CN107021515B - The method for controlling precipitated calcium carbonate length of particle ratio - Google Patents
The method for controlling precipitated calcium carbonate length of particle ratio Download PDFInfo
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- CN107021515B CN107021515B CN201710276192.2A CN201710276192A CN107021515B CN 107021515 B CN107021515 B CN 107021515B CN 201710276192 A CN201710276192 A CN 201710276192A CN 107021515 B CN107021515 B CN 107021515B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a kind of methods for controlling precipitated calcium carbonate length of particle ratio, include the following steps: A, the calcium hydroxide suspension that preparation concentration is 100-120 grams per liter；B, before carbonation reaction starting, the water-soluble zinc salt for being equivalent to weight of calcium carbonate 0.05-1% is added into the calcium hydroxide suspension of step A, stirs 5-10 minutes, is uniformly mixed it；C, carbonation reaction is opened, carbon dioxide gas mixture is blasted into calcium hydroxide suspension by air compressor, when calcium hydroxide reaction tends to terminate, when its pH value is less than 8, the aminocarboxylic acids for being equivalent to weight of calcium carbonate 0.01-0.1% is added into newborn precipitated calcium carbonate clinker slurry to control auxiliary agent as crystal form or be equivalent to the hydroxycarboxylic acid metal-chelator of weight of calcium carbonate 0.1-1% as crystal form control auxiliary agent, row bubbling carbonizing reacts 10 minutes to get this product again.The mobility of manufactured goods can be enhanced in the present invention, improves tensile strength, impact strength, and low in cost.
Description
Technical field
The present invention relates to a kind of methods for controlling precipitated calcium carbonate length of particle ratio, belong to the preparation method of precipitated calcium carbonate
Technical field.
Background technique
The particle morphology of precipitated calcium carbonate is typical thin, soft plain-weave silk fabric hammer body structure, sees attached drawing 1 and attached drawing 2, minor axis about 0.5-1
Micron, about 1-3 microns of major diameter, draw ratio about 1: 3 is typical micron order product type.Such particle shape and particle ruler
Very little product only has filling capacity, without toughening, reinforcing property.
Currently, for rubber product toughening, reinforcement material mainly include the following types:
First is that addition carbon black and white carbon black, both materials have the partial size of nanoscale, and particle size is received in 20-30
Rice, and regular appearance, particle size is uniform, is ideal supporting material, but expensive.
Second is that selecting chemical additives and its dosage, usage can by the carbonation reaction temperature of control precipitated calcium carbonate
The nanometer calcium carbonate with reinforcing property is made, but particle is meticulous, and viscosity increases, especially with the charcoal with nanoscale
When black, white carbon black is used cooperatively, the specific surface area that excessive nanoparticle and rubber infiltrate mutually increases, so that the leaching to rubber
Profit and the dispersion of particle become difficult, and cause mixing viscosity big, and temperature is high, and vulcanization is fast, sizing material is precocious and mill be difficult to discharging,
The problems such as lower roll.
Third is that being surface-treated by organic additives such as resin acid and silane coupling agents to precipitated calcium carbonate, calcium carbonate
The dispersion of particle, mobility and having with the tackness of rubber improves by a relatively large margin, and application performance significantly improves, but price is at double
Liter is turned over, market competition is unfavorable for.
Fourth is that addition wollastonite in powder can be improved the mechanical property of product and have certain reinforcing effect.Wollastonite belongs to one
Kind chain metasilicate, particle morphology is in fibrous, needle-shaped.Its special crystal habit structure determines its reinforcing feature,
But wollastonite with light gray, pale red tone, can seriously affect the form and aspect of product sometimes when for light color article.In addition, increasingly reducing
Resource also product be used for a long time form restriction.
Above-mentioned patent or the contained content of document, technical conditions are harsh, are unsuitable for industrialized production and application, it is difficult to promote real
It applies.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for controlling precipitated calcium carbonate length of particle ratio, to improve rubber wheel
The tensile break strength and resistance to tearing of the rubber soft goods such as tire, offset plate, cable.
The present invention is realized by following technological means and measure: this control precipitated calcium carbonate length of particle ratio
Method includes the following steps:
A, preparation concentration is the calcium hydroxide suspension of 100-120 grams per liter；
B, it before carbonation reaction starting, is added into the calcium hydroxide suspension of step A and is equivalent to weight of calcium carbonate
The water-soluble zinc salt of 0.05-1% stirs 5-10 minutes, is uniformly mixed it；
C, carbonation reaction is opened, blasts carbon dioxide mix gas into calcium hydroxide suspension by air compressor
Body is added in the precipitated calcium carbonate clinker slurry of Xiang Xinsheng and is equivalent to when calcium hydroxide reaction tends to terminate, and pH value is less than 8
The aminocarboxylic acids of weight of calcium carbonate 0.01-0.1% controls auxiliary agent as crystal form or is equivalent to the hydroxyl of weight of calcium carbonate 0.1-1%
Yl carboxylic acid metalloid chelating agent controls auxiliary agent as crystal form, then row bubbling carbonizing reacts 10 minutes to get this product.
The method for controlling precipitated calcium carbonate length of particle ratio, calcium hydroxide suspension described in step A are made by the following method
It is standby: to take 100 grams of calcium oxide, digested with 60 DEG C of clear water, 1000 milliliters of calcium hydroxide suspensions are made, then with titration with hydrochloric acid to carbon
Sour 100 grams per liter of calcium content, it is spare.
The method of the control precipitated calcium carbonate length of particle ratio, water-soluble zinc salt salt described in step B includes zinc sulfate
Or zinc chloride.
The method of the control precipitated calcium carbonate length of particle ratio, the method for addition water-soluble zinc salt described in step B include:
An aperture is opened after air compressor, is welded a diameter and is 0.5 centimeter of stainless steel tube, and installs controlled valve；Later,
It takes 0.5 gram of white vitriol to be added in the calcium hydroxide suspension of step A, stirs evenly, control starting carburizing temperature is 40
DEG C, stainless steel tube is inserted into calcium hydroxide suspension, Open valve is passed through the carbon dioxide gas mixture from limekiln,
Carbon dioxide volumetric concentration is 29%, is reacted 90 minutes, and the pH value of measurement carbonic acid calcium clinker slurry is 7.5.
The method of the control precipitated calcium carbonate length of particle ratio, amino carboxylic acid metalloid chelating agent packet described in step C
Include ethylenediamine tetra-acetic acid (EDTA) and its salt, aminotriacetic acid (NTA) and its salt or diethylene-triamine pentaacetic acid (DTPA) and
Its salt.
The method of the control precipitated calcium carbonate length of particle ratio, hydroxycarboxylic acid metal-chelator packet described in step C
Include citric acid, tartaric acid or gluconic acid.
Technological progress effect of the invention is shown: the light calcium carbonate product via the method for the present invention preparation has uniqueness
Raphioid fiber fibre structure, 0.1-0.5 microns of particle minor axis, 3-5 microns of major diameter, draw ratio about 1: 10-1: 15 is soft with rubber and plastic
Product is capable of forming winding arrangement, can be enhanced the mobility of manufactured goods, improve tensile strength, impact strength, linear stretch and
Mould shrinking percentage.
Detailed description of the invention
Fig. 1 is conventional lightweight calcium carbonate electromicroscopic photograph
Fig. 2 precipitated calcium carbonate electromicroscopic photograph of the present invention
Specific embodiment
Embodiment 1
1,100 grams of calcium oxide are taken, is digested with 60 DEG C of clear water, 1000 milliliters of calcium hydroxide suspensions are made, then use hydrochloric acid
It is titrated to 100 grams per liter of calcium carbonate content, it is spare；
2, an aperture is opened after air compressor, is welded a diameter and is 0.5 centimeter of stainless steel tube, and installs switch
Valve.Later, it takes 0.5 gram of white vitriol to be added in spare calcium hydroxide suspension, stirs evenly, control starting carbonization
Temperature is 40 DEG C, stainless steel tube is inserted into calcium hydroxide suspension, Open valve, and it is mixed to be passed through the carbon dioxide from limekiln
Gas is closed, carbon dioxide volumetric concentration is 29%, is reacted 90 minutes, and the pH value of measurement carbonic acid calcium clinker slurry is 7.5.
3, it after carbonation reaction, weighs 0.1 gram of ethylenediamine tetra-acetic acid (EDTA) and is added in carbonic acid calcium clinker slurry again
Row carbonization 10 minutes, after the slurry filtration, drying, sieve powder, measuring its particle morphology with electronic scanner microscope (SEM) is needle
Shape, draw ratio 1: 10.
Embodiment 2
1,2, with embodiment 1；
3, after carbonation reaction, 0.1 gram of aminotriacetic acid (NTA) is added into carbonic acid calcium clinker slurry, then row carbonization
10 minutes, after the slurry filtration, drying, sieve powder, measuring its particle morphology with electronic scanner microscope (SEM) was needle-shaped, length
Diameter ratio is 1: 11.
Embodiment 3
1,2, with embodiment 1；
3, after carbonation reaction, diethylene-triamine pentaacetic acid (DTPA) 0.15 is added into carbonic acid calcium clinker slurry
Gram, then row carbonization 10 minutes, after the slurry filtration, drying, sieve powder, its particle shape is measured with electronic scanner microscope (SEM)
Looks are needle-shaped, draw ratio 1: 12.
Embodiment 4
1,2, with embodiment 1；
3, after carbonation reaction, 0.5 gram of citric acid, then row carbonization 10 minutes are added into carbonic acid calcium clinker slurry, it will
After the slurry filtration, drying, sieve powder, measuring its particle morphology with electronic scanner microscope (SEM) is needle-shaped, draw ratio 1:
12。
Embodiment 5
1,2, with embodiment 1；
3, after carbonation reaction, 0.5 gram of tartaric acid, then row carbonization 10 minutes are added into carbonic acid calcium clinker slurry, it will
After the slurry filtration, drying, sieve powder, measuring its particle morphology with electronic scanner microscope (SEM) is needle-shaped, draw ratio 1: 9.
Embodiment 6
1,2, with embodiment 1；
3, after carbonation reaction, 1.0 grams of gluconic acid, then row carbonization 10 minutes are added into carbonic acid calcium clinker slurry,
After the slurry filtration, drying, sieve powder, measuring its particle morphology with electronic scanner microscope (SEM) is needle-shaped, draw ratio 1:
8。
Embodiment 7
1, calcium hydroxide suspension 40m is produced3, measuring suspension temperature is 40 DEG C, and Baume degrees is 7 degree, converts into calcium carbonate
Gram liter ratio is 110, and calcium carbonate butt total content is 4400kg.
2, under stirring condition, white vitriol 22kg is added into the suspension by 0.5% dosage, is stirred 10 minutes,
The calcium hydroxide suspension is pumped in carburizing reagent kettle, air compressor is opened, is passed through the carbon dioxide from limekiln
Mixed gas, carbon dioxide volumetric concentration are 31%, are reacted about 110 minutes, and the pH value for measuring carbonic acid calcium clinker slurry is 7.5.
3, it after carbonation reaction, weighs ethylenediamine tetra-acetic acid (EDTA) 3.52kg and is added to the calcium carbonate being carbonized
Continue carbonization 10 minutes in clinker slurry, after the slurry filtration, drying, sieve powder, measures its grain with electronic scanner microscope (SEM)
Sub- pattern is needle-shaped, draw ratio 1: 11.
Embodiment 8
1, calcium hydroxide suspension 40m is produced3, measuring suspension temperature is 43 DEG C, and Baume degrees is 7.5 degree, converts into carbonic acid
Calcium gram liter ratio is 120, and calcium carbonate butt total content is 4800kg.
2, under stirring condition, white vitriol 19.2kg is added into the suspension by 0.4% dosage, stirs 10 points
The calcium hydroxide suspension is pumped in carburizing reagent kettle by clock, is opened air compressor, is passed through the titanium dioxide from limekiln
Carbon mixed gas, carbon dioxide volumetric concentration are 32%, are reacted about 130 minutes, and the pH value for measuring carbonic acid calcium clinker slurry is 7.5.
3, it weighs citric acid 12kg and is added in the carbonic acid calcium clinker slurry being carbonized and continue carbonization 10 minutes, by the slurry
After filtering, dry, sieve powder, measuring its particle morphology with electronic scanner microscope (SEM) is needle-shaped, draw ratio 1: 13.See attached
Fig. 2.
Claims (5)
1. the method for controlling precipitated calcium carbonate length of particle ratio, includes the following steps:
A, preparation concentration is the calcium hydroxide suspension of 100-120 grams per liter；
B, it before carbonation reaction starting, is added into the calcium hydroxide suspension of step A and is equivalent to weight of calcium carbonate 0.05-
1% water-soluble zinc salt stirs 5-10 minutes, is uniformly mixed it；
Specific method includes: that an aperture is opened after air compressor, welds a diameter and is 0.5 centimeter of stainless steel tube, and pacifies
Install controlled valve；Later, it takes 0.5 gram of white vitriol to be added in the calcium hydroxide suspension of step A, stirs evenly, control
System starting carburizing temperature is 40 DEG C, stainless steel tube is inserted into calcium hydroxide suspension, Open valve is passed through from limekiln
Carbon dioxide gas mixture, carbon dioxide volumetric concentration are 29%, are reacted 90 minutes, and the pH value of measurement carbonic acid calcium clinker slurry is
7.5；
C, carbonation reaction is opened, carbon dioxide gas mixture is blasted into calcium hydroxide suspension by air compressor, when
Calcium hydroxide reaction tends to terminate, and when pH value is less than 8, is added in the precipitated calcium carbonate clinker slurry of Xiang Xinsheng and is equivalent to calcium carbonate
The aminocarboxylic acids of weight 0.01-0.1% controls auxiliary agent as crystal form or is equivalent to the hydroxycarboxylic acid of weight of calcium carbonate 0.1-1%
Metalloid chelating agent controls auxiliary agent as crystal form, then row bubbling carbonizing reacts 10 minutes to get this product.
2. controlling the method for precipitated calcium carbonate length of particle ratio according to claim 1, it is characterised in that: hydrogen described in step A
Calcium oxide suspension is prepared via a method which: being taken 100 grams of calcium oxide, is digested with 60 DEG C of clear water, 1000 milliliters of hydroxides are made
Calcium suspension, it is spare then with titration with hydrochloric acid to 100 grams per liter of calcium carbonate content.
3. controlling the method for precipitated calcium carbonate length of particle ratio according to claim 1, it is characterised in that: described in step B
Water-soluble zinc salt includes zinc sulfate or zinc chloride.
4. controlling the method for precipitated calcium carbonate length of particle ratio according to claim 1, it is characterised in that: described in step C
It includes ethylenediamine tetra-acetic acid (EDTA) and its salt, aminotriacetic acid (NTA) and its salt or diethylenetriamines that crystal form, which controls auxiliary agent,
Pentaacetic acid (DTPA) and its salt.
5. controlling the method for precipitated calcium carbonate length of particle ratio according to claim 1, it is characterised in that: described in step C
Hydroxycarboxylic acid metal-chelator includes citric acid, tartaric acid or gluconic acid.
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| CN108840359A (en) * | 2018-04-11 | 2018-11-20 | 立达超微工业（苏州）有限公司 | A kind of technique using calcite production porous spherical super fine calcium carbonate |
| CN110563015B (en) * | 2019-09-27 | 2022-03-29 | 河北立信化工有限公司 | Preparation method of light calcium carbonate for food |
| CN114455622B (en) * | 2022-02-23 | 2024-01-23 | 河北立信新材料科技有限公司 | Preparation method of super-dispersed functional calcium carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1179401A (en) * | 1996-10-16 | 1998-04-22 | 长春市迪瑞检验制品有限责任公司 | Method for producing crystalline form nm-class calcium carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179401A (en) * | 1996-10-16 | 1998-04-22 | 长春市迪瑞检验制品有限责任公司 | Method for producing crystalline form nm-class calcium carbonate |
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