JPS6177622A - Forming method of amorphous or crystalline calcium carbonate such as vaterite - Google Patents
Forming method of amorphous or crystalline calcium carbonate such as vateriteInfo
- Publication number
- JPS6177622A JPS6177622A JP20004284A JP20004284A JPS6177622A JP S6177622 A JPS6177622 A JP S6177622A JP 20004284 A JP20004284 A JP 20004284A JP 20004284 A JP20004284 A JP 20004284A JP S6177622 A JPS6177622 A JP S6177622A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- amorphous
- vaterite
- crystalline calcium
- water
- 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.)
- Pending
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
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- 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
- C01F11/184—Preparation of calcium carbonate by carbonation of solutions based on non-aqueous solvents
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
Description
【発明の詳細な説明】
産業上の利用分野゛
本発明は非晶質又はバテライト等の結晶質炭酸カルシウ
ムの生成方法に関するものである０
従来技術
一般に炭酸カルシウムには結晶系によって次の３つの型
がある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing crystalline calcium carbonate such as amorphous or vaterite.0 Prior Art Generally, calcium carbonate has the following three types depending on its crystal system. There is.
（１）バテライト （Ｖａｔａｒｉｔｅ ）（２）アラ
ゴナイト （Ａｒａｇｏｎｉｔｅ ）（３）カルサイト
（０ａｌｃｉｔｅ ）このほかに結晶していない、す
なわち非結晶質炭酸カルシウム（アモルファス炭酸カル
シウムとも言う。）がある。(1) Vatarite (2) Aragonite (3) Calcite (0alcite) In addition to these, there is also non-crystalline calcium carbonate (also called amorphous calcium carbonate).
自然界に於ける安定性はカルサイトが圧倒的に大きく、
アラブナイトは小さい。 バテライト、非晶質炭酸カル
シウムは不安定なので天然に産しない。 その中でも非
晶質炭酸カルシウムは特に不安定なのでそれを生成させ
取り出し、存在させるのにかなりの技術を要する。Calcite has overwhelmingly high stability in the natural world.
The Arab Nights are small. Vaterite, amorphous calcium carbonate, is unstable and does not occur naturally. Among these, amorphous calcium carbonate is particularly unstable and requires considerable technology to generate, extract, and bring into existence.
しかし、性質面でバテライトや非晶質炭酸カルシウムは
種々の特徴をもつ。 それは大きな溶解度、大きな比表
面積、小さな比重、などなどである。 その特徴を生か
す事によって食品工業、セラミック工業、ゴム工業、紙
工業、電子工業及び医薬品工業などに従来のカルサイト
、アラブナイトでは対応出来ない分野の用途開発が期待
される。However, vaterite and amorphous calcium carbonate have various characteristics in terms of properties. It has large solubility, large specific surface area, small specific gravity, etc. By taking advantage of its characteristics, it is expected that it will be used in fields that conventional calcite and arabite cannot be used in, such as the food industry, ceramic industry, rubber industry, paper industry, electronic industry, and pharmaceutical industry.
又実際の工業界での炭酸カルシウムは石灰石゛を機械的
に微粉砕した重質炭酸カルシウムと化学的沈降法により
生成される沈降炭酸カルシウムに大別される。 さらに
沈降炭酸カルシウムを分類すると粒子径１〜３μ位の軽
質炭酸カルシウムと粒子径０．０２〜０．１μ位のコロ
イド性炭酸カルシウムになる。 現在日本の市場には重
質炭酸カルシウム、沈降炭酸カルシウムはあるが、カル
サイトが主体で、アジゴナイトの純粋なものはまだまだ
開発が遅れているようだ０
従来の沈降炭酸カルシウムの製法を大別すると次のよう
である。In actual industry, calcium carbonate is roughly divided into heavy calcium carbonate, which is produced by mechanically pulverizing limestone, and precipitated calcium carbonate, which is produced by chemical precipitation. Further, precipitated calcium carbonate is classified into light calcium carbonate with a particle size of about 1 to 3 μm and colloidal calcium carbonate with a particle size of about 0.02 to 0.1 μm. Currently, there are heavy calcium carbonate and precipitated calcium carbonate on the Japanese market, but the main ingredient is calcite, and the development of pure azigonite seems to be lagging behind.The conventional production methods for precipitated calcium carbonate can be roughly divided into It is as follows.
（１）塩化カルシウムと炭酸ソーダ溶液から作る方法
０ａＯ１，＋ ＮＪＬ！ ００． ＝ ２Ｎａｏ１＋
０ａＯＯ。(1) Method of making from calcium chloride and soda carbonate solution 0aO1, + NJL! 00. = 2Nao1+
0aOO.
（２）水酸化カルシウムと炭酸ソーダの反応によって作
る方法
Ｏａ （ＯＨ）！ ＋ Ｈａ、 ００ｇ ＝ ２ＮａＯ
Ｈ＋ ０ａＯ０３（３）水酸化カルシウムと炭酸ガスと
の反応によって作る方法
Ｏａ （ＣＩＨ）１ ＋ ００１ ＝Ｈｚ Ｏ＋ ０
ａＧＯ３しかし、日本で工業的に行なわれているのは（
３）の方法がほとんどである。 すなわち、消石灰スラ
リーに石灰焼成炉からＣＯ２を含む排ガスを除塵して吹
込み反応させて炭酸カルシウムを作る方法である。(2) Method of making Oa (OH) by reaction of calcium hydroxide and soda carbonate! + Ha, 00g = 2NaO
H+ 0aO03 (3) Method of making by reaction of calcium hydroxide and carbon dioxide Oa (CIH)1 + 001 =Hz O+ 0
aGO3However, what is being done industrially in Japan is (
Method 3) is the most common method. That is, this is a method of producing calcium carbonate by blowing CO2-containing exhaust gas from a lime kiln into slaked lime slurry after removing dust and causing a reaction.
発明が解決しようとする問題点
以上のような消石灰スラリーに石灰焼成炉からのａＯｔ
を含む排ガスを除塵して吹込み反応させて作った炭酸カ
ルシウムはカルサイト系かカルサイトにアジゴナイトが
混在する系が大部分であり、バテライト系や非晶質系が
出来てもそれをコントロールして存続させ、単体として
取り出すことは至難の技であるといわれる。Problems to be solved by the invention
Calcium carbonate, which is made by removing dust from exhaust gas containing carbon dioxide and injecting it into a reaction, is mostly calcite-based or a mixture of calcite and azigonite, and even if vaterite-based or amorphous systems are formed, it is necessary to control them. It is said that it is extremely difficult to keep it alive and extract it as a single entity.
従来法のコロイド性炭酸カルシウムが生成する条件下で
は、反応初期に導電率曲線に大きな下降が見られ、この
降下過程で生成する炭酸カルシウムは微小な非晶質炭酸
カルシウムであるといわれる。 しかし水酸化カルシウ
ム−水系ではこの生成した非晶質炭酸カルシウムがさま
ざまな生成条件によって結晶化し、結晶成長し、種々の
結晶状態と粒径の炭酸カルシウムになり、それら種々形
態での保持やコントロールが非常にむずかしく、単体の
取出しが困難である。Under the conditions in which colloidal calcium carbonate is produced in the conventional method, a large drop in the conductivity curve is observed in the early stage of the reaction, and the calcium carbonate produced during this descending process is said to be minute amorphous calcium carbonate. However, in a calcium hydroxide-water system, the amorphous calcium carbonate that is produced crystallizes and grows depending on various formation conditions, resulting in calcium carbonate with various crystalline states and particle sizes, and it is difficult to maintain and control these various forms. It is extremely difficult to take out a single unit.
一本頁以下崇白次頁に続く−
問題点を解決するための手段
したがって本発明の技術的課題は非晶質炭酸カルシウム
又はパテティトでもかなり純粋に近い状態で生成させ単
体として簡単に取り出し安定化できる非晶質又はバテラ
イト等の結晶質炭酸カルシウムの生成方法を提供しよう
とするものである。 この技術的課題を解決する本発明
の枝体的手段は水酸化カルシウム−水−アルコール類の
懸濁液系に００２を含むガスを吹き込んで非晶質又はバ
テライト等の結晶質炭酸カルシウムを生成させることを
特徴とするものである。The technical problem of the present invention is to produce amorphous calcium carbonate or putty in a fairly pure state and to easily take it out and stabilize it as a single substance. The present invention aims to provide a method for producing amorphous or crystalline calcium carbonate such as vaterite. A branch of the present invention to solve this technical problem is to generate amorphous or crystalline calcium carbonate such as vaterite by blowing a gas containing 002 into a calcium hydroxide-water-alcohol suspension system. It is characterized by this.
発明の効果
本発明によれば水酸化カルシウムの溶媒として水のほか
に性質面（表面張力、ＣＯ，の溶解度、比重、融点、沸
点）で異なるアルコール類例えばメタノールを用いて○
ｏ２ を含むガスを導入したから結晶化をコントロール
でき、場合によっては非晶炭酸カルシウムだけに保持し
ておくことができる
本発明の炭酸カルシウムは沈降炭酸カルシウムに属する
が、結晶系はバテライト、アラブナイト、カルサイトの
選択が自由に出来、さらには非晶質炭酸カルシウムにす
ることも出来る〇又、最初に非晶質炭酸カルシウムを生
成させ、それから特殊処理により、バテライト、アラブ
ナイト、カルサイトに転移させることも出来る。Effects of the Invention According to the present invention, in addition to water, alcohols having different properties (surface tension, solubility of CO, specific gravity, melting point, boiling point), such as methanol, are used as a solvent for calcium hydroxide.
Since the gas containing O2 is introduced, crystallization can be controlled, and in some cases it can be retained only in amorphous calcium carbonate.The calcium carbonate of the present invention belongs to precipitated calcium carbonate, but the crystal system is vaterite, arabite, etc. , Calcite can be freely selected, and even amorphous calcium carbonate can be made.Also, amorphous calcium carbonate is first generated, and then through special treatment, it is transformed into vaterite, arabite, and calcite. You can also do it.
そして非晶質炭酸カルシウム、又はバテライトででも、
かなり純粋に近い状態で生成させ取り出せる画期的なも
のである。 周知の通り非晶質炭酸カルシウム、バテラ
イト、あるいはアラブナイトだけを混り気なく生成し、
取り出すことはかなりの技術を要するが、本発明の方法
によれば容易にかなりに近い純粋のものを生成し、取り
出すことが出来る。And even with amorphous calcium carbonate or vaterite,
It is an epoch-making product that can be produced and extracted in a state that is close to pure. As is well known, only amorphous calcium carbonate, vaterite, or arabite is produced without any confusion.
Although taking it out requires considerable skill, according to the method of the present invention, it is possible to easily produce and take out a product that is nearly pure.
何れにしても本発明によれば、非晶質炭酸カルシウムで
も、バテライト等のような結晶質炭酸カルシウムでも容
易にコントロールして生成させることが出来、それを必
要に応じて非晶質からバテライトへ、まなバテライトか
らアラブナイトへというふうに転移させることも出来る
という特徴を有するものである。In any case, according to the present invention, it is possible to easily control and generate both amorphous calcium carbonate and crystalline calcium carbonate such as vaterite, and convert it from amorphous to vaterite as necessary. , it has the characteristic that it can be transferred from Mana Vaterite to Arabite.
実施例り
工業用生石灰：水−１＝ｗ（重量比）の比率で石灰スラ
リーを作る。Ｊ工Ｓ篩で＋１４９μを除去し、−１４９
μのスラリーを約３時間熟成後に脱水して固形分４５％
の消石灰（０＆（ＯＨ）りのペーストを得る。Example: A lime slurry is prepared in a ratio of industrial quicklime:water-1=w (weight ratio). Remove +149μ with J-S sieve, -149
After maturing μ slurry for about 3 hours, it is dehydrated to give a solid content of 45%.
A paste of slaked lime (0 & (OH)) is obtained.
その消石灰ペース） ５０９−を約５００ ｓｌのメタ
ノールに分散させ、液温７Ｃとする。The slaked lime paste) 509- is dispersed in about 500 sl of methanol and the liquid temperature is 7C.
この分散液に００．ガスを３１ ／ ！１ｌｉｎで吹き
込み、化合を完了させ、生成した炭酸カルシウムを真空
ポンプで吸引濾過分離し、デシケータ内で温度をかけず
に乾燥し、供試サンプルとした。00.00 to this dispersion. 31/ gas! The mixture was blown in at 1 liter to complete the combination, and the produced calcium carbonate was separated by suction filtration using a vacuum pump, and dried in a desiccator without applying any temperature to obtain a test sample.
第１図にＸ線回折パターンを、また第９図にＳＫＭ写真
の写を示すが、バテライトが生成し、Ｘ線回折に他の結
晶ピークもな−ので純度も高い事がわかる。 その比表
面積は１５．８ ｔｓｌ／９−であった。The X-ray diffraction pattern is shown in FIG. 1, and the SKM photograph is shown in FIG. 9. It can be seen that vaterite is formed and there are no other crystal peaks in the X-ray diffraction, so the purity is high. Its specific surface area was 15.8 tsl/9-.
以下実施例に使用した原材料について記すと１） 生石
灰：工業ｍａｒ ｘ ｓ符号、比表面積２．７〜４．６
ｍ’／ ｆ
２） 水：井戸水（約７０Ｃに保持して生石灰と反応さ
せる）
３） メタノール；試薬用 １級
４）Ｃｏ、ガスじ工Ｓ第３種 ボンベ品なお比表面積の
測定には
柴田化李器械工業製 迅速表面積測定装置（ＢＩＴ 簡
便法）を使用した。The raw materials used in the examples are described below: 1) Quicklime: industrial mar x s code, specific surface area 2.7 to 4.6
m'/f 2) Water: Well water (maintained at about 70C and reacted with quicklime) 3) Methanol: For reagent grade 1 4) Co, Gasjiko S grade 3 Although it is a cylinder product, Shibata is suitable for measuring the specific surface area. A rapid surface area measuring device (BIT simple method) manufactured by Kairi Kikai Kogyo Co., Ltd. was used.
実施例２
実施例りと同じように石灰スラリーを作り、−１４９μ
のスラリーを約９６時間熟成後に脱水して固形分約５０
％の消石灰ペーストを得る。Example 2 Lime slurry was made in the same manner as in Example 2, and -149μ
After aging the slurry for about 96 hours, it is dehydrated to reduce the solid content to about 50.
Obtain % slaked lime paste.
その消石灰ペース） ５０９−を約１ｊのメタノールに
分散させ液温８Ｃにして、００．ガスを３４ｔ／ｍｉｎ
で吹き込み、化合を完了させ、生成した炭酸カルシウム
を真空ポンプで吸引濾過分離し、デシケータ内で温度を
かけずに乾燥し、供試サンプルとした０
第２図にＸ線回折ノセターンを、また第１０ 、１１図
に８１Ｍ写真の写を示すが、非晶質（アモルファス）で
ある。The slaked lime paste) 509- was dispersed in about 1J of methanol and the liquid temperature was 8C. Gas at 34t/min
The calcium carbonate produced was suction filtered and separated using a vacuum pump, and dried in a desiccator without applying any temperature to prepare a test sample. Figures 10 and 11 show 81M photographs, and it is amorphous.
その比表面積は５ｅ、３ｄ／ｆであった。Its specific surface area was 5e, 3d/f.
上記の非晶質炭酸カルシウムを１００ Ｃ、２時間加熱
したが非晶質に変化はなかった。The above amorphous calcium carbonate was heated at 100 C for 2 hours, but there was no change in the amorphous state.
第３図にｘ１１回線で示す。It is shown in FIG. 3 as an x11 line.
また、生成した非晶質炭酸カルシウムに水を加えて１０
ｏ ｚ 、 ２時間加熱したら、結晶化してカルサイト
に転移した。 第４図にＸ線回線で示す。In addition, by adding water to the amorphous calcium carbonate produced,
After heating for 2 hours, it crystallized and transformed into calcite. Figure 4 shows the X-ray line.
次に生成した非晶質炭醗カルシウムを６００ ＣＩ２時
ａ加熱したら、結晶化してカルサイトに転移した。 そ
の比表面積は非常に小さくなり４．７ｄｌＦとなった。Next, the produced amorphous calcium charcoal was heated at 600 CI 2 hours a, and then crystallized and transformed into calcite. Its specific surface area became extremely small and became 4.7 dlF.
第５図にＸ線回折パターンを示す。Figure 5 shows the X-ray diffraction pattern.
実施例＆
実施例りと同じように石灰スラリーを作り、−１４９μ
のスラリーを°約ａ時間熟成後、脱水して、固形分約５
８％の消石灰ペーストを得る。Example & Make lime slurry in the same manner as in Example, -149μ
After aging the slurry for about a hour, it was dehydrated to reduce the solid content to about 5.
An 8% slaked lime paste is obtained.
込み、化合を完了させる。complete the combination.
今回は生成した炭酸カルシウムを溶媒と真空ポンプで吸
引濾過分離し、デシケータ（あるいけ真空デシケータ）
に入れて温度を上げずに乾燥させたもの（Ａ）と電気乾
燥器にて１００Ｃで乾燥させた（Ｂ）の相違点を調べて
みた。This time, the generated calcium carbonate is separated by suction filtration using a solvent and a vacuum pump, and then placed in a desiccator (Aike vacuum desiccator).
We investigated the differences between (A), which was dried in a dryer without raising the temperature, and (B), which was dried at 100C in an electric dryer.
比表面積二４ Ａ−１２４，５ｍ’／ ７ ｔ Ｂ−７
２，３ｉ／ ｆ／であった。 ＡのＸＩ！回折を第６図
に、Ｂのもの全第７図に示すが、Ａ、Ｂ共に非晶質炭酸
カルシウムである。Specific surface area 24 A-124,5m'/7t B-7
It was 2,3i/f/. A's XI! The diffraction is shown in Figure 6, and the diffraction of B is shown in Figure 7. Both A and B are amorphous calcium carbonate.
実施側番
実施例＆と同じ消石灰ペースト５０？を約１ｊのメタノ
ールに分散させ、液温７ＣにしてＣＯ。The same slaked lime paste as the implementation example & 50? Disperse it in about 1j of methanol, bring the liquid temperature to 7C, and add CO.
ガスを３１７ｍ１ｍで吹き込み、化合を完了させる。Blow in gas at 317ml to complete the combination.
今回は生成した炭酸カルシウムを溶媒から分離する前に
５〜１０ Ｃで約加時間熟成させた後、吸引濾過分離し
て電気乾燥器にて１００Ｃで乾燥した。 比表面積１３
３，６ ｔｒｔ”／９−と大きかった。This time, before separating the produced calcium carbonate from the solvent, it was aged at 5 to 10 C for about an hour, separated by suction filtration, and dried at 100 C in an electric dryer. Specific surface area 13
It was large at 3.6 trt”/9-.
第８図にｘｍ回折パターンを示すが非晶質炭酸カルシウ
ムである。The xm diffraction pattern shown in FIG. 8 is amorphous calcium carbonate.
第１図乃至第８図は、Ｘ線回折パターン図、第９ 、１
ｏ 、 １１図け３１８Ｍ写真の写を示す。
Ｉｓ Ｚ） ２
５第５図
３５ ４Ｑ ４５
植第１０図Figures 1 to 8 are X-ray diffraction pattern diagrams, Figures 9 and 1.
o, Figure 11 shows a copy of the 318M photograph. Is Z) 2
5Figure 5 35 4Q 45
Fig. 10
Claims (1)
テライト等の結晶質炭酸カルシウムを生成させることを
特徴とする非晶質又はバテライト等の結晶質炭酸カルシ
ウムの生成方法。[Claims] Amorphous or crystalline calcium carbonate such as amorphous or vaterite is produced by blowing a gas containing CO_2 into a calcium hydroxide-water-alcohol suspension system. A method for producing crystalline calcium carbonate such as vaterite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20004284A JPS6177622A (en) | 1984-09-25 | 1984-09-25 | Forming method of amorphous or crystalline calcium carbonate such as vaterite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20004284A JPS6177622A (en) | 1984-09-25 | 1984-09-25 | Forming method of amorphous or crystalline calcium carbonate such as vaterite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6177622A true JPS6177622A (en) | 1986-04-21 |
Family
ID=16417859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20004284A Pending JPS6177622A (en) | 1984-09-25 | 1984-09-25 | Forming method of amorphous or crystalline calcium carbonate such as vaterite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6177622A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020082813A (en) * | 2002-09-06 | 2002-10-31 | 한국지질자원연구원 | Treatment process of Amorphous Calcium Carbonate which is made from a carbonation reaction in Ethanol-Ethylene Glycol system |
| US6685908B1 (en) * | 2000-03-06 | 2004-02-03 | 3P Technologies Ltd. | Precipitated aragonite and a process for producing it |
| JP2006193411A (en) * | 2004-12-15 | 2006-07-27 | Fuji Photo Film Co Ltd | Method for producing carbonate |
| JP2007277036A (en) * | 2006-04-05 | 2007-10-25 | Hokkaido Kyodo Sekkai Kk | Vaterite-type spherical calcium carbonate and method for producing the same |
| JP2008280191A (en) * | 2007-05-08 | 2008-11-20 | Yahashi Kogyo Kk | Method for producing silicon-eluting vaterite |
| JP2013060320A (en) * | 2011-09-13 | 2013-04-04 | Concurrent Corp | Method for producing spherical calcium carbonate fine particle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56124368A (en) * | 1980-02-25 | 1981-09-30 | Monsanto Co | Stabilized amorphous calcium carbonate |
-
1984
- 1984-09-25 JP JP20004284A patent/JPS6177622A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56124368A (en) * | 1980-02-25 | 1981-09-30 | Monsanto Co | Stabilized amorphous calcium carbonate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6685908B1 (en) * | 2000-03-06 | 2004-02-03 | 3P Technologies Ltd. | Precipitated aragonite and a process for producing it |
| KR20020082813A (en) * | 2002-09-06 | 2002-10-31 | 한국지질자원연구원 | Treatment process of Amorphous Calcium Carbonate which is made from a carbonation reaction in Ethanol-Ethylene Glycol system |
| JP2006193411A (en) * | 2004-12-15 | 2006-07-27 | Fuji Photo Film Co Ltd | Method for producing carbonate |
| JP2007277036A (en) * | 2006-04-05 | 2007-10-25 | Hokkaido Kyodo Sekkai Kk | Vaterite-type spherical calcium carbonate and method for producing the same |
| JP2008280191A (en) * | 2007-05-08 | 2008-11-20 | Yahashi Kogyo Kk | Method for producing silicon-eluting vaterite |
| JP2013060320A (en) * | 2011-09-13 | 2013-04-04 | Concurrent Corp | Method for producing spherical calcium carbonate fine particle |
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