kiln |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1583570A (en) | 2005-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100545092C (en) | A kind of preparation method of submicron grade superfine calcium carbonate dispersion particle | |
| CN1253373C (en) | Method for manufacturing super fine calcium carbonate dispersing particles | |
| CA2686416C (en) | Process for production of pcc | |
| KR101585312B1 (en) | Process for the production of precipitated calcium carbonate, precipitated calcium carbonate and uses thereof | |
| CN100455515C (en) | Method for preparing nano calcium carbonate particle | |
| CN101774623B (en) | Industrial preparation method of rice-shaped ultra-fine activated calcium carbonate | |
| EP0722422B1 (en) | Preparation of spheroidal aggregates of platy synthetic hydrotalcite | |
| CA2290816C (en) | Seeding of aragonite calcium carbonate and the product thereof | |
| AU2004252070A1 (en) | Process for the production of platy precipitated calcium carbonates, product produced thereby, and paper incorporating same | |
| JP2002510737A (en) | Precipitated calcium carbonate and its manufacturing method and use | |
| CN1429772A (en) | Method for preparing calcium carbonate with actual forms | |
| CN105745283B (en) | It is used to prepare the method for composite particles | |
| JPH08209029A (en) | Spherical delustering agent for coating material and coating material composition | |
| JP2612663B2 (en) | Mixed carbonates and method for producing the same | |
| CN1634767A (en) | Method for producing nano calcium carbonate particles for printing ink | |
| EP0844213A1 (en) | Precipitates and their production | |
| JP2706384B2 (en) | Particle size adjustment method of aragonite columnar calcium carbonate | |
| Nakanishi et al. | Using phenolic polymers to control the size and morphology of calcium carbonate microparticles | |
| CN101265112A (en) | Suspending agent of mica mineral in water solution | |
| CN1361063A (en) | One-step carbonization process of preparing cubic calcium carbonate of 80-100 nm size | |
| CN102796414A (en) | Similar light calcium carbonate, active similar light calcium carbonate and preparation methods and uses thereof | |
| JP2787620B2 (en) | Method for producing needle-like aragonite crystalline calcium carbonate | |
| JP2001302238A (en) | Method for producing spindle-shaped calcium carbonate having small particle diameter | |
| CN105800658A (en) | Method for efficiently preparing nano calcium carbonate | |
| JP2005170733A (en) | Production method for scallop-shell-derived light precipitated calcium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 Termination date: 20210614 |