WO2007078017A1 - Novel manufacturing method of aragonite calcium carbonate - Google Patents

Novel manufacturing method of aragonite calcium carbonate Download PDF

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Publication number
WO2007078017A1
WO2007078017A1 PCT/KR2005/004690 KR2005004690W WO2007078017A1 WO 2007078017 A1 WO2007078017 A1 WO 2007078017A1 KR 2005004690 W KR2005004690 W KR 2005004690W WO 2007078017 A1 WO2007078017 A1 WO 2007078017A1
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Prior art keywords
aragonite
carbon dioxide
manufacture
calcium carbonate
magnesium chloride
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PCT/KR2005/004690
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French (fr)
Inventor
Ji-Whan Ahn
Jeong-Hwan Kim
Sang-Jin Ko
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Korea Institute Of Geoscience And Mineral Resources
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Priority to CA2635233A priority Critical patent/CA2635233C/en
Publication of WO2007078017A1 publication Critical patent/WO2007078017A1/en

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention is to provide methods of manufacture of aragonite-type precipitated calcium carbonate with increased yield and particle size according to the carbonation method.
  • Precipitated calcium carbonate is synthesized according to various methods including the carbonation method in which carbon dioxide is blown into the suspension of calcium hydroxide and reacted, solution process in which the aqueous solution of calcium chloride is reacted with caustic soda and the aqueous solution of sodium carbonate, precipitation method in which the solution of calcium bicarbonate made by blowing carbon dioxide to calcium carbonate is heated and precipitated, etc. Industrially, the method of carbonation is applied.
  • Such precipitated calcium carbonate is an inorganic material which is not readily soluble in pure water, has a proper specific gravity, high whiteness, incombustibility, etc., and is applicable extensively as inorganic filler in various areas of industry such as rubber, paint, plastic, paper, cosmetics, toothpaste, etc.
  • calcite which is stable at a room temperature is cubic or spindle shaped
  • aragonite which is meta-stable is navicular or needle shaped
  • unstable vaterite is spherical mostly.
  • aragonite-type sedimentary calcium carbonate is expected to be a new functional inorganic material that can grant mechanical functionality and optical functionality in that it is of needle shape having a very large aspect ratio (the ratio of length with respect to size of a crystal), and it is possible not only to increase strength but also to improve whiteness and to control opaqueness owing to the complicated surface structure of a needle shape when it is used as a filler for rubbers, plastics, or coating materials, or as an industrial raw material for the pigments for paper, etc.
  • the needle-shaped aragonite having the appearance of 0.05- ⁇ m fine hair is expected to have an affect of increasing its strength if it is mixed with a conformation control thermoplastic resin or polypropylene resin as a filler in that the absorptivity may be increased as the specific surface area is increased, and the needle shape having a length of 50 ⁇ 60 ⁇ m has a superior impact resistance.
  • aragonite has been a meta-stable phase which has existed stably in the temperature region below 75K, and therefore, it has been difficult to synthesize it, especially when it has a large particle size, as the rate of transition of thermodynamically more stable calcite has been fast.
  • the present invention is devised in order to solve the above- described problems.
  • the inventors of the present invention found out that it was possible to increase the particle size of aragonite-type precipitated calcium carbonate and to manufacture 100%-pure single-phase aragonite-type precipitated calcium carbonate by making aragonite-type calcium carbonate seeds in the slurry form firstly, and performing the carbonation reaction repeatedly and continuously by using the above seeds when synthesizing sedimentary calcium carbonate according to the carbonation reaction, and that it was possible to provide new methods of manufacture of aragonite- type calcium carbonate in which the aspect ratio was controlled.
  • the present invention is illustrated in more detail below:
  • the present invention is devised from the findings that, in the method of manufacture of aragonite according to the carbonation process, it is possible to control the particle size and aspect ratio in that aragonite having a very large particle size may be obtained by repeating the carbonation reaction, and it is possible to manufacture practically 100%- pure single-phase aragonite.
  • the present invention provides methods of manufacture of new aragonite-type sedimentary calcium carbonate having a practically 100% purity, large particle size, and increased aspect ratio comprising the steps of: making aragonite-type sedimentary calcium carbonate seeds by using calcium hydroxide, magnesium chloride, and carbon dioxide; growing the seeds by having calcium hydroxide, magnesium chloride, and lowly concentrated carbon dioxide come in contact with the slurry containing the above seeds at a flow rate of 70 ml/min; and repeating the above step of growing the seeds more than once .
  • Aragonite manufactured according to the method of manufacture of the present invention in the form of a calcium carbonate slurry containing seeds shows 100% yield as a result of analysis using XRD, and it is seen that aragonite having an average particle diameter of about 40 ⁇ 50 im is manufactured as the particle size is increased nearly twice if the above carbonation reaction is repeated more than twice as a result of measuring SEM images.
  • the present invention is characterized by injecting carbon dioxide to the above seeds at a low flow rate, and by the method of manufacture of aragonite with increased average particle diameter as well as aspect ratio by repeating the carbonation reaction more than twice.
  • the present invention is comprised of the steps of: a) manufacturing aragonite seeds by mixing 0.2 ⁇ 0.6 M suspension of calcium hydroxide and 0.4 ⁇ 0.8 M magnesium chloride, and inserting carbon dioxide at a flow rate of 100 ml/minute while mixing at 60 ⁇ 90 ° C inserting b) manufacturing aragonite-type precipitated calcium carbonate by mixing and inputting 0.2 ⁇ 0.6 M calcium hydroxide and 0.4
  • the method of manufacture of aragonite is further comprised of the step of washing, filtering, and drying after the above step c) . It is preferable to use ethyl alcohol during the processes of washing and filtering, and to progress the process of drying at 60 ⁇ 90°Cfor 10 ⁇ 15 hours.
  • carbon dioxide in the above step b) is inserted at a flow rate of 10 ⁇ 70 ffl ⁇ /minute, more preferably, at a flow rate of 50 m.£/minute, in order to increase the particle size as well as aspect ratio by reducing the rate of production of the initial nucleus.
  • the particle size of aragonite manufactured is affected by the rate of flow-in of the above carbon dioxide, and it is shown that the best results are obtained when carbon dioxide is inputted at a flow rate in the range of 10 ⁇ 70 md/minute . Moreover, if carbon dioxide is passed at a flow rate in the above range, remarkable effects of manufacturing practically 100%-pure single-phase aragonite are obtained.
  • the reason for limiting the contents of magnesium chloride and calcium hydroxide in the present invention is that the yield of aragonite is most superior when they are within the above ranges.
  • Figure 1 is a flow chart showing the processes of manufacture of aragonite according to the present invention.
  • seeds are manufactured in the step of the first carbonation reaction
  • the second carbonation reaction is progressed by inputting calcium hydroxide and magnesium chloride and passing lowly concentrated (low-rate) carbon dioxide, terminating the reaction by performing the same reaction once more under the same conditions as those of the second carbonation reaction, filtering, washing, drying, and analyzing.
  • Figure 1 is a flow chart showing the processes of manufacture of aragonite according to the present invention
  • Figure 2 is a graph showing the XRD data of pure single-phase aragonite according to Preferred Embodiment 1 of the present invention
  • Figure 3 shows two photographs to compare the sizes of seeds and particles after the second growth according to Preferred Embodiment 2 of the present invention.
  • Figure 4 is a graph showing the sizes and shapes of particles according to the flow rate of carbon dioxide during the growth reaction.
  • the seeds of aragonite-type precipitated calcium carbonate were manufactured by adding 0.8 M magnesium chloride (Junsei Company) to 0.4 M suspension of calcium hydroxide (Sigma Company) in a 1.5-liter reactor, inserting carbon dioxide to the mixture at a flow rate of 100 mi/minute, and reacting the mixture at 80 ° Cfor 2 hours.
  • the seeds of aragonite-type sedimentary calcium carbonate were manufactured by adding again 0.4 M suspension of calcium hydroxide and 0.8 M magnesium chloride (Junsei Company) to the above seed slurry, inserting carbon dioxide to the mixture at a flow rate of 50 m£/minute, and reacting the mixture at 80 °C for 2 hours.
  • [Preferred Embodiment 2] Manufacture of the seeds of aragonite-type precipitated calcium carbonate
  • the seeds of aragonite-type precipitated calcium carbonate were manufactured by adding 0.8 M magnesium chloride (Junsei Company) to 0.4 M suspension of calcium hydroxide (Sigma Company) in a 1.5-liter reactor, inputting carbon dioxide to the mixture at a flow rate of 100 m ⁇ /minute, and reacting the mixture at 80 ° C for 2 hours.
  • the seeds of aragonite-type sedimentary calcium carbonate were manufactured by adding again 0.4 M suspension of calcium hydroxide and 0.8 M magnesium chloride (Junsei Company) to the above seed slurry, inserting carbon dioxide to the mixture at a flow rate of 50 ml/minute, and reacting the mixture at 80 °C for 2 hours.
  • the seeds of aragonite-type precipitated calcium carbonate were manufactured by adding 0.4 M suspension of calcium hydroxide and 0.8 M magnesium chloride (Junsei).
  • Aragonite was manufactured in the same method as that in
  • Preferred Embodiment 1 except that carbon dioxide was inputted at flow rates of 100 m ⁇ /minute and 500 m£/minute in the primary growth reaction and the secondary growth reaction, respectively. As seen in Figure 4, no definite aragonite-type needle-shaped crystals were formed, and crystals were not formed readily and the particle size was reduced as the flow rate of carbon dioxide was increased.

Abstract

The present invention is related to the methods of manufacture of aragonite in the carbonation method, in which the particle size and aspect ratio may be controlled and practically 100%-pure and single-phase aragonite may be obtained by repeating the carbonation reaction.

Description

NOVEL MANUFACTURING METHOD OF ARAGONITE CALCIUM CARBONATE
[Technical Field]
The present invention is to provide methods of manufacture of aragonite-type precipitated calcium carbonate with increased yield and particle size according to the carbonation method.
[Background Art] Precipitated calcium carbonate is synthesized according to various methods including the carbonation method in which carbon dioxide is blown into the suspension of calcium hydroxide and reacted, solution process in which the aqueous solution of calcium chloride is reacted with caustic soda and the aqueous solution of sodium carbonate, precipitation method in which the solution of calcium bicarbonate made by blowing carbon dioxide to calcium carbonate is heated and precipitated, etc. Industrially, the method of carbonation is applied.
Such precipitated calcium carbonate is an inorganic material which is not readily soluble in pure water, has a proper specific gravity, high whiteness, incombustibility, etc., and is applicable extensively as inorganic filler in various areas of industry such as rubber, paint, plastic, paper, cosmetics, toothpaste, etc. There are three representative polymorphs of calcium carbonate: calcite which is stable at a room temperature is cubic or spindle shaped; aragonite which is meta-stable is navicular or needle shaped; and unstable vaterite is spherical mostly. Particularly, aragonite-type sedimentary calcium carbonate is expected to be a new functional inorganic material that can grant mechanical functionality and optical functionality in that it is of needle shape having a very large aspect ratio (the ratio of length with respect to size of a crystal), and it is possible not only to increase strength but also to improve whiteness and to control opaqueness owing to the complicated surface structure of a needle shape when it is used as a filler for rubbers, plastics, or coating materials, or as an industrial raw material for the pigments for paper, etc.
Further, the needle-shaped aragonite having the appearance of 0.05-μm fine hair is expected to have an affect of increasing its strength if it is mixed with a conformation control thermoplastic resin or polypropylene resin as a filler in that the absorptivity may be increased as the specific surface area is increased, and the needle shape having a length of 50 ~ 60 μm has a superior impact resistance. However, it has been known that aragonite has been a meta-stable phase which has existed stably in the temperature region below 75K, and therefore, it has been difficult to synthesize it, especially when it has a large particle size, as the rate of transition of thermodynamically more stable calcite has been fast.
[Disclosure]
[Technical Problem]
The present invention is devised in order to solve the above- described problems. As a result of repeating studies to improve the yield of aragonite according to the carbonation reaction, the inventors of the present invention found out that it was possible to increase the particle size of aragonite-type precipitated calcium carbonate and to manufacture 100%-pure single-phase aragonite-type precipitated calcium carbonate by making aragonite-type calcium carbonate seeds in the slurry form firstly, and performing the carbonation reaction repeatedly and continuously by using the above seeds when synthesizing sedimentary calcium carbonate according to the carbonation reaction, and that it was possible to provide new methods of manufacture of aragonite- type calcium carbonate in which the aspect ratio was controlled.
It is another object of the present invention to provide methods of manufacture of 100% aragonite by making seeds according to the methods of manufacture of the present invention and controlling the particle size and aspect ratio by adding the carbonation reaction by using the above seeds.
[Technical Solution]
The present invention is illustrated in more detail below: The present invention is devised from the findings that, in the method of manufacture of aragonite according to the carbonation process, it is possible to control the particle size and aspect ratio in that aragonite having a very large particle size may be obtained by repeating the carbonation reaction, and it is possible to manufacture practically 100%- pure single-phase aragonite.
In other words, the present invention provides methods of manufacture of new aragonite-type sedimentary calcium carbonate having a practically 100% purity, large particle size, and increased aspect ratio comprising the steps of: making aragonite-type sedimentary calcium carbonate seeds by using calcium hydroxide, magnesium chloride, and carbon dioxide; growing the seeds by having calcium hydroxide, magnesium chloride, and lowly concentrated carbon dioxide come in contact with the slurry containing the above seeds at a flow rate of 70 ml/min; and repeating the above step of growing the seeds more than once . Aragonite manufactured according to the method of manufacture of the present invention in the form of a calcium carbonate slurry containing seeds shows 100% yield as a result of analysis using XRD, and it is seen that aragonite having an average particle diameter of about 40 ~ 50 im is manufactured as the particle size is increased nearly twice if the above carbonation reaction is repeated more than twice as a result of measuring SEM images.
Accordingly, the present invention is characterized by injecting carbon dioxide to the above seeds at a low flow rate, and by the method of manufacture of aragonite with increased average particle diameter as well as aspect ratio by repeating the carbonation reaction more than twice.
More concretely, in the method of manufacture of aragonite according to the carbonation reaction by using the suspension of calcium hydroxide, magnesium chloride, and carbon dioxide, the present invention is comprised of the steps of: a) manufacturing aragonite seeds by mixing 0.2 ~ 0.6 M suspension of calcium hydroxide and 0.4 ~ 0.8 M magnesium chloride, and inserting carbon dioxide at a flow rate of 100 ml/minute while mixing at 60 ~ 90 °C inserting b) manufacturing aragonite-type precipitated calcium carbonate by mixing and inputting 0.2 ~ 0.6 M calcium hydroxide and 0.4
~ 0.8 M magnesium chloride while supplying continuously carbon dioxide to the seeds manufactured in the above, and inputting lowly concentrated carbon dioxide at 60 ~ 90 "Cat a flow rate of 10 ~ 70 ml/minute; and c) manufacturing aragonite-type sedimentary calcium carbonate by repeating the above step b) more than once. In the present invention, the method of manufacture of aragonite is further comprised of the step of washing, filtering, and drying after the above step c) . It is preferable to use ethyl alcohol during the processes of washing and filtering, and to progress the process of drying at 60 ~ 90°Cfor 10 ~ 15 hours.
In the present invention, it is preferable that carbon dioxide in the above step b) is inserted at a flow rate of 10 ~ 70 ffl^/minute, more preferably, at a flow rate of 50 m.£/minute, in order to increase the particle size as well as aspect ratio by reducing the rate of production of the initial nucleus.
Accordingly, in the present invention, the particle size of aragonite manufactured is affected by the rate of flow-in of the above carbon dioxide, and it is shown that the best results are obtained when carbon dioxide is inputted at a flow rate in the range of 10 ~ 70 md/minute . Moreover, if carbon dioxide is passed at a flow rate in the above range, remarkable effects of manufacturing practically 100%-pure single-phase aragonite are obtained. The reason for limiting the contents of magnesium chloride and calcium hydroxide in the present invention is that the yield of aragonite is most superior when they are within the above ranges.
Figure 1 is a flow chart showing the processes of manufacture of aragonite according to the present invention. According to the method of manufacture of aragonite shown in Figure 1 of the present invention, seeds are manufactured in the step of the first carbonation reaction, the second carbonation reaction is progressed by inputting calcium hydroxide and magnesium chloride and passing lowly concentrated (low-rate) carbon dioxide, terminating the reaction by performing the same reaction once more under the same conditions as those of the second carbonation reaction, filtering, washing, drying, and analyzing.
[Brief Description of the Drawings] A more complete appreciation of this invention, and many of the attendant advantages thereof, will be readily apparent as the same becomes better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings, wherein: Figure 1 is a flow chart showing the processes of manufacture of aragonite according to the present invention; Figure 2 is a graph showing the XRD data of pure single-phase aragonite according to Preferred Embodiment 1 of the present invention; Figure 3 shows two photographs to compare the sizes of seeds and particles after the second growth according to Preferred Embodiment 2 of the present invention; and
Figure 4 is a graph showing the sizes and shapes of particles according to the flow rate of carbon dioxide during the growth reaction.
[Description of Preferred Embodiments of the Invention]
The present invention is illustrated in terms of a few preferred embodiments below:
[Preferred Embodiment 1]
Manufacture of the seeds of aragonite-type sedimentary calcium carbonate The seeds of aragonite-type precipitated calcium carbonate were manufactured by adding 0.8 M magnesium chloride (Junsei Company) to 0.4 M suspension of calcium hydroxide (Sigma Company) in a 1.5-liter reactor, inserting carbon dioxide to the mixture at a flow rate of 100 mi/minute, and reacting the mixture at 80°Cfor 2 hours.
Primary aragonite growth reaction
The seeds of aragonite-type sedimentary calcium carbonate were manufactured by adding again 0.4 M suspension of calcium hydroxide and 0.8 M magnesium chloride (Junsei Company) to the above seed slurry, inserting carbon dioxide to the mixture at a flow rate of 50 m£/minute, and reacting the mixture at 80 °C for 2 hours.
As a result of diffraction analysis using XRD, it was found that thus manufactured aragonite was of needle shape, and all components produced according to the reaction time, except for a minute amount of aragonite formed as aragonite came in contact with air in the early stage, were obtained in the form of 100%-pure single-phase aragonite. That is, as shown in Figure 2, it was seen that it was possible to manufacture very superior and practically 100%-pure aragonite- type precipitated calcium carbonate by reducing the content of carbon dioxide in the primary growth reaction since the content of calcite (C component) produced as an impurity of aragonite produced during the process of polymerization of the seeds was not at all increased as a result of the reaction by flowing lowly concentrated carbon dioxide at a flow rate of 50 ml/minute. It was, therefore, seen that it was very critical to use a small amount of carbon dioxide in order to manufacture pure aragonite-type calcium carbonate since it was seen that the content of calcite was increased somewhat when carbon dioxide was flowed in at a flow rate of 100 ml/minute during the primary growth reaction.
[Preferred Embodiment 2] Manufacture of the seeds of aragonite-type precipitated calcium carbonate The seeds of aragonite-type precipitated calcium carbonate were manufactured by adding 0.8 M magnesium chloride (Junsei Company) to 0.4 M suspension of calcium hydroxide (Sigma Company) in a 1.5-liter reactor, inputting carbon dioxide to the mixture at a flow rate of 100 m^/minute, and reacting the mixture at 80 °C for 2 hours.
Primary aragonite growth reaction The seeds of aragonite-type sedimentary calcium carbonate were manufactured by adding again 0.4 M suspension of calcium hydroxide and 0.8 M magnesium chloride (Junsei Company) to the above seed slurry, inserting carbon dioxide to the mixture at a flow rate of 50 ml/minute, and reacting the mixture at 80 °C for 2 hours.
Secondary aragonite growth reaction
The seeds of aragonite-type precipitated calcium carbonate were manufactured by adding 0.4 M suspension of calcium hydroxide and 0.8 M magnesium chloride (Junsei
Company) to the aragonite slurry obtained in the above primary growth reaction, inserting carbon dioxide to the mixture at a flow rate of 50 m£/minute, and reacting the mixture at 80°Cfor
2 hours. As seen in Figure 3, it was seen that aragonite manufactured according to the present invention by using seeds had very large particle size as well as aspect ratio during the growth reaction after the seed reaction compared to aragonite obtained through the secondary reaction without using seeds, as a result of observation of their SEM images.
[Comparative Examples 1 and 2]
Aragonite was manufactured in the same method as that in
Preferred Embodiment 1 except that carbon dioxide was inputted at flow rates of 100 m^/minute and 500 m£/minute in the primary growth reaction and the secondary growth reaction, respectively. As seen in Figure 4, no definite aragonite-type needle-shaped crystals were formed, and crystals were not formed readily and the particle size was reduced as the flow rate of carbon dioxide was increased.
[industrial Applicability]
Therefore, it is seen that based on findings that it is possible to manufacture needle-shaped practically single-phase 100%-pure aragonite-type sedimentary calcium carbonate by performing repeatedly a multiple number of growth reaction for growing particles along with the seed reaction as in the present invention, it is possible to manufacture particulate aragonite-type precipitated calcium carbonate having more diversified, economical, and wide application areas by applying the methods of manufacture according to the present invention.
While certain present preferred embodiments of the invention have been shown and described, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously embodied and practiced within the scope of the following claims.

Claims

[What is claimed is:]
1. A method of manufacture of aragonite according to the carbonation reaction to control the particle size and aspect ratio by using the suspension of calcium hydroxide, magnesium chloride, and carbon dioxide comprising the steps of: a) making an aragonite seed slurry by inputting carbon dioxide after mixing said suspension of calcium hydroxide and said magnesium chloride; b) growing particles of aragonite through the continuous carbonation reaction of carbon dioxide after mixing said suspension of calcium hydroxide and said magnesium chloride with said aragonite seed slurry; and c) growing said particles of aragonite further by repeating said step of b) growing particles of aragonite more than once .
2. The method of manufacture of aragonite in Claim 1, characterized by that said aragonite seed slurry is mixed with 0.2 - 0.6 M of said suspension of calcium hydroxide and 0.4 ~ 0.8 M of said magnesium chloride, and the mixture is reacted with carbon dioxide while mixing at 60 ~ 90 °C
3. The method of manufacture of aragonite in Claim 2, characterized by that said carbon dioxide is inputted at a flow rate of 10 ~ 70 ml/minute with respect to the contents of said suspension of calcium hydroxide and said magnesium chloride in said step of growing said particles.
4. The method of manufacture of aragonite in any of Claims 1 through 3, further comprising the step of washing, filtering, and drying said particles of aragonite.
5. The method of manufacture of aragonite in Claim 3, characterized by that said carbon dioxide is inserted at a flow rate of 50 ml/minute.
PCT/KR2005/004690 2005-12-31 2005-12-31 Novel manufacturing method of aragonite calcium carbonate WO2007078017A1 (en)

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CN114212814A (en) * 2021-12-16 2022-03-22 浙江大学 Preparation method of nano calcium carbonate
WO2022220673A1 (en) * 2021-04-16 2022-10-20 Petroliam Nasional Berhad (Petronas) System and process for producing aragonite
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018877A (en) * 1974-02-14 1977-04-19 Imperial Chemical Industries Limited Production of calcium carbonate
US6221146B1 (en) * 1998-04-03 2001-04-24 Imerys Pigments, Inc. Method for the production of precipitated calcium carbonate having a selected crystal form, products produced thereby and their uses
WO2004035476A1 (en) * 2002-10-15 2004-04-29 Maruo Calcium Company Limited Agglomerate and resin composition containing the same
KR20040087063A (en) * 2003-04-04 2004-10-13 한국지질자원연구원 Preparation of Aragonite from Calcium Hydroxide Suspensions by Homogeneous Precipitation
US20040234443A1 (en) * 2001-12-31 2004-11-25 Jianfeng Chen Calcium carbonate of different shapes and the preparation process thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018877A (en) * 1974-02-14 1977-04-19 Imperial Chemical Industries Limited Production of calcium carbonate
US6221146B1 (en) * 1998-04-03 2001-04-24 Imerys Pigments, Inc. Method for the production of precipitated calcium carbonate having a selected crystal form, products produced thereby and their uses
US20040234443A1 (en) * 2001-12-31 2004-11-25 Jianfeng Chen Calcium carbonate of different shapes and the preparation process thereof
WO2004035476A1 (en) * 2002-10-15 2004-04-29 Maruo Calcium Company Limited Agglomerate and resin composition containing the same
KR20040087063A (en) * 2003-04-04 2004-10-13 한국지질자원연구원 Preparation of Aragonite from Calcium Hydroxide Suspensions by Homogeneous Precipitation

Cited By (8)

* Cited by examiner, † Cited by third party
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US11498029B2 (en) 2015-02-23 2022-11-15 Carbonfree Chemicals Holdings, Llc Carbon dioxide sequestration with magnesium hydroxide and regeneration of magnesium hydroxide
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WO2022220673A1 (en) * 2021-04-16 2022-10-20 Petroliam Nasional Berhad (Petronas) System and process for producing aragonite
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