CN108893775B - Preparation method of high-purity calcium carbonate whisker - Google Patents

Preparation method of high-purity calcium carbonate whisker Download PDF

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CN108893775B
CN108893775B CN201810779834.5A CN201810779834A CN108893775B CN 108893775 B CN108893775 B CN 108893775B CN 201810779834 A CN201810779834 A CN 201810779834A CN 108893775 B CN108893775 B CN 108893775B
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calcium carbonate
purity
solution
whisker
calcium oxide
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CN108893775A (en
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王宗荣
李庆蕾
尹翀
戴正冠
杜丕一
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Wuyuan Shengli Plastic Rubber Co ltd
Zhejiang Anlian Mining Co ltd
Zhejiang University ZJU
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Wuyuan Shengli Plastic Rubber Co ltd
Zhejiang Anlian Mining Co ltd
Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles

Abstract

The invention discloses a preparation method of high-purity calcium carbonate whiskers, which comprises the following steps: firstly, calcium carbonate raw materials are calcined and decomposed into calcium oxide, then the calcium oxide is added into deionized water to be digested at a certain temperature, then the calcium oxide is sprayed and added into a crystal form control agent solution to be uniformly stirred, carbon dioxide is introduced at a certain speed by utilizing an aeration device, so that the bubble volume and the dispersity of the introduced gas, namely the concentration of carbonate ions, are controlled, and the carbonization reaction is uniform and consistent, thereby preparing the high-purity whisker. The method solves the problem of low whisker purity caused by uneven dispersion of gas in the solution in the conventional preparation process of ventilation by using the latex tube, and the gas is in more full contact with the solution, so that the method not only can prepare the whisker with higher purity, but also can save the used carbon dioxide gas to a great extent and reduce the preparation cost.

Description

Preparation method of high-purity calcium carbonate whisker
Technical Field
The invention relates to the technical field of inorganic filling material preparation, in particular to a preparation method of high-purity calcium carbonate whiskers.
Background
The inorganic whisker has a complete structure and few defects, the strength and the modulus of the inorganic whisker are close to theoretical values of a complete crystal, and the flame retardant property of the inorganic whisker is better than that of the organic whisker, so that the inorganic whisker becomes an ideal reinforcing and toughening material of a composite material, such as ZnO, SiC, potassium titanate, mullite, aluminum borate and the like, which has already realized industrial production but obstructs large-scale application due to high cost, and the calcium carbonate whisker has wide raw material sources and low production cost, can be prepared even by using industrial waste residues, and is expected to become the most important inorganic whisker material.
At present, scholars at home and abroad make a great deal of research on the preparation of aragonite calcium carbonate whiskers, and five preparation methods are mainly adopted: (1) a double decomposition method; (2) ca (HCO)3)2A thermal decomposition method; (3) urea hydrolysis; (4) sol-gel method; (5) carbonation method. The carbonation method is the most and mature method studied at home and abroad, and is expected to realize the industrialization of calcium carbonate at the earliest because of simple preparation process and low cost. The general process of the carbonation method is that calcium oxide is digested into suspension slurry in deionized water, the suspension is mixed with a crystal form control agent solution, then carbon dioxide gas is introduced, and calcium carbonate crystal whiskers are generated through reaction under the crystal form control action of the crystal form control agent. The key problem of preparing the high-purity whisker is that carbonate ions are unevenly distributed in the suspension, so that the supersaturation degree of a partial area is too high, calcite phase calcium carbonate is easily generated, and the purity of the whisker is reduced; the main reason is that when the latex tube is used for ventilation, large bubbles are generated at the bottom of the solution, the distribution range of the large bubbles is small, the concentration of carbonate ions at the position where the bubbles emerge and above the bubble is too high, calcite is rapidly generated, and aragonite phase whiskers are slowly generated at other positions with low saturation, which is not beneficial to the preparation of high-purity calcium carbonate whiskers.
Therefore, the invention provides a method for preparing high-purity calcium carbonate whiskers by introducing carbon dioxide gas through an aeration device, wherein the aeration device such as quartz bubble stone is a porous gas distributor, the pores are fine, the introduced carbon dioxide gas can be broken into a plurality of bubbles with small volume, the small bubbles are dispersed after being introduced into a solution, the gas distribution range is expanded, so that the generated carbonate ions are uniformly distributed in the solution, and the supersaturation degree of the carbonate ions in each part of the solution is controlled by adjusting the aeration rate of the carbon dioxide, so that the high-purity calcium carbonate whiskers are generated. In addition, the aeration device is adopted to ensure that the carbon dioxide gas and the solution are in more sufficient contact, the utilization rate of the introduced carbon dioxide is high, the required ventilation volume is much lower than that of the latex tube, and the production cost is reduced to a great extent.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity calcium carbonate whiskers, which is based on a carbonation method and comprises the steps of firstly calcining a calcium carbonate raw material to decompose the calcium oxide into calcium oxide, then digesting the calcium oxide in deionized water at high temperature, taking a magnesium chloride solution as a crystal form control agent, spraying and adding a digested calcium hydroxide suspension into the magnesium chloride solution, introducing carbon dioxide at a certain speed by utilizing an aeration device with a certain pore diameter, controlling the volume and the dispersity of bubbles introduced with gas so as to uniformly distribute carbonate ions in the solution, stirring at a certain speed to carry out a carbonation reaction until the pH value of the solution is reduced to 7, and reacting to obtain the high-purity calcium carbonate whiskers. The concrete implementation is as follows:
the method comprises the following steps: calcium carbonate ore obtained by mining in a mining area is calcined and decomposed into calcium oxide at high temperature after being screened and ground; the high temperature is higher than the decomposition temperature of calcium carbonate.
Step two: adding the calcium oxide into deionized water to fully digest to obtain Ca (OH)2A suspension;
step three: dissolving magnesium chloride as crystal form control agent in water, and adding the digested Ca (OH)2Adding the suspension into a magnesium chloride solution in an atomization spraying manner, and uniformly stirring to obtain a mixed solution;
step four: and introducing carbon dioxide gas into the mixed solution through an aeration device, stirring to perform carbonization reaction, stopping the reaction until the pH value of the solution is reduced to 7, and performing suction filtration, washing and drying on the obtained precipitate to obtain the high-purity calcium carbonate whisker.
In the above technical solution, further, the average particle size of the calcium carbonate ore after being screened and ground in the first step is 1.29 to 4.24 μm;
further, in the second step, calcium oxide is added into deionized water at the temperature of 80-100 ℃, and the digestion time is at least 1 h;
further, the amount of magnesium chloride in the third step is such that the molar concentration ratio C of magnesium to calcium atomsMg/CCaBetween 1.5 and 2.5;
further, the aeration device adopted in the fourth step comprises quartz bubble stones, porous ceramics or porous bricks, and the pore diameter of the quartz bubble stones is as small as possible and is not more than 5 mm.
Further, the stirring speed in the fourth step is between 100 and 200 r/min.
Further, the aeration device in the fourth step is placed at the bottom of the mixed liquid.
Compared with the prior art for preparing calcium carbonate crystal whisker, the invention has the outstanding characteristics and remarkable progress that:
1. an aeration device such as air bubble stones is used as an aeration device, the introduced carbon dioxide gas is broken, the gas is favorably and uniformly dispersed in the solution, the concentration of carbonate in the solution is further favorably uniform, the same low supersaturation degree of reaction ions at all positions is favorably maintained, and the air bubble stones with smaller air holes are found to be favorable for generating whiskers with higher purity; meanwhile, the bubbles are in more sufficient contact with the solution, so that the utilization efficiency of carbon dioxide is improved, and the preparation cost is reduced.
2. The digested calcium hydroxide suspension is added into the magnesium chloride solution in an atomization spraying mode, the atomized suspension is dispersed to a certain extent in the spraying process, the magnesium chloride solution is favorable for being quickly and uniformly distributed, and the integral uniformity of a solution system is very important for preparing high-purity whiskers.
The purity of the calcium carbonate crystal whisker prepared by the method can reach 99.7 percent.
Drawings
FIG. 1 is an optical microscope picture of calcium carbonate whiskers;
figure 2 is an XRD spectrum of whiskers prepared in an example of the invention.
Detailed Description
The technical solution of the present invention will be described clearly and completely by the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments, and the aeration device of the present invention includes, but is not limited to, quartz bubble stones, and aeration devices such as porous ceramics, porous bricks, etc. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of protection of the present invention.
Example 1
The method comprises the following steps: calcining calcium carbonate with the average particle size of 1.29 mu m at high temperature to decompose the calcium carbonate into calcium oxide;
step two: weighing 7.84g of calcium oxide, adding into 600ml of deionized water, and fully digesting at 100 ℃;
step three: 42.693g of magnesium chloride was weighed as a crystal form control agent (magnesium calcium atom molar ratio was 1.5), 100ml of water was added to dissolve it, and Ca (OH) after digestion was added2Adding the suspension into a magnesium chloride solution by atomization spraying, and uniformly stirring;
step four: introducing carbon dioxide gas to the bottom of the reaction device at a flow rate of 10ml/min by using quartz air stones with an average pore diameter of 0.92mm, stirring at a speed of 100r/min, carrying out a carbonization reaction until the pH value of the solution is 7, stopping the reaction, and finally carrying out suction filtration, washing and drying on the obtained precipitate.
The SEM image of the prepared calcium carbonate whisker is shown in figure 1(1 #).
Example 2
The method comprises the following steps: calcining calcium carbonate with the average particle size of 2.77 mu m at high temperature to decompose the calcium carbonate into calcium oxide;
step two: weighing 7.84g of calcium oxide, adding into 600ml of deionized water, and fully digesting at 90 ℃;
step three: 56.942g of magnesium chloride (to give a molar ratio of magnesium to calcium of 2) was weighed as a crystal form controlling agent, 100ml of water was added to dissolve it, and Ca (OH) after digestion was added2Spraying the suspension into a magnesium chloride solution, and uniformly stirring;
step four: introducing carbon dioxide gas to the bottom of the reaction device at a flow rate of 25ml/min by using air stones with air hole diameters of 2.82mm, stirring at a speed of 150r/min, carrying out carbonization reaction until the pH value of the solution is 7, stopping the reaction, and finally carrying out suction filtration, washing and drying on the obtained precipitate.
The SEM image of the prepared calcium carbonate whisker is shown in figure 1(2 #).
Example 3
The method comprises the following steps: calcining calcium carbonate with the average particle size of 4.24 mu m at high temperature to decompose the calcium carbonate into calcium oxide;
step two: weighing 7.84g of calcium oxide, adding into 600ml of deionized water, and fully digesting at 80 ℃;
step three: 71.155g of magnesium chloride (to give a molar ratio of magnesium to calcium of 2.5) was weighed as a crystal form controlling agent, 100ml of water was added to dissolve it, and the digested Ca (OH) was added2Spraying the suspension into a magnesium chloride solution, and uniformly stirring;
step four: introducing carbon dioxide gas to the bottom of the reaction device at the flow rate of 40ml/min by using quartz air stones with the pore diameters of 4.94mm, stirring at the speed of 200r/min, carrying out carbonization reaction until the pH value of the solution is 7, stopping the reaction, and finally carrying out suction filtration, washing and drying on the obtained precipitate.
The SEM image of the prepared calcium carbonate whisker is shown in figure 1(3 #).
In addition, the invention also carries out a plurality of groups of control experiments to obtain 4-6# samples: compared with the example 1, only the following conditions are changed, and the other conditions are the same, wherein the No. 4 is added by directly pouring the calcium hydroxide suspension into the magnesium chloride solution instead of atomizing and spraying; no. 5 is the aeration with air stones with the average pore diameter of 10 mm; no. 6 is aerated with a soft rubber tube (diameter about 6mm) instead of air stones. The SEM images of the 6 samples are detailed in fig. 1, and the XRD patterns are detailed in fig. 2.
The whisker purity is calculated by the integrated intensity Ia of the highest peak of the aragonite phase and the integrated intensity Ic of the highest peak of the calcite phase in the XRD map:
Figure BDA0001732288310000061
the purity of the whisker prepared in example 1(1#) is calculated to be 99.7%; the purity of the whisker prepared in example 2(2#) is 99.3%; the purity of the whisker prepared in example 3(3#) is 99.1%; the purity of control 4# was 92.4%, the purity of control 5# was 95.2%, and the purity of control 6# was 90.1%. From this it can be concluded that: the purity of the whiskers can be obviously improved by using an aeration device such as quartz bubbled stone as an aeration device and adopting a method of adding calcium hydroxide suspension by mist spraying.

Claims (6)

1. A preparation method of high-purity calcium carbonate whiskers is characterized by comprising the following steps:
the method comprises the following steps: calcium carbonate ore obtained by mining in a mining area is calcined and decomposed into calcium oxide at high temperature after being screened and ground;
step two: adding the calcium oxide into deionized water to fully digest to obtain Ca (OH)2A suspension;
step three: dissolving magnesium chloride as crystal form control agent in water, and adding the digested Ca (OH)2Adding the suspension into a magnesium chloride solution in an atomization spraying manner, and uniformly stirring to obtain a mixed solution;
step four: introducing carbon dioxide gas into the mixed solution through an aeration device, stirring for carbonization reaction, stopping the reaction until the pH value of the solution is reduced to 7, and performing suction filtration, washing and drying on the obtained precipitate to obtain high-purity calcium carbonate whiskers; the aeration device comprises quartz bubble stone, porous ceramics or porous bricks, and the aperture of the quartz bubble stone is not more than 5 mm.
2. The method for preparing high-purity calcium carbonate whiskers as claimed in claim 1, wherein: and in the first step, the average particle size of the calcium carbonate ore after screening and grinding is 1.29-4.24 microns.
3. The method for preparing high-purity calcium carbonate whiskers as claimed in claim 1, wherein: and in the second step, calcium oxide is added into deionized water at the temperature of 80-100 ℃, and the digestion time is at least 1 h.
4. The method for preparing high-purity calcium carbonate whiskers as claimed in claim 1, wherein: the amount of magnesium chloride in step three is such that the molar concentration ratio of magnesium to calcium atomsCMg/CCaBetween 1.5 and 2.5.
5. The method for preparing high-purity calcium carbonate whiskers as claimed in claim 1, wherein: in the fourth step, the stirring speed is 100-200 r/min.
6. The method for preparing high-purity calcium carbonate whiskers as claimed in claim 1, wherein: and in the fourth step, the aeration device is placed at the bottom of the mixed liquid.
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CN112410882A (en) * 2020-11-19 2021-02-26 成都新柯力化工科技有限公司 Whitening calcium carbonate whisker for plastic reinforcement and preparation method thereof
CN113564688B (en) * 2021-07-09 2023-11-28 沈阳化工大学 Preparation method of calcium carbonate whisker
CN114314629B (en) * 2021-12-16 2022-09-30 浙江大学 Preparation method of nano calcium carbonate based on surface potential control

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CN1552959A (en) * 2003-05-26 2004-12-08 青海海兴科技开发有限公司 Preparing process for calcium carbonate crystal whisker
CN1303264C (en) * 2004-01-13 2007-03-07 中国人民解放军国防科学技术大学 Method for preparing aragonite type calcium carbonate whisker
CN104790024A (en) * 2015-04-15 2015-07-22 广西大学 Preparation method for aragonite calcium carbonate whisker with high length-diameter ratio
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