JPH054342B2 - - Google Patents
Info
- Publication number
- JPH054342B2 JPH054342B2 JP63133914A JP13391488A JPH054342B2 JP H054342 B2 JPH054342 B2 JP H054342B2 JP 63133914 A JP63133914 A JP 63133914A JP 13391488 A JP13391488 A JP 13391488A JP H054342 B2 JPH054342 B2 JP H054342B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- lime
- milk
- reaction
- spherical
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 118
- 239000000920 calcium hydroxide Substances 0.000 claims description 63
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 63
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 27
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 239000013078 crystal Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021532 Calcite Inorganic materials 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、球状の形状を有するバテライト型炭
酸カルシウムを製造する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing vaterite-type calcium carbonate having a spherical shape.
［発明の背景］
炭酸カルシウムは、紙、ゴム、プラスチツクス
および塗料などの充填剤として幅広く利用されて
おり、産業上重要な粉体のひとつとなつている。
産業において実際利用されている炭酸カルシウム
には、天然の白色石灰石を微粉砕して製造される
重質炭酸カルシウムと、化学的に合成される軽質
炭酸カルシウムとがある。軽質炭酸カルシウムの
工業的な製造方法としては、石灰乳に二酸化炭素
を導入して反応させる炭酸ガス化合法が広く採用
されており、この方法により紡錘状炭酸カルシウ
ムをはじめ立方体状、針状などの形状を有する炭
酸カルシウムが製造されている。[Background of the Invention] Calcium carbonate is widely used as a filler in paper, rubber, plastics, paints, etc., and is one of the industrially important powders.
Calcium carbonate actually used in industry includes heavy calcium carbonate, which is produced by pulverizing natural white limestone, and light calcium carbonate, which is chemically synthesized. As an industrial method for producing light calcium carbonate, the carbonation method, which involves introducing carbon dioxide into milk of lime and reacting it, is widely used.This method produces spindle-shaped calcium carbonate, cube-shaped, needle-shaped, etc. Calcium carbonate with a shape is produced.
炭酸カルシウムの結晶型にはカルサイト型、ア
ラゴナイト型、バテライト型の三種の同質異像が
知られている。天然に産出するものでは石灰石、
チヨークがカルサイト型で、真珠、サンゴがアラ
ゴナイト型である。バテライト型結晶は天然には
知られておらず、化学合成によつてのみその存在
が知られているが、非常に不安定な結晶で水中で
は、常温でカルサイト型に転移する。しかし、バ
テライト型の結晶習癖は通常には球状晶であるの
で、球状の形状を有する炭酸カルシウムを合成す
るために有利である。 There are three known crystal forms of calcium carbonate: calcite, aragonite, and vaterite. Naturally occurring limestone,
Chiyoke is calcite type, and pearls and coral are aragonite type. Vaterite-type crystals are not known in nature, and their existence is only known through chemical synthesis, but they are extremely unstable crystals that transform into calcite-type crystals at room temperature in water. However, since the vaterite crystal habit is usually spheroidal, it is advantageous for synthesizing calcium carbonate having a spherical shape.
従来、炭酸ガス化合法による球状炭酸カルシウ
ムの製造方法は、特公昭54−17719号公報、およ
び特開昭60−90822号公報に開示された方法など
が公知となつている。 Conventionally, methods for producing spherical calcium carbonate by the carbonation method include methods disclosed in Japanese Patent Publication No. 17719/1982 and Japanese Patent Application Laid-open No. 90822/1982.
特公昭54−17719号公報に開示された方法は、
炭酸ガスに対して10ppm以上の亜硫酸ガスを含んだ
混合ガスを温度20℃未満で石灰乳と反応させるこ
とを特徴とする球状炭酸カルシウムの製造方法で
あるが、カルシウムは本質的に亜硫酸と反応しや
すいので炭酸カルシウムの他に亜硫酸カルシウム
も生成し、高純度の球状炭酸カルシウムを製造す
ることは困難である。 The method disclosed in Japanese Patent Publication No. 54-17719 is
This method for producing spherical calcium carbonate is characterized by reacting a mixed gas containing 10 ppm or more of sulfur dioxide gas with milk of lime at a temperature below 20°C, but calcium essentially reacts with sulfur dioxide. Because of this, calcium sulfite is also produced in addition to calcium carbonate, making it difficult to produce highly pure spherical calcium carbonate.
また、特開昭60−90822号公報に開示された方
法は、マグネシウム化合物を含む水酸化カルシウ
ム水懸濁液の液温を０〜30℃とし、二酸化炭素を
導入して炭酸化を行ない、粘稠なにかわ状乳濁液
になつた時点で縮合リン酸あるいはそのアルカリ
金属塩を添加することを特徴とする球状炭酸カル
シウムの製造方法であるが、生成する球状炭酸カ
ルシウムの形状が歪のある球状になるため、充填
剤としてはあまり好ましくない。 In addition, the method disclosed in Japanese Patent Application Laid-open No. 60-90822 is such that the temperature of an aqueous suspension of calcium hydroxide containing a magnesium compound is set to 0 to 30°C, and carbon dioxide is introduced to cause carbonation. This method for producing spherical calcium carbonate is characterized by adding condensed phosphoric acid or its alkali metal salt when the emulsion becomes a thick, glue-like emulsion, but the shape of the spherical calcium carbonate produced is distorted. Therefore, it is not very preferable as a filler.
［発明の目的］
本発明は、紙、ゴム、プラスチツクスおよび塗
料などの充填剤として好適に利用される球状炭酸
カルシウムの新規な製造方法を提供することを目
的とする。[Object of the Invention] An object of the present invention is to provide a novel method for producing spherical calcium carbonate, which is suitably used as a filler for paper, rubber, plastics, paints, and the like.
［発明の要旨］
本発明は、モノエタノールアミンを含有する石
灰乳に二酸化炭素を導入して炭酸化反応を行なう
ことを特徴とするバテライト型球状炭酸カルシウ
ムの製造方法にある。[Summary of the Invention] The present invention resides in a method for producing vaterite-type spherical calcium carbonate, which is characterized by introducing carbon dioxide into milk of lime containing monoethanolamine to carry out a carbonation reaction.
本発明のバテライト型の球状炭酸カルシウムの
製造方法における好ましい実施の態様を以下に記
載する。 Preferred embodiments of the method for producing vaterite-type spherical calcium carbonate of the present invention will be described below.
(1) 石灰乳中のモノエタノールアミンの含有量
が、該石灰乳中に含有される水酸化カルシウム
に対して8.0〜100重量％であることを特徴とす
る球状炭酸カルシウムの製造方法。(1) A method for producing spherical calcium carbonate, characterized in that the content of monoethanolamine in the milk of lime is 8.0 to 100% by weight based on the calcium hydroxide contained in the milk of lime.
(2) 石灰乳が水100mlに対して３〜25gの水酸化
カルシウムを含むものであることを特徴とする
球状炭酸カルシウムの製造方法。(2) A method for producing spherical calcium carbonate, characterized in that the milk of lime contains 3 to 25 g of calcium hydroxide per 100 ml of water.
(3) 二酸化炭素の導入速度が、該石灰乳中に含有
される水酸化カルシウム1g当り７ml／分以上
であることを特徴とする球状炭酸カルシウムの
製造方法。(3) A method for producing spherical calcium carbonate, characterized in that the introduction rate of carbon dioxide is 7 ml/min or more per 1 g of calcium hydroxide contained in the milk of lime.
(4) 反応開始時の石灰乳の温度を20℃以下に調整
することを特徴とする球状炭酸カルシウムの製
造方法。(4) A method for producing spherical calcium carbonate, which comprises adjusting the temperature of milk of lime to 20°C or less at the start of the reaction.
(5) 炭酸化反応の温度を30℃以下に保つことを特
徴とする球状炭酸カルシウムの製造方法。(5) A method for producing spherical calcium carbonate, characterized by maintaining the carbonation reaction temperature at 30°C or lower.
［発明の詳細な記述］
本発明のバテライト型の球状炭酸カルシウムの
製造方法は、石灰乳にあらかじめモノエタノール
アミンを添加したのち、該石灰乳を炭酸化するこ
とを特徴とするものである。[Detailed Description of the Invention] The method for producing vaterite-type spherical calcium carbonate of the present invention is characterized by adding monoethanolamine to milk of lime in advance, and then carbonating the milk of lime.
本発明の炭酸カルシウムの製造に際して、まず
石灰乳（水酸化カルシウム水懸濁液）を調製す
る。石灰乳の調製に用いる水酸化カルシウム源と
して、通常の生石灰あるいは消石灰を用いること
ができる。生石灰及び消石灰の例としては、生石
灰粉、塊状生石灰、塩焼き生石灰および通常の消
石灰を挙げることができる。 In producing the calcium carbonate of the present invention, milk of lime (aqueous suspension of calcium hydroxide) is first prepared. Ordinary quicklime or slaked lime can be used as a source of calcium hydroxide for preparing milk of lime. Examples of quicklime and slaked lime include quicklime powder, lump quicklime, salt-baked quicklime and ordinary slaked lime.
上記のような生石灰および消石灰を水中に投入
して石灰乳を調製する。石灰乳中に含有される水
酸化カルシウムの濃度は、通常３〜25g／100ml、
好ましくは５〜16g／100mlの範囲である。石灰
乳に含有される水酸化カルシウムの濃度が3g／
100ml未満では濃度が低すぎて経済的でなく、濃
度が25g／100mlを越えると石灰乳の粘度が高く
なり、作業性が低下する。 Milk of lime is prepared by adding quicklime and slaked lime as described above into water. The concentration of calcium hydroxide contained in milk of lime is usually 3 to 25 g/100 ml,
Preferably it is in the range of 5 to 16 g/100 ml. The concentration of calcium hydroxide contained in milk of lime is 3g/
If the concentration is less than 100 ml, the concentration is too low and it is not economical, and if the concentration exceeds 25 g/100 ml, the viscosity of the milk of lime increases and workability decreases.
次に、炭酸化反応を開始する時点の石灰乳の温
度は一般に20℃以下、好ましくは、10〜17℃の範
囲に調整される。また、炭酸化反応中は、温度を
通常30℃以下、好ましくは25℃以下に保つ。石灰
乳の温度の制御は、炭酸化反応が発熱反応である
ため、例えば反応容器に冷却装置を付設して行な
うことができる。 Next, the temperature of the milk of lime at the time of starting the carbonation reaction is generally adjusted to below 20°C, preferably in the range of 10 to 17°C. Further, during the carbonation reaction, the temperature is usually maintained at 30°C or lower, preferably 25°C or lower. Since the carbonation reaction is an exothermic reaction, the temperature of the milk of lime can be controlled by, for example, attaching a cooling device to the reaction vessel.
モノエタノールアミンの添加量は、石灰乳中に
含有される水酸化カルシウムに対して通常8.0〜
100重量％、好ましくは10.0〜60重量％である。
通常、第１回目の球状炭酸カルシウムの製造時に
は、あらかじめモノエタノールアミンを石灰乳に
該石灰乳中に含有される水酸化カルシウムに対し
て8.0重量％以上添加する必要があるが、第１回
目製造以後の場合については、第１回目の反応液
の濾液を使用することが可能なため、モノエタノ
ールアミンを、新たな石灰乳中に含有される水酸
化カルシウムに対して3.0重量％程度添加すれば
よく省資源の面からも有利である。 The amount of monoethanolamine added is usually 8.0 to 8.0 to the amount of calcium hydroxide contained in milk of lime.
100% by weight, preferably 10.0-60% by weight.
Normally, during the first production of spherical calcium carbonate, it is necessary to add monoethanolamine to the milk of lime in advance in an amount of 8.0% by weight or more based on the calcium hydroxide contained in the milk of lime. In subsequent cases, it is possible to use the filtrate of the first reaction solution, so by adding about 3.0% by weight of monoethanolamine to the calcium hydroxide contained in the new milk of lime. It is also advantageous in terms of resource saving.
炭酸化反応を行なう際の二酸化炭素の導入速度
は、石灰乳中に含有される水酸化カルシウム1g
に対して通常７ml／分以上好ましくは８ml／分以
上に設定する。 The rate of introduction of carbon dioxide during carbonation reaction is 1g of calcium hydroxide contained in milk of lime.
It is usually set at 7 ml/min or more, preferably 8 ml/min or more.
導入する二酸化炭素は、二酸化炭素単独であつ
ても、あるいは水酸化カルシウムと実質的に反応
性を有していない気体（例：空気、窒素ガス）と
二酸化炭素との混合ガスであつてもよい。また、
石灰石の焼成の際に排出される二酸化炭素含有気
体を用いることもできる。混合ガスを用いる場合
は、混合ガス中の二酸化炭素の濃度が、通常10容
量％以上、好ましくは20容量％以上のものを使用
する。 The carbon dioxide to be introduced may be carbon dioxide alone, or a mixed gas of carbon dioxide and a gas that is not substantially reactive with calcium hydroxide (e.g., air, nitrogen gas). . Also,
It is also possible to use carbon dioxide-containing gas discharged during calcining of limestone. When using a mixed gas, the concentration of carbon dioxide in the mixed gas is usually 10% by volume or more, preferably 20% by volume or more.
なお、上記の炭酸化反応は、撹拌下に行なうこ
とが望ましい。 Note that the above carbonation reaction is preferably carried out under stirring.
［発明の効果］
本発明の製造方法により、従来炭酸ガス化合法
では製造することが困難であつた球状を有するバ
テライト型炭酸カルシウムを容易に製造すること
ができる。[Effects of the Invention] According to the production method of the present invention, vaterite-type calcium carbonate having a spherical shape, which has been difficult to produce by conventional carbonation methods, can be easily produced.
また、本発明の製造方法により得られる球状炭
酸カルシウムはバテライト型結晶のものとなり、
そのバテライト型結晶の特質として歪のない球状
のものが得られる。 In addition, the spherical calcium carbonate obtained by the production method of the present invention has vaterite type crystals,
As a characteristic of the vaterite type crystal, a spherical shape without distortion can be obtained.
従つて、本発明により得られる球状炭酸カルシ
ウムは、紙、ゴム、プラスチツクおスおよび塗料
などの各種材料の充填剤として好適に使用するこ
とができる。 Therefore, the spherical calcium carbonate obtained according to the present invention can be suitably used as a filler for various materials such as paper, rubber, plastic oxide, and paint.
次に本発明の実施例を示す。 Next, examples of the present invention will be shown.
［実施例 １］
冷却装置を備えた容量３の反応容器に工業用
生石灰粉および水を投入して、水酸化カルシウム
濃度8.0／100mlの石灰乳２を調製した。次に、
この石灰乳中に含有される水酸化カルシウムに対
して25重量％になるようにモノエタノールアミン
を添加した。[Example 1] Industrial quicklime powder and water were put into a reaction vessel with a capacity of 3 and equipped with a cooling device to prepare milk of lime 2 with a calcium hydroxide concentration of 8.0/100ml. next,
Monoethanolamine was added in an amount of 25% by weight based on the calcium hydroxide contained in this milk of lime.
この石灰乳を冷却し、反応開始温度17℃で純度
99.5％以上の二酸化炭素を二酸化炭素の導入速度
が石灰乳中に含有される水酸化カルシウム1gに
対して9.4ml／分となるように撹拌しながら導入
し、反応温度17℃で炭酸化反応を行なつた。 This milk of lime is cooled and purity is achieved at a reaction initiation temperature of 17℃.
Carbon dioxide of 99.5% or more was introduced with stirring at a rate of 9.4 ml/min per 1 g of calcium hydroxide contained in the milk of lime, and the carbonation reaction was carried out at a reaction temperature of 17°C. I did it.
反応終了後、得られた反応液に対し濾過、脱水
およびメチルアルコール洗浄の各操作を順次行な
つた後、110℃で乾燥して炭酸カルシウムを210g
得た。炭酸化反応に要した時間は33分であつた。 After the reaction was completed, the resulting reaction solution was sequentially filtered, dehydrated, and washed with methyl alcohol, and then dried at 110°C to obtain 210g of calcium carbonate.
Obtained. The time required for the carbonation reaction was 33 minutes.
得られた炭酸カルシウムの電子顕微鏡写真を詳
細に検討したところ、平均粒子径が約1μmの粒子
径の揃つた歪の少ない球状の形状を有する炭酸カ
ルシウムであつた。本実施例で得られた球状炭酸
カルシウムを添付した図面（第１図）に示す。 A detailed examination of the electron micrograph of the obtained calcium carbonate revealed that the calcium carbonate had a spherical shape with uniform particle size and little distortion, with an average particle size of about 1 μm. The spherical calcium carbonate obtained in this example is shown in the accompanying drawing (FIG. 1).
さらにＸ線回折の結果、得られた炭酸カルシウ
ムはバテライト型結晶であることが判明した。 Further, as a result of X-ray diffraction, it was found that the obtained calcium carbonate was a vaterite type crystal.
［実施例 ２］
実施例１で用いた反応容器と同一の反応容器
に、実施例１で得られた反応液の濾液1.7と工
業用生石灰粉及び水を投入して、水酸化カルシウ
ム濃度8.0g／100mlの石灰乳２を調製した。次
に、この石灰乳中に含有される水酸化カルシウム
に対して4.5重量％のモノエタノールアミンを添
加した。[Example 2] Into the same reaction container as that used in Example 1, 1.7 g of the filtrate of the reaction solution obtained in Example 1, industrial quicklime powder, and water were charged to give a calcium hydroxide concentration of 8.0 g. /100ml of milk of lime 2 was prepared. Next, 4.5% by weight of monoethanolamine was added to the calcium hydroxide contained in this milk of lime.
この石灰乳を冷却し、反応開始温度17℃で純度
99.5％以上の二酸化炭素を二酸化炭素の導入速度
が石灰乳中に含有される水酸化カルシウム1gに
対して12.5ml／分となるように撹拌しながら導入
し、反応温度17℃で炭酸化反応を行なつた。 This milk of lime is cooled and purity is achieved at a reaction initiation temperature of 17℃.
99.5% or more of carbon dioxide was introduced with stirring at a rate of 12.5 ml/min per 1 g of calcium hydroxide contained in the milk of lime, and the carbonation reaction was carried out at a reaction temperature of 17°C. I did it.
反応終了後、得られた反応液に対し濾過、脱水
およびメチルアルコール洗浄の各操作を順次行な
つた後、110℃で乾燥して炭酸カルシウムを210g
得た。炭酸化反応に要した時間は25分であつた。 After the reaction was completed, the resulting reaction solution was sequentially filtered, dehydrated, and washed with methyl alcohol, and then dried at 110°C to obtain 210g of calcium carbonate.
Obtained. The time required for the carbonation reaction was 25 minutes.
得られた炭酸カルシウムの電子顕微鏡写真を詳
細に検討したところ、平均粒子径が約0.9μmの粒
子径の揃つた歪の少ない球状の形状を有する炭酸
カルシウムであつた。 A detailed examination of the electron micrograph of the obtained calcium carbonate revealed that the calcium carbonate had a spherical shape with uniform particle size and little distortion, with an average particle size of about 0.9 μm.
さらにＸ線回折の結果、得られた炭酸カルシウ
ムはバテライト型結晶であることが判明した。 Further, as a result of X-ray diffraction, it was found that the obtained calcium carbonate was a vaterite type crystal.
［実施例 ３］
冷却装置を備えた容量６の反応容器に消石灰
および水を投入して、水酸化カルシウム濃度
12.0g／100mlの石灰乳５を調製した。次に、こ
の石灰乳中に含有される水酸化カルシウムに対し
て12重量％になるようにモノエタノールアミンを
添加した。[Example 3] Slaked lime and water were put into a reaction vessel with a capacity of 6 equipped with a cooling device, and the concentration of calcium hydroxide was
12.0g/100ml of milk of lime 5 was prepared. Next, monoethanolamine was added in an amount of 12% by weight based on the calcium hydroxide contained in this milk of lime.
この石灰乳を冷却し、反応開始温度17℃で二酸
化炭素含有気体（二酸化炭素濃度30容量％、窒素
ガス濃度70容量％）を二酸化炭素の導入速度が石
灰乳中に含有される水酸化カルシウム1gに対し
て9.4ml／分となるように撹拌しながら導入し、
反応温度17℃で炭酸化反応を行なつた。 This milk of lime is cooled, and at a reaction starting temperature of 17°C, carbon dioxide-containing gas (carbon dioxide concentration: 30% by volume, nitrogen gas concentration: 70% by volume) is introduced at a rate of 1g of calcium hydroxide contained in the milk of lime. Introduced while stirring at a rate of 9.4 ml/min.
The carbonation reaction was carried out at a reaction temperature of 17°C.
反応終了後、得られた反応液に対し濾過、脱水
およびメチルアルコール洗浄の各操作を順次行な
つた後、110℃で乾燥して炭酸カルシウムを525g
得た。炭酸化反応に要した時間は35分であつた。 After the reaction was completed, the resulting reaction solution was sequentially filtered, dehydrated, and washed with methyl alcohol, and then dried at 110°C to obtain 525g of calcium carbonate.
Obtained. The time required for the carbonation reaction was 35 minutes.
得られた炭酸カルシウムの電子顕微鏡写真を詳
細に検討したところ、平均粒子径が約0.7μmの粒
子径の揃つた歪の少ない球状の形状を有する炭酸
カルシウムであつ。 A detailed examination of the electron micrograph of the obtained calcium carbonate revealed that the calcium carbonate had a spherical shape with uniform particle size and little distortion, with an average particle size of about 0.7 μm.
さらにＸ線回折の結果、得られた炭酸カルシウ
ムはバテライト型結晶であることが判明した。 Further, as a result of X-ray diffraction, it was found that the obtained calcium carbonate was a vaterite type crystal.
［比較例 １］
モノエタノールアミンを全く添加しなかつた以
外は、実施例１と同様にして炭酸カルシウムを製
造した。[Comparative Example 1] Calcium carbonate was produced in the same manner as in Example 1, except that no monoethanolamine was added.
生成した炭酸カルシウムは、微細な不定型であ
つた。さらにＸ線回折の結果、得られた炭酸カル
シウムはカルサイト型結晶であることが判明し
た。 The produced calcium carbonate was of a fine amorphous type. Further, as a result of X-ray diffraction, it was found that the obtained calcium carbonate was a calcite type crystal.
［実施例 ４］
モノエタノールアミンの使用量を19重量％
（0.50モル）に替えた以外は実施例１と同様にし
て炭酸カルシウムを得た。得られた炭酸カルシウ
ムは球状で、Ｘ線回折測定の結果、バテライト型
結晶であることが確認された。[Example 4] The amount of monoethanolamine used was 19% by weight
Calcium carbonate was obtained in the same manner as in Example 1 except that the amount was changed to (0.50 mol). The obtained calcium carbonate was spherical, and as a result of X-ray diffraction measurement, it was confirmed that it was a vaterite type crystal.
［比較例 ２］
モノエタノールアミンの代わりに同モル（0.50
モル、33重量％）のジエタノールアミンを用いた
以外は実施例４と同様にして炭酸カルシウムを得
た。得られた炭酸カルシウムは立方体状粒子を中
心とする各種形状の粒子で、Ｘ線回折測定の結
果、カルサイト型結晶であることが確認された。[Comparative Example 2] The same mole (0.50
Calcium carbonate was obtained in the same manner as in Example 4, except that diethanolamine (mol, 33% by weight) was used. The obtained calcium carbonate had particles of various shapes, mainly cubic particles, and as a result of X-ray diffraction measurement, it was confirmed that they were calcite-type crystals.
［比較例 ３］
モノエタノールアミンの代わりに同モル（0.50
モル、47重量％）のトリエタノールアミンを用い
た以外は実施例４と同様にして炭酸カルシウムを
得た。得られた炭酸カルシウムは微細の各種形状
の粒子で、Ｘ線回折測定の結果、カルサイト型結
晶であることが確認された。[Comparative Example 3] The same mole (0.50
Calcium carbonate was obtained in the same manner as in Example 4, except that triethanolamine (mol, 47% by weight) was used. The obtained calcium carbonate was fine particles of various shapes, and as a result of X-ray diffraction measurement, it was confirmed that they were calcite-type crystals.
第１図は、実施例１で得られたバテライト型の
球状炭酸カルシウムの形状を示す5000倍の電子顕
微鏡写真の複製図であり、写真中のバーの長さは
10μmを示す。
Figure 1 is a reproduction of a 5000x electron micrograph showing the shape of vaterite-type spherical calcium carbonate obtained in Example 1, and the length of the bar in the photograph is
10μm is shown.
Claims (1)
酸化炭素を導入して炭酸化反応を行なうことを特
徴とするバテライト型球状炭酸カルシウムの製造
方法。1. A method for producing vaterite-type spherical calcium carbonate, which comprises introducing carbon dioxide into milk of lime containing monoethanolamine to carry out a carbonation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13391488A JPH01301511A (en) | 1988-05-31 | 1988-05-31 | Production of spherical calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13391488A JPH01301511A (en) | 1988-05-31 | 1988-05-31 | Production of spherical calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01301511A JPH01301511A (en) | 1989-12-05 |
| JPH054342B2 true JPH054342B2 (en) | 1993-01-19 |
Family
ID=15116042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13391488A Granted JPH01301511A (en) | 1988-05-31 | 1988-05-31 | Production of spherical calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01301511A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011051834A (en) * | 2009-09-02 | 2011-03-17 | Taiheiyo Cement Corp | Method of producing high purity vaterite-type spherical calcium carbonate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2203210C (en) * | 1997-04-21 | 2005-11-15 | Goldcorp Inc. | Manufacture of precipitated calcium carbonate |
| CA2237960A1 (en) * | 1997-06-18 | 1998-12-18 | Goldcorp Inc. | Manufacture of precipitated calcium carbonate of improved colour with stable crystalline form |
| KR20010080481A (en) * | 1999-10-26 | 2001-08-22 | 추후제출 | calcium carbonates and their preparation methods |
| JP6044015B2 (en) * | 2011-07-28 | 2016-12-14 | 学校法人北里研究所 | Production method of alkaline earth metal carbonate using carbon dioxide in air and its utilization |
-
1988
- 1988-05-31 JP JP13391488A patent/JPH01301511A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011051834A (en) * | 2009-09-02 | 2011-03-17 | Taiheiyo Cement Corp | Method of producing high purity vaterite-type spherical calcium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01301511A (en) | 1989-12-05 |
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