JPH0319166B2 - - Google Patents
Info
- Publication number
- JPH0319166B2 JPH0319166B2 JP61120412A JP12041286A JPH0319166B2 JP H0319166 B2 JPH0319166 B2 JP H0319166B2 JP 61120412 A JP61120412 A JP 61120412A JP 12041286 A JP12041286 A JP 12041286A JP H0319166 B2 JPH0319166 B2 JP H0319166B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- calcium
- carbon dioxide
- sample
- acicular
- 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.)
- Expired - Lifetime
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
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)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は種々の産業分野において充填剤、補強
剤等として多く使用されている炭酸カルシウム、
とくに針状粒子炭酸カルシウムの生成方法に関す
るものである。Detailed Description of the Invention (Industrial Application Field) The present invention is directed to calcium carbonate, which is widely used as a filler, reinforcing agent, etc. in various industrial fields.
In particular, it relates to a method for producing acicular particle calcium carbonate.
（従来技術）
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。重質炭酸カルシウムの粒子は不定形で、
粒子径は数μｍ〜150μｍ位までの範囲にある。
又、沈降炭酸カルシウムを分類すると粒子径１〜
3μｍ位の軽微性炭酸カルシウムと称されるもの
と粒子径0.02〜0.1μｍ位のコロイド性炭酸カルシ
ウムと称されるものとなる。さらに、その形状も
立方形、紡錘形、柱状形等で特殊なものとして突
起を有する炭酸カルシウム粒子が特公昭57−
30815号公報に掲載されており、更に炭酸カルシ
ウム針絡合体が特公昭57−31530号公報に掲載さ
れている。(Prior Art) Calcium carbonate in actual industry is roughly divided into heavy calcium carbonate, which is produced by mechanically pulverizing limestone, and precipitated calcium carbonate, which is produced by chemical precipitation. The particles of heavy calcium carbonate are amorphous;
The particle size ranges from several μm to about 150 μm.
In addition, when precipitated calcium carbonate is classified, the particle size is 1~
There are two types: what is called minor calcium carbonate, which has a particle size of about 3 μm, and what is called colloidal calcium carbonate, which has a particle size of about 0.02 to 0.1 μm. In addition, calcium carbonate particles with special protrusions such as cubic, spindle, and columnar shapes were produced by the Special Publication in 1983.
It is published in Japanese Patent Publication No. 30815, and a calcium carbonate needle entangled body is also published in Japanese Patent Publication No. 31530/1983.
沈降炭酸カルシウムの製法は、炭酸イオンを含
む溶液（炭酸ナトリウム、炭酸アンモニウム等）
とカルシウム化合物の溶液（塩化カルシウム、酢
酸カルシウム等）を接触反応させて作る“液＝
液”法と、水酸化カルシウムと炭酸ガスの反応に
よつて作る“液＝ガス”法とがある。中でも日本
で工業的に主に行なわれているのは“液＝ガス”
法であり、反応条件（水酸化カルシウムスラリー
の濃度、反応温度、反応方法、添加剤の種類と有
無等）により種々の粒径、形状の炭酸カルシウム
が開発されている。又、“液＝液”法では、特開
昭59−203728に、針状（直径２〜3μｍ、長さ30
〜60μｍ）の炭酸カルシウム結晶の製法が掲載さ
れている。 Precipitated calcium carbonate is produced using a solution containing carbonate ions (sodium carbonate, ammonium carbonate, etc.)
A “liquid” made by contacting and reacting calcium compound solutions (calcium chloride, calcium acetate, etc.) with
There are two methods: the "liquid" method and the "liquid=gas" method, which is produced by the reaction of calcium hydroxide and carbon dioxide gas.Among these, the "liquid=gas" method is mainly used industrially in Japan.
Calcium carbonate with various particle sizes and shapes has been developed depending on the reaction conditions (concentration of calcium hydroxide slurry, reaction temperature, reaction method, type and presence of additives, etc.). In addition, in the "liquid=liquid" method, in Japanese Patent Application Laid-Open No. 59-203728, needle-shaped (2 to 3 μm in diameter, 30 μm in length)
A method for producing calcium carbonate crystals (~60 μm) is published.
（発明が解決しようとする問題点）
以上の如く種々の粒径、形状の炭酸カルシウム
が開発されているが、“液＝ガス”法で、長径５
〜100μｍ、短径0.2〜5μｍのような粒子で、しか
も単結晶の様を呈した針状粒子炭酸カルシウムは
従来の工業生産にはない。(Problems to be Solved by the Invention) As mentioned above, calcium carbonate with various particle sizes and shapes has been developed.
Acicular particle calcium carbonate particles with a particle size of ~100 μm and a minor axis of 0.2 to 5 μm, and which have the appearance of a single crystal, are not available in conventional industrial production.
（問題点を解決するための手段）
したがつて本発明の技術的課題は長径５〜
100μｍ、短径0.2〜5μｍのような粒子で、しかも
単結晶の様を呈した画期的な針状粒子炭酸カルシ
ウムを提供することを目的とするもので、その技
術的課題を解決する本発明の技術的手段は、炭酸
ガス又は炭酸ガスを含むガス体が吹き込まれてい
る70℃以上の水１に（水は撹拌されてもよい）、
水酸化カルシウム水溶液（各種薬品、たとえばサ
ツカロース等で水酸化カルシウムの溶解度を上げ
た溶液を含む）を適切な流量調整（150ml／分以
下）のうえ、滴下あるいは注入して、炭酸カルシ
ウムを生成させることである。(Means for solving the problem) Therefore, the technical problem of the present invention is to
The present invention aims to provide an innovative acicular particle calcium carbonate having a particle size of 100 μm and a minor axis of 0.2 to 5 μm, and which has the appearance of a single crystal.The present invention solves this technical problem. The technical means is to add carbon dioxide or a gas containing carbon dioxide to water 1 at a temperature of 70°C or higher (the water may be stirred),
Calcium carbonate is produced by dripping or injecting an aqueous calcium hydroxide solution (including solutions in which the solubility of calcium hydroxide is increased with various chemicals such as satucalose) after adjusting the flow rate appropriately (150 ml/min or less). It is.
（発明の効果）
この方法によれば、さきに出願人が出願した特
願昭60−16543号“針状粒子炭酸カルシウムの生
成方法”すなわち炭酸水素カルシウム水溶液に適
切な加熱制御を施すことにより針状粒子炭酸カル
シウムを生成させる方法よりも、少なくとも数倍
の生産性をあげることが出来、しかもそれにより
相当のコストダウンが可能になる。なかでも、各
種薬品、たとえばサツカロース等で、水酸化カル
シウムの溶解度を上げた方が、生産性やコストダ
ウンに大きく寄与する。(Effects of the Invention) According to this method, Japanese Patent Application No. 60-16543 previously filed by the applicant entitled "Method for producing acicular particle calcium carbonate", that is, by applying appropriate heating control to an aqueous solution of calcium hydrogen carbonate, This method can increase productivity at least several times as much as the method of producing particulate calcium carbonate, and it also makes it possible to reduce costs considerably. Among these, increasing the solubility of calcium hydroxide with various chemicals such as satucalose will greatly contribute to productivity and cost reduction.
又、針状粒子の大きさの調節については、適切
な操作条件を選択することにより、たとえば、水
酸化カルシウムの滴下や注入速度、あるいは反応
中の温度等を適切に選ぶことにより、比較的簡単
に出来る。 In addition, the size of the acicular particles can be adjusted relatively easily by selecting appropriate operating conditions, such as the dropping and injection rate of calcium hydroxide, or the temperature during the reaction. I can do it.
（実施例）
以下、実施例にもとづき、その内容を説明す
る。(Example) Hereinafter, the content will be explained based on an example.
実施例 １
酸化カルシウムを温度約80℃の撹拌されている
蒸留水中に投入し、水酸化カルシウムスラリーを
生成させ、室温まで放冷後、フイルターにより濾
過し、水酸化カルシウム水溶液を得、これを50
ml／分の流量で、撹拌されている80℃以上の蒸留
水１中に滴下して、針状粒子炭酸カルシウムを
生成させた。この時、その蒸溜水中に吹き込んで
いる炭酸ガスは１／分、1.5Kg／cm2であつた。Example 1 Calcium oxide was poured into distilled water being stirred at a temperature of about 80°C to produce a calcium hydroxide slurry. After cooling to room temperature, it was filtered using a filter to obtain an aqueous calcium hydroxide solution, which was
Acicular particle calcium carbonate was produced by dropping it into distilled water 1 at a temperature of 80° C. or higher that was being stirred at a flow rate of ml/min. At this time, the amount of carbon dioxide gas being blown into the distilled water was 1/min, 1.5 kg/cm 2 .
生成した針状粒子炭酸カルシウムをフイルター
にて濾過脱水し、電気乾燥機にて、約100℃で乾
燥してサンプルＡを得る。第４図にこのサンプル
ＡのSEMによる観察写真を示す。また第１図は
サンプルＡのＸ線回析パターンで、ほとんどアラ
ゴナイト結晶であることを示している。 The produced acicular calcium carbonate particles are filtered and dehydrated using a filter, and dried at about 100°C using an electric dryer to obtain sample A. FIG. 4 shows an SEM photograph of this sample A. FIG. 1 shows the X-ray diffraction pattern of sample A, which shows that it is mostly aragonite crystal.
実施例 ２
実施例１と同様な方法で得た水酸化カルシウム
水溶液を150ml／分（実施例１と比較して３倍）
の流量で、撹拌されている70℃以上の蒸留水１
に滴下して、針状粒子炭酸カルシウムを生成させ
た。この時の蒸留水中に吹き込んでいる炭酸ガス
は１／分、1.5Kg／cm2であつた。実施例１と同
様に、脱水、乾燥してサンプルＢを得る。第５図
にこのサンプルＢのSEMによる観察写真を示す。
第４図のもの（サンプルＡ）と比較して、小さい
形状の針状粒子炭酸カルシウムが生成されてい
る。第２図はサンプルＢのＸ線回析パターンを示
し、アラゴナイトに混つてカルサイトのピークが
認められる。Example 2 Calcium hydroxide aqueous solution obtained in the same manner as Example 1 at 150 ml/min (3 times as much as Example 1)
Distilled water at 70℃ or higher being stirred at a flow rate of 1
to form acicular particle calcium carbonate. The carbon dioxide gas being blown into the distilled water at this time was 1/min, 1.5 kg/cm 2 . Sample B is obtained by dehydration and drying in the same manner as in Example 1. FIG. 5 shows an SEM photograph of this sample B.
Compared to the sample in FIG. 4 (sample A), smaller acicular particle calcium carbonate particles are produced. FIG. 2 shows the X-ray diffraction pattern of Sample B, in which a peak of calcite is observed mixed with aragonite.
実施例 ３
水酸化カルシウムスラリー（濃度：Ca
（OH）20.75ｇ／H2O−100ml）約１にサツカロ
ース50ｇを添加し、フイルターにより濾過する。
この濾液を50ml／分の流量で撹拌されている80℃
以上の蒸留水１に適下して針状粒子炭酸カルシ
ウムを生成させた。この時の蒸留水中に吹き込ん
でいる炭酸ガスは１／分、1.5Kg／cm2であつた。
実施例１と同様に、脱水、乾燥してサンプルＣと
する。サツカロース添加により、水酸化カルシウ
ムの溶解度が増し、針状粒子炭酸カルシウムの収
量は実施例１のそれよりも約４倍に達した。第６
図に、このサンプルＣのSEMにより観察写真を
示す。また、第３図はサンプルＣのＸ線回析パタ
ーンでほとんどアラゴナイト結晶であることを示
している。Example 3 Calcium hydroxide slurry (concentration: Ca
(OH) 2 0.75 g/H 2 O-100 ml), add 50 g of sutucarose to approx. 1, and filter through a filter.
This filtrate was stirred at a flow rate of 50 ml/min at 80°C.
It was dropped into the above distilled water 1 to produce acicular particle calcium carbonate. The carbon dioxide gas being blown into the distilled water at this time was 1/min, 1.5 kg/cm 2 .
Sample C was obtained by dehydration and drying in the same manner as in Example 1. The addition of sutucarose increased the solubility of calcium hydroxide, and the yield of acicular particle calcium carbonate reached about 4 times that of Example 1. 6th
The figure shows an SEM photograph of this sample C. Furthermore, FIG. 3 shows the X-ray diffraction pattern of sample C, which shows that it is mostly aragonite crystal.
第１，２，３図はＸ線回析パターン図、第４，
５，６図は各異なる針状粒子炭酸カルシウムの図
面代用の結晶写真である。
Figures 1, 2, and 3 are X-ray diffraction pattern diagrams;
Figures 5 and 6 are crystal photographs substituted for drawings of different acicular particle calcium carbonate.
Claims (1)
まれていて、しかも適切な加熱制御がなされてい
る水に、水酸化カルシウム水溶液を適切な流量調
整のうえ、滴下あるいは注入して、炭酸カルシウ
ムを生成させることを特徴とする針状粒子炭酸カ
ルシウムの生成方法。1. Calcium hydroxide aqueous solution is dripped or injected into water into which carbon dioxide gas or a gaseous body containing carbon dioxide gas has been blown and which has been appropriately heated, with appropriate flow rate adjustment, to produce calcium carbonate. A method for producing acicular particle calcium carbonate, the method comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12041286A JPS62278123A (en) | 1986-05-26 | 1986-05-26 | Production of acicular calcium carbonate particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12041286A JPS62278123A (en) | 1986-05-26 | 1986-05-26 | Production of acicular calcium carbonate particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62278123A JPS62278123A (en) | 1987-12-03 |
| JPH0319166B2 true JPH0319166B2 (en) | 1991-03-14 |
Family
ID=14785581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12041286A Granted JPS62278123A (en) | 1986-05-26 | 1986-05-26 | Production of acicular calcium carbonate particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62278123A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2602274B2 (en) * | 1988-03-12 | 1997-04-23 | 奥多摩工業 株式会社 | Method for producing fibrous calcium carbonate |
| PT2537900E (en) * | 2011-06-21 | 2016-01-22 | Omya Int Ag | Process for the production of precipitated calcium carbonate |
-
1986
- 1986-05-26 JP JP12041286A patent/JPS62278123A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62278123A (en) | 1987-12-03 |
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