CA2635233C - Novel manufacturing method of aragonite calcium carbonate - Google Patents
Novel manufacturing method of aragonite calcium carbonate Download PDFInfo
- Publication number
- CA2635233C CA2635233C CA2635233A CA2635233A CA2635233C CA 2635233 C CA2635233 C CA 2635233C CA 2635233 A CA2635233 A CA 2635233A CA 2635233 A CA2635233 A CA 2635233A CA 2635233 C CA2635233 C CA 2635233C
- Authority
- CA
- Canada
- Prior art keywords
- aragonite
- carbon dioxide
- calcium carbonate
- manufacture
- magnesium chloride
- 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.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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
[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
2 PCT/KR2005/004690 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-/_cm 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 gm 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,
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-/_cm 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 gm 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,
3 PCT/KR2005/004690 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
[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
4 PCT/KR2005/004690 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 mt/min; and repeating the above step of growing the seeds more than once.
Aragonite manufactured according to the method of
[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 mt/min; and repeating the above step of growing the seeds more than once.
Aragonite manufactured according to the method of
5 PCT/KR2005/004690 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 /cm 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 ~ 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
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 ~ 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
6 PCT/KR2005/004690 lowly concentrated carbon dioxide at 60 - 90 C at 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 d/minute, more preferably, at a flow rate of 50 mt/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 d/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
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 d/minute, more preferably, at a flow rate of 50 mt/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 d/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
7 PCT/KR2005/004690 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
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
8 PCT/KR2005/004690 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 mk/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
[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 mk/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
9 PCT/KR2005/004690 above seed slurry, inserting carbon dioxide to the mixture at a flow rate of 50 mi/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 mt/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]
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 mt/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]
10 PCT/KR2005/004690 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 0/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 mt/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 0/minute, and reacting the mixture at 80 Cfor 2 hours.
As seen in Figure 3, it was seen that aragonite
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 mt/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 0/minute, and reacting the mixture at 80 Cfor 2 hours.
As seen in Figure 3, it was seen that aragonite
11 PCT/KR2005/004690 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 0/minute and 500 mt/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
[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 0/minute and 500 mt/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
12 PCT/KR2005/004690 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.
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 (4)
1. A method of manufacture of aragonite according to carbonation reaction to increase the particle size and aspect ratio by using a suspension of calcium hydroxide, magnesium chloride, and carbon dioxide, comprising the steps of:
a. mixing said suspension of calcium hydroxide with said magnesium chloride, and performing the carbonation reaction by inputting carbon dioxide to the mixture to make an aragonite seed slurry;
b. mixing said aragonite seed slurry with said suspension of calcium hydroxide and said magnesium chloride, and performing the carbonation reaction by inputting carbon dioxide to the mixture at 60~90°C and low speed of 10~70 ml/min to grow particles of aragonite; and c. repeating step b) once or more to further grow said particles of aragonite, wherein steps a) to b) are continuously performed in one reactor.
a. mixing said suspension of calcium hydroxide with said magnesium chloride, and performing the carbonation reaction by inputting carbon dioxide to the mixture to make an aragonite seed slurry;
b. mixing said aragonite seed slurry with said suspension of calcium hydroxide and said magnesium chloride, and performing the carbonation reaction by inputting carbon dioxide to the mixture at 60~90°C and low speed of 10~70 ml/min to grow particles of aragonite; and c. repeating step b) once or more to further grow said particles of aragonite, wherein steps a) to b) are continuously performed in one reactor.
2. The method of manufacture of aragonite in claim 1, characterized in that in step a), 0.2~0.6 M of said suspension of calcium hydroxide is mixed with 0.4~0.8 M of said magnesium chloride, and the carbonation reaction is performed at 60~90°C.
3. The method of claim 1 or 2, further comprising a step of washing said particles of aragonite of step c) with ethyl alcohol, filtering said particles of aragonite, and drying said particles of aragonite at 60~90°C for 10~15 hours.
4. The method of claim 3, characterized in that in step b), carbon dioxide is added to the mixture at a flow rate of 50 ml/minute.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2005/004690 WO2007078017A1 (en) | 2005-12-31 | 2005-12-31 | Novel manufacturing method of aragonite calcium carbonate |
| KR1020050136204A KR100720865B1 (en) | 2005-12-31 | 2005-12-31 | Novel manufacturing method of aragonite calcium carbonate |
| KR10-2005-0136204 | 2005-12-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2635233A1 CA2635233A1 (en) | 2007-07-12 |
| CA2635233C true CA2635233C (en) | 2012-04-10 |
Family
ID=38228352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2635233A Active CA2635233C (en) | 2005-12-31 | 2005-12-31 | Novel manufacturing method of aragonite calcium carbonate |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100720865B1 (en) |
| CA (1) | CA2635233C (en) |
| WO (1) | WO2007078017A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK2442749T3 (en) | 2009-06-15 | 2019-05-27 | Cartiheal 2009 Ltd | FIXED FORMS OF REPAIR OF TISSUE |
| WO2012006601A2 (en) | 2010-07-08 | 2012-01-12 | Skyonic Corporation | Carbon dioxide sequestrations involving two-salt-based thermolytic processes |
| ES2961349T3 (en) | 2015-02-23 | 2024-03-11 | Carbonfree Chemicals Holdings Llc | Carbon dioxide capture with magnesium hydroxide and magnesium hydroxide regeneration |
| KR101656035B1 (en) * | 2015-04-30 | 2016-09-08 | 한국지질자원연구원 | A method for the synthesis of precipitated calcium carbonate from dolomite kiln dust |
| KR101727985B1 (en) * | 2016-04-29 | 2017-04-18 | 한국지질자원연구원 | Method for synthesis of aragonite |
| KR101727983B1 (en) * | 2016-04-29 | 2017-04-18 | 한국지질자원연구원 | Nano precipitation calcium carbonates |
| CN107916452B (en) * | 2017-11-14 | 2020-03-03 | 浙江大学 | Preparation method of calcium carbonate whiskers with continuously controllable morphology |
| KR102240348B1 (en) * | 2019-06-11 | 2021-04-14 | 한국해양대학교 산학협력단 | A method for producing high purity aragonite calcium carbonate using seawater |
| WO2022220673A1 (en) * | 2021-04-16 | 2022-10-20 | Petroliam Nasional Berhad (Petronas) | System and process for producing aragonite |
| CN113264597A (en) * | 2021-04-22 | 2021-08-17 | 四川绵阳岷山实业集团有限公司 | Method for inhibiting scale by using calcium carbonate aragonite seed crystals |
| CN114212814B (en) * | 2021-12-16 | 2023-08-01 | 浙江大学 | Preparation method of nano calcium carbonate |
| KR102505738B1 (en) * | 2022-09-29 | 2023-03-03 | 김동기 | manufacturing method of filter material using Aragonite adsorbed with organic Germanium |
| JP7382091B1 (en) | 2022-10-07 | 2023-11-16 | 白石工業株式会社 | Calcium carbonate production method, calcium carbonate and paper making filler |
| CN116282997A (en) * | 2023-02-27 | 2023-06-23 | 武汉理工大学 | Calcium carbonate cement, calcium carbonate cement hardened body and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1447566A (en) * | 1974-02-14 | 1976-08-25 | Ici Ltd | Production of calcium carbonate |
| AU3378199A (en) * | 1998-04-03 | 1999-10-25 | Ecc International Inc. | Precipitated calcium carbonate and its production and use |
| AU2002359958A1 (en) * | 2001-12-31 | 2003-07-15 | Beijing University Of Chemical Technology | Calcium carbonate of different shapes and the preparing process thereof |
| US7199173B2 (en) * | 2002-10-15 | 2007-04-03 | Maruo Calcium Company Limited | Agglomerate and resin composition containing the same |
| KR100508437B1 (en) | 2003-04-04 | 2005-08-17 | 한국지질자원연구원 | Preparation of Aragonite from Calcium Hydroxide Suspensions by Homogeneous Precipitation |
-
2005
- 2005-12-31 KR KR1020050136204A patent/KR100720865B1/en active IP Right Grant
- 2005-12-31 CA CA2635233A patent/CA2635233C/en active Active
- 2005-12-31 WO PCT/KR2005/004690 patent/WO2007078017A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CA2635233A1 (en) | 2007-07-12 |
| KR100720865B1 (en) | 2007-05-23 |
| WO2007078017A1 (en) | 2007-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2635233C (en) | Novel manufacturing method of aragonite calcium carbonate | |
| Jimoh et al. | Synthesis of precipitated calcium carbonate: a review | |
| EP2552835B1 (en) | Process for obtaining precipitated calcium carbonate | |
| US5910214A (en) | Process for preparing calcium carbonate | |
| TWI491564B (en) | Process for the production of precipitated calcium carbonate, precipitated calcium carbonate and uses thereof | |
| US5811070A (en) | Process for producing calcium carbonate particles having a size of 0.1 to 1.0 μm | |
| Ramakrishna et al. | A brief review of aragonite precipitated calcium carbonate (PCC) synthesis methods and its applications | |
| US4124688A (en) | Process for preparing cubic crystals of calcium carbonate | |
| EP3209610B1 (en) | Pcc with reduced portlandite content | |
| CA2939418C (en) | Process for producing high grade hydromagnesite and magnesium oxide | |
| KR101078602B1 (en) | Manufacturing method of calcite | |
| Altiner et al. | Ultrasonic-assisted production of precipitated calcium carbonate particles from desulfurization gypsum | |
| KR101727983B1 (en) | Nano precipitation calcium carbonates | |
| JPS6411571B2 (en) | ||
| JP2001270713A (en) | Method for producing calcium carbonate having aragonite crystal system | |
| JP2002234725A (en) | Method for producing calcium carbonate of aragonite crystal system | |
| KR100508437B1 (en) | Preparation of Aragonite from Calcium Hydroxide Suspensions by Homogeneous Precipitation | |
| JPS63260815A (en) | Production of calcium carbonate having aragonite crystal form | |
| KR101656035B1 (en) | A method for the synthesis of precipitated calcium carbonate from dolomite kiln dust | |
| Ryu et al. | Synthesis of calcium carbonate in ethanol-ethylene glycol solvent | |
| KR20240077663A (en) | Calcium carbonate having candy type crystal structure and preparing method the same | |
| AU768281B2 (en) | Process for producing calcium carbonate | |
| JPH05221634A (en) | Production of cubic calcium carbonate | |
| JP2009173794A (en) | Resin-calcium carbonate composite particles, emulsion liquid containing resin emulsion-calcium carbonate composite particles and method for producing the emulsion liquid | |
| OA18676A (en) | PCC with reduced portlandite content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |