JP2001270713A - Method for producing calcium carbonate having aragonite crystal system - Google Patents
Method for producing calcium carbonate having aragonite crystal systemInfo
- Publication number
- JP2001270713A JP2001270713A JP2000087846A JP2000087846A JP2001270713A JP 2001270713 A JP2001270713 A JP 2001270713A JP 2000087846 A JP2000087846 A JP 2000087846A JP 2000087846 A JP2000087846 A JP 2000087846A JP 2001270713 A JP2001270713 A JP 2001270713A
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- JP
- Japan
- Prior art keywords
- calcium carbonate
- carbon dioxide
- aragonite
- mol
- lime
- 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.)
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は各種素材の充填材・
顔料として有用なアラゴナイト結晶系炭酸カルシウムの
製造方法に関するものであり、さらに詳しくは生石灰又
は/及び消石灰を懸濁させる時にアルカリ性水溶液を用
い、その後に炭酸ガスを導入することにより各種素材の
充填材・顔料として有用なアラゴナイト結晶系炭酸カル
シウムを製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a filler for various materials.
The present invention relates to a method for producing aragonite crystalline calcium carbonate useful as a pigment, and more specifically, to use an alkaline aqueous solution when suspending quicklime or / and slaked lime, and thereafter introducing a carbon dioxide gas into the filler material of various materials. The present invention relates to a method for producing aragonite crystalline calcium carbonate useful as a pigment.
【０００２】[0002]
【従来の技術】炭酸カルシウムは製紙、ゴム、プラスチ
ック等の広範囲な工業分野で利用されており、特に製紙
分野ではその使用量が急増している。これらの理由は
(1)安価、(2)高白色度、（3）様々な形状を有する、な
どが挙げられる。その結果、炭酸カルシウムの利用価値
は高い。炭酸カルシウムにはカルサイト、アラゴナイ
ト、バテライトの3種類の結晶多形があり、天然にはカ
ルサイトがほとんどであり、貝殻などの一部にアラゴナ
イトが存在しているだけでバテライトは一般には存在し
ていない。これらの結晶多形の内、アラゴナイトは針
状、柱状、イガグリ状などの特徴的な晶癖を有している
ため、非常に有用である。しかしながら天然にはほとん
ど産出しないため人工的に製造する方法が採用されてい
る。2. Description of the Related Art Calcium carbonate is used in a wide range of industrial fields such as papermaking, rubber, plastics and the like, and its use is rapidly increasing especially in the papermaking field. These reasons are
(1) low cost, (2) high whiteness, (3) various shapes, and the like. As a result, the utility value of calcium carbonate is high. Calcium carbonate has three types of crystalline polymorphs: calcite, aragonite, and vaterite.Naturally, calcite is mostly present, and vaterite is generally present only in the presence of aragonite in some shells. Not. Among these polymorphs, aragonite is very useful because it has a characteristic crystal habit such as a needle shape, a column shape, and a wiggle shape. However, since it is hardly produced in nature, an artificial production method is employed.
【０００３】炭酸カルシウムの製造方法としては(1)炭
酸ガスと水酸化カルシウムの水性懸濁液との反応である
炭酸ガス法、(2)炭酸ナトリウムと塩化カルシウムとの
反応による塩化カルシウムソーダ法、(3)炭酸ナトリウ
ムと石灰乳との反応による石灰ソーダ法等の反応が挙げ
られる。これらの内、アラゴナイト結晶系炭酸カルシウ
ムの製造方法としては(1)の炭酸ガス法を用いてリン酸
化合物などの添加物を用いる方法（特開昭63-256514
号）、水酸化カルシウムの水性懸濁液の粘度を規定する
方法（特開平4-295010号公報）などの特許が開示されて
いる。The methods for producing calcium carbonate include: (1) a carbon dioxide gas method, which is a reaction between carbon dioxide gas and an aqueous suspension of calcium hydroxide; (2) a calcium chloride soda method, a reaction between sodium carbonate and calcium chloride; (3) A reaction such as a lime soda method by a reaction between sodium carbonate and milk of lime. Among them, as a method for producing aragonite crystalline calcium carbonate, a method using an additive such as a phosphoric acid compound using the carbon dioxide method of (1) (JP-A-63-256514)
And a method of defining the viscosity of an aqueous suspension of calcium hydroxide (Japanese Patent Application Laid-Open No. 4-250010).
【０００４】上記炭酸ガス法では炭酸ガスの水への溶解
度が非常に低いため、全般的に反応時間が非常に長くな
ってしまう欠点がある。より生産性を向上させる目的で
炭酸ガスの流量を高くすると、カルサイトの生成が多く
なってしまうため、アラゴナイトを生成させるためには
やはり反応時間を長くさせなければならず、生産性の向
上は困難であると言える。一方、石灰ソーダ法では炭酸
カルシウムの他に生成する水酸化ナトリウムを分離する
装置が必要であるという問題がある。[0004] In the above-mentioned carbon dioxide method, since the solubility of carbon dioxide in water is very low, there is a disadvantage that the reaction time generally becomes very long. If the flow rate of carbon dioxide gas is increased for the purpose of further improving productivity, calcite will be generated more.Therefore, in order to generate aragonite, the reaction time must also be lengthened, and the improvement in productivity is not achieved. It can be said that it is difficult. On the other hand, the lime soda method has a problem that a device for separating sodium hydroxide generated in addition to calcium carbonate is required.
【０００５】[0005]
【発明が解決しようとする課題】以上のような状況に鑑
み、炭酸ガス法を用いたアラゴナイト結晶系炭酸カルシ
ウムの製造方法を改良し、炭酸ガスの流量を高めた場合
でも高アラゴナイト含量であるアラゴナイト結晶系炭酸
カルシウムを製造することを本発明の課題とした。In view of the above situation, the method for producing aragonite crystalline calcium carbonate using the carbon dioxide method has been improved, and aragonite having a high aragonite content even when the flow rate of carbon dioxide gas is increased. An object of the present invention is to produce crystalline calcium carbonate.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、硫酸塩法
又はソーダ法によるパルプ製造工程の苛性化工程を利用
して、生石灰の濃度が1〜60重量％になるように、生石
灰又は/及び消石灰に生石灰換算で1 molに対して特定濃
度範囲の炭酸イオンを含む特定濃度以下のアルカリ水溶
液を添加し、攪拌させ石灰乳を調製した後、緑液を連続
的に添加し、その添加速度及び反応温度を制御すること
によってアラゴナイト結晶が得られることを見出した。Means for Solving the Problems The present inventors utilize a causticizing step of a pulp production process by a sulfate method or a soda method so that quick lime or quick lime may be adjusted to a concentration of 1 to 60% by weight. Add an aqueous alkali solution containing a specific concentration range of carbonate ion to specific mol per mol of quick lime and / or to slaked lime, stir to prepare lime milk, and then add green liquor continuously and add it It has been found that aragonite crystals can be obtained by controlling the rate and the reaction temperature.
【０００７】そこで本発明者らは、さらに鋭意研究を重
ねた結果、アルカリ存在下で炭酸化を行うとアラゴナイ
ト結晶が析出しやすいことを突き止め、アルカリ水溶液
を用いて石灰乳を調製した後、炭酸ガスの流量と反応温
度を制御することによってアラゴナイト結晶が得られる
ことを見出し、この知見に基づいて本発明をなすに至っ
た。本発明の方法により、高アラゴナイト結晶含有でか
つ形状コントロールした炭酸カルシウムの製造が可能と
なり、粒子の短径が0.1〜1.5μｍで、長径が0.2〜25μ
ｍの、針状、柱状、イガグリ状の炭酸カルシウムが調製
されることが分かった。これらは例えば製紙用填料とし
て用いると、白色度、ワイヤー摩耗性、嵩、不透明度、
こし等の改善の効果が表れる。しかもこの方法は従来の
水を用いた石灰乳と炭酸ガスとの反応による方法に比べ
てアルカリ水溶液を用いると水酸化カルシウムからのカ
ルシウムイオンの溶出速度も低下するが、炭酸ガス流量
が高い場合、炭酸ガスのアルカリ水溶液への吸収速度の
方が大きく向上し、炭酸カルシウムの生成速度も向上す
る。これにより炭酸カルシウム生産量の向上につなげる
ことができる。特に高温側で比べるとその差は大きくな
る。The inventors of the present invention have conducted further studies and found that aragonite crystals are liable to precipitate when carbonation is performed in the presence of an alkali. After preparing lime milk using an alkaline aqueous solution, It has been found that aragonite crystals can be obtained by controlling the gas flow rate and the reaction temperature, and the present invention has been accomplished based on this finding. By the method of the present invention, it is possible to produce calcium carbonate having a high aragonite crystal content and shape control, the minor axis of the particles is 0.1 to 1.5 μm, the major axis is 0.2 to 25 μm
It was found that m, needle-shaped, columnar, and wiggly-shaped calcium carbonate were prepared. For example, when used as a filler for papermaking, whiteness, wire abrasion, bulk, opacity,
The effect of improvement such as straining appears. Moreover, this method reduces the elution rate of calcium ions from calcium hydroxide when using an alkaline aqueous solution as compared with the conventional method using a reaction between lime milk and carbon dioxide using water, but when the carbon dioxide gas flow rate is high, The rate of absorption of carbon dioxide into the aqueous alkali solution is significantly improved, and the rate of generation of calcium carbonate is also improved. This can lead to an increase in calcium carbonate production. In particular, the difference increases when compared on the high temperature side.
【０００８】[0008]
【発明の実施の形態】本発明の石灰乳の調製において使
用する生石灰は、炭酸カルシウムを主成分とする石灰石
を焼成したものであればよい。なお、その際の焼成装置
に関しては、ベッケンバッハ炉、メルツ炉、ロータリー
キルン、国井式炉、KHD（カーハーディー）炉、コマ式
炉、カルマチック炉、流動焼成炉、混合焼き立炉等、炭
酸カルシウムを生石灰（酸化カルシウム）に転化する装
置であれば特に制限されない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Quick lime used in the preparation of lime milk of the present invention may be any one obtained by calcining limestone mainly containing calcium carbonate. In addition, regarding the sintering apparatus at that time, a calcium carbonate such as a Beckenbach furnace, a Melz furnace, a rotary kiln, a Kunii type furnace, a KHD (Car Hardy) furnace, a Koma type furnace, a calmatic furnace, a fluidized sintering furnace, a mixed sintering furnace, etc. There is no particular limitation as long as it is a device that converts lime into quick lime (calcium oxide).
【０００９】得られる炭酸カルシウム中の不純物の含量
については、特に着色成分（Fe、Mn等）が問題となる
が、用途に合わせて着色成分含量の少ない原料石灰石か
ら得られる生石灰を適宜選択する。また生石灰中の炭酸
カルシウム含量はできるだけ少ない原料が好ましい。ま
た石灰乳の調製において使用する消石灰は前記生石灰を
湿式及び乾式で消和されたものでよいが、乾式で消和さ
れた消石灰の方が生成するアラゴナイト結晶の含有率及
び形状にとってはより好ましい。The content of impurities in the obtained calcium carbonate is particularly problematic in terms of coloring components (Fe, Mn, etc.), but quick lime obtained from raw limestone having a low coloring component content is appropriately selected according to the application. A raw material having a calcium carbonate content in quicklime which is as small as possible is preferable. The slaked lime used in the preparation of lime milk may be one obtained by slaking the quick lime by a wet method and a dry method, but slaked lime slaked by a dry method is more preferable in terms of the content and shape of aragonite crystals generated.
【００１０】石灰乳の調製において添加する液としては
生石灰1 molに対して0.25 mol以下、好ましくは0.10mol
以下、より好ましくは0.01mol以下の炭酸イオンを含む
水酸化物イオン濃度で0.01〜2M、好ましくは0.1〜1Mの
アルカリ水溶液を利用する。ここで用いるアルカリ水溶
液の濃度は0.01M以下ではアルカリの添加効果が認めら
れず、2M以上ではコストがかさんでしまう。また、この
アルカリ水溶液はどのようなアルカリでも可能である
が、炭酸ガスとの反応によって炭酸カルシウムより溶解
度が高い炭酸塩を生成しなければならず、また反応性を
向上させるためには溶解度がかなり高い炭酸塩を生成す
るアルカリ水溶液、例えば水酸化ナトリウムや水酸化カ
リウム水溶液などを用いるのが好ましい。また、この
時、生石灰1molに対して炭酸イオンが0.25 molより多く
なると生成する炭酸カルシウムは紡錘状もしくは塊状の
カルサイト結晶になる。さらに高品質のアラゴナイト結
晶の炭酸カルシウムを得ようとするならば炭酸イオンが
ほとんどない0.1〜1Mの水酸化ナトリウム水溶液を用い
た方がより好ましい。The liquid to be added in the preparation of lime milk is 0.25 mol or less, preferably 0.10 mol per mol of quick lime.
In the following, an alkali aqueous solution having a hydroxide ion concentration of 0.01 to 2 M, more preferably 0.1 to 1 M, preferably 0.1 to 1 M, more preferably 0.01 mol or less is used. If the concentration of the aqueous alkali solution used here is 0.01M or less, no effect of adding the alkali is observed, and if it is 2M or more, the cost increases. In addition, although any alkali can be used for this aqueous alkali solution, it is necessary to generate a carbonate having a higher solubility than calcium carbonate by reaction with carbon dioxide gas, and the solubility is considerably high in order to improve the reactivity. It is preferable to use an aqueous alkali solution that generates a high carbonate, such as an aqueous sodium hydroxide or potassium hydroxide solution. Also, at this time, if the carbonate ion is more than 0.25 mol per 1 mol of quick lime, the calcium carbonate formed becomes a spindle-shaped or massive calcite crystal. In order to obtain high quality calcium carbonate of aragonite crystals, it is more preferable to use a 0.1 to 1 M aqueous sodium hydroxide solution having almost no carbonate ion.
【００１１】石灰乳の調製時の石灰濃度は生石灰換算で
5〜30重量％の条件、好ましくは5〜20重量％で行う必要
がある。ここで石灰濃度が30重量％を超えると反応途中
でも粘度が高すぎて現実的に攪拌が困難となる。一方、
石灰濃度が5重量％未満では生産性が悪く、実用的では
ない。The lime concentration in the preparation of lime milk is calculated as quick lime.
It is necessary to carry out the reaction at 5 to 30% by weight, preferably 5 to 20% by weight. Here, if the lime concentration exceeds 30% by weight, the viscosity is too high even during the reaction, and it becomes practically difficult to stir. on the other hand,
If the lime concentration is less than 5% by weight, the productivity is poor and not practical.
【００１２】生石灰の消和および消石灰の溶解での混合
には、一般的な攪拌羽根式等を粘度にあわせて適宜選定
して使用すれば良い。本発明で用いる炭酸ガスは炭酸ガ
スの含有率が10〜100容量％のものを用いることができ
るが、生産性を考慮するとより高含有率のものが好まし
い。炭酸ガスの導入はガスを懸濁液中に吹き込みバブリ
ングさせることによって行い、その流量は炭酸ガスとし
て水酸化カルシウム1kgあたり0.5〜10L/minの範囲で添
加する必要がある。この時10L/minより高い流量で導入
するとカルサイト結晶の混入が激しくなる。また、0.5L
/minより低い流量であると生産性向上に寄与できない。For slaking quicklime and mixing in dissolving slaked lime, a general stirring blade type or the like may be appropriately selected and used according to the viscosity. The carbon dioxide used in the present invention may have a carbon dioxide content of 10 to 100% by volume, but a higher content is preferred in view of productivity. The introduction of carbon dioxide gas is performed by blowing the gas into the suspension and bubbling, and the flow rate needs to be added as carbon dioxide in the range of 0.5 to 10 L / min per kg of calcium hydroxide. At this time, if introduced at a flow rate higher than 10 L / min, the mixing of calcite crystals becomes severe. Also, 0.5L
If the flow rate is lower than / min, it cannot contribute to productivity improvement.
【００１３】反応温度については20〜80℃で行う必要が
あるが20℃より低い温度では冷却などの新たな設備が必
要なためコストが高くなってしまう。また80℃より高く
なるとカルサイトが多く生成してしまう。これらのカル
サイト結晶は例えば製紙填料として用いた場合、不透明
度低下等の原因になってしまう。The reaction must be carried out at a temperature of 20 to 80 ° C., but at a temperature lower than 20 ° C., new equipment such as cooling is required, so that the cost increases. If the temperature is higher than 80 ° C., a large amount of calcite is generated. When these calcite crystals are used, for example, as a papermaking filler, they cause a reduction in opacity and the like.
【００１４】反応時の攪拌には、一般的な攪拌羽根式な
どを使用し、生石灰の消和および消石灰の溶解により調
製された石灰乳と炭酸ガスが均一に混合できるものを適
宜選定して使用すれば良い。For the stirring during the reaction, a general stirring blade type or the like is used, and a lime milk prepared by slaking quick lime and dissolving slaked lime and carbon dioxide gas can be appropriately selected and used. Just do it.
【００１５】水酸化カルシウムのほとんどが反応して炭
酸カルシウムになった後に残る石灰乳の調製において添
加したアルカリ水溶液は炭酸ガスを過剰に導入すること
により炭酸水素塩になり反応後のスラリーは中性から弱
アルカリ性になり、例えば製紙用填料としてはそのまま
利用できるが、中性であることが必要な場合はろ過・洗
浄などを行えば良い。ろ過、洗浄には、公知のシックナ
ー（沈降分離型）、真空ろ過器、加圧ろ過器、遠心分離
器などを用いることができる。これらの中で特に真空ろ
過器、加圧ろ過器、遠心分離器を用いてアルカリ水溶液
と分離することが好ましく、その後に必要であれば水で
置換洗浄などをすれば良い。以上のような条件下におい
て、粒子の短径が0.1〜1.5μｍで、長径が0.3〜25μｍ
の、針状、柱状、イガグリ状の炭酸カルシウムが調製さ
れる。Alkaline aqueous solution added in the preparation of lime milk remaining after most of the calcium hydroxide has reacted to form calcium carbonate becomes bicarbonate by introducing excessive carbon dioxide gas, and the slurry after the reaction becomes neutral. Thus, it becomes weakly alkaline and can be used as it is as a filler for papermaking, for example, but if it needs to be neutral, filtration and washing may be performed. For filtration and washing, a known thickener (sedimentation separation type), a vacuum filter, a pressure filter, a centrifuge, or the like can be used. Among them, it is particularly preferable to separate from the alkaline aqueous solution using a vacuum filter, a pressure filter, or a centrifugal separator, and then, if necessary, replacement washing with water may be performed. Under the above conditions, the minor axis of the particles is 0.1 to 1.5 μm and the major axis is 0.3 to 25 μm.
A needle-shaped, column-shaped, and wiggly-shaped calcium carbonate is prepared.
【００１６】このとき、アラゴナイト結晶含有率は、７
０％以上、好ましくは、８０重量％以上が必要となる。
アラゴナイト結晶含有率が７０％未満であるとアラゴナ
イト結晶由来のアスペクト比の大きい針状・柱状粒子の
他にアスペクト比の小さい粒状などの凝集した形状が多
く混入し、各種素材の充填剤としての性能を低下させ
る。特に、プラスチックの充填剤として用いたときにそ
の強度特性を著しく低下させる。また、ここで洗浄して
得られたアラゴナイト結晶系炭酸カルシウムは例えば、
紙の填料として用いる際、粒子径が大きい場合、湿式又
は乾式処理した後に利用するのが好ましい。At this time, the aragonite crystal content is 7
0% or more, preferably 80% by weight or more is required.
When the aragonite crystal content is less than 70%, many aggregated shapes such as small particles having a small aspect ratio are mixed in addition to needle-like and columnar particles having a large aspect ratio derived from aragonite crystals, and the performance as a filler for various materials. Lower. In particular, when used as a filler in plastics, it significantly reduces its strength properties. The aragonite crystalline calcium carbonate obtained by washing here is, for example,
When used as a filler for paper, when the particle size is large, it is preferable to use it after wet or dry treatment.
【００１７】本発明によって得られるアラゴナイト結晶
系炭酸カルシウムは製紙用填料・顔料やゴム、プラスチ
ック等の各種素材の充填材・顔料として利用できる。特
に製紙用填料として利用した時は紙の嵩、不透明度、白
色度、こし等の改善効果があり、粉砕して顔料として使
用した場合、印刷後光沢、表面強度の向上効果がある。The aragonite crystalline calcium carbonate obtained by the present invention can be used as fillers and pigments for papermaking, fillers and pigments for various materials such as rubber and plastics. In particular, when used as a filler for papermaking, it has the effect of improving the bulk, opacity, whiteness, and stiffness of the paper, and when crushed and used as a pigment, has the effect of improving gloss and surface strength after printing.
【００１８】[0018]
【作用】本発明のメカニズムについては充分に解明され
ていないが、アルカリ水溶液中に炭酸ガスを導入すると
炭酸ナトリウムや炭酸カリウムなどの溶解度が高い炭酸
塩の水溶液となり、これらの炭酸塩と水酸化カルシウム
が反応することによって炭酸カルシウムが生成する。こ
の時、反応が起こる環境下でアルカリが存在するとアラ
ゴナイト結晶が優先的に析出しやすいものと思われる。
しかし、この時に過剰の炭酸イオンが溶液内に存在する
とカルサイト結晶が生成しやすい。従って石灰乳の調製
の際に易溶性の炭酸塩を多く含んだアルカリ水溶液を用
いた場合や過剰に炭酸ガスの流量を高めると、アラゴナ
イト結晶の含有率が低下する傾向にある。Although the mechanism of the present invention has not been fully elucidated, the introduction of carbon dioxide into an aqueous alkaline solution results in an aqueous solution of a highly soluble carbonate such as sodium carbonate or potassium carbonate. Reacts to produce calcium carbonate. At this time, it is considered that aragonite crystals are likely to preferentially precipitate when alkali is present in an environment where the reaction occurs.
However, at this time, if excess carbonate ions are present in the solution, calcite crystals are likely to be generated. Therefore, the content of aragonite crystals tends to decrease when an alkaline aqueous solution containing a large amount of readily soluble carbonate is used in preparing lime milk or when the flow rate of carbon dioxide gas is excessively increased.
【００１９】[0019]
【実施例】以下に本発明を実施例および比較例をあげて
より詳細に説明するが、当然ながら、本発明は実施例の
みに限定されるものではない。 ［試験法］ 形態観察：生成物を水洗濾過し、乾燥後走査型電子顕
微鏡(日本電子株製JSM-5300)で形態を観察した。ここで
の観察をもとに30個の粒子の短径、長径を測定した。 結晶構造：Rigaku製 X線回折RAD-2Cにより測定し
た。 アラゴナイト結晶含有率の測定：Ca(NO3)2-(NH4)2CO
系で調製した純度 99.3%のアラゴナイト結晶と99.99%
の超高純度試薬のカルサイト結晶を任意の 割合で混合
し、Ｘ線回折で2θ=26.2（アラゴナイト）、2θ=29.4
（カルサ イト）のピーク強度を測定した。強度比と混
合比率の関係の検量線を作成し、 これを用いてアラゴ
ナイト結晶含有率を求めた。 ［実施例１］適当な容量の４ツ口フラスコ容器(以下の
実施例・比較例についても同じ容器使用)に、消石灰と１
mol/L-NaOH水溶液を用い、生石灰濃度として10重量％に
なる割合で混合して石灰乳をつくり、炭酸ガス含有率10
0容量％の炭酸ガスを流量2L/min/kg CaOで吹き込み、温
度50℃、攪拌速度400rpm（KYOEI POWER STIRRER TYPEPS
-2N使用、以下の実施例・比較例について同じ攪拌機使
用）の条件で炭酸化反応を行わせた。反応終了後、得ら
れた炭酸カルシウムのスラリーはＮｏ．５Ｃのろ紙を用
いて、ブフナー漏斗で吸引ろ過し、さらに水で数回洗浄
し、分析に供した。生成反応物のX線回折測定及び形態
観察を行った結果、生成物は平均長径8.0μｍ、平均短
径0.5μｍであるアラゴナイト結晶含有率が99%の針状炭
酸カルシウムが認められた。実験条件および結果を表１
に示す。 ［実施例２］炭酸ガスの流量を10L/min/kg CaOの条件で
炭酸化反応を行った以外は実施例１の条件で行った。生
成物は平均長径3.5μｍ、平均短径0.3μｍであるアラゴ
ナイト結晶含有率87%の針状炭酸カルシウムが認められ
た。実験条件および結果を表１に示す。 ［実施例３］生石灰濃度として20重量％になる割合で石
灰乳をつくり、炭酸ガスの流量を2L/min/kg CaOで吹き
込み、温度75℃の条件で炭酸化反応を行わせた以外は実
施例１と同様に行った。生成物は平均長径9.0μｍ、平
均短径0.5μｍのアラゴナイト結晶含有率99%の柱状炭酸
カルシウムであることが認められた。実験条件および結
果を表１に示す。 ［比較例１］石灰乳の調製に水を用いた以外は実施例２
と同様に行った。この時の反応生成物は、アラゴナイト
結晶含有率59%でウニ状と粒状の形状の混合した炭酸カ
ルシウムであることが認められた。実験条件および結果
を表１に示す。 ［比較例２］石灰乳の調製に水を用い、温度50℃で行っ
た以外は実施例３と同様に行った。この時の反応生成物
は、アラゴナイト結晶含有率41%で粒状と柱状の形状が
混合した炭酸カルシウムであることが認められた。実験
条件および結果を表１に示す。EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to only Examples. [Test Method] Morphological observation: The product was washed with water, filtered, dried, and observed with a scanning electron microscope (JSM-5300 manufactured by JEOL Ltd.). The minor axis and major axis of 30 particles were measured based on the observation here. Crystal structure: Measured by X-ray diffraction RAD-2C manufactured by Rigaku. Measurement of aragonite crystal content: Ca (NO 3 ) 2- (NH 4 ) 2 CO
Aragonite crystals of 99.3% purity and 99.99%
The ultra-high purity reagent calcite crystals were mixed at an arbitrary ratio, and 2θ = 26.2 (aragonite) and 2θ = 29.4 by X-ray diffraction.
(Calcite) peak intensity was measured. A calibration curve was prepared for the relationship between the intensity ratio and the mixing ratio, and the aragonite crystal content was determined using this. [Example 1] In a four-neck flask container having an appropriate capacity (the same container is used for the following Examples and Comparative Examples), slaked lime and 1
mol / L-NaOH aqueous solution, mixed at a ratio of 10% by weight as quick lime concentration to make lime milk, carbon dioxide content 10%
0% by volume of carbon dioxide gas is blown in at a flow rate of 2 L / min / kg CaO, at a temperature of 50 ° C and a stirring speed of 400 rpm (KYOEI POWER STIRRER TYPEPS
-2N, the same stirrer was used for the following Examples and Comparative Examples). After the completion of the reaction, the obtained slurry of calcium carbonate Using a filter paper of 5C, the solution was subjected to suction filtration with a Buchner funnel, washed several times with water, and subjected to analysis. As a result of X-ray diffraction measurement and morphological observation of the reaction product, acicular calcium carbonate having an average major axis of 8.0 μm and an average minor axis of 0.5 μm and having an aragonite crystal content of 99% was observed. Table 1 shows the experimental conditions and results.
Shown in [Example 2] The reaction was performed under the same conditions as in Example 1 except that the carbonation reaction was performed at a flow rate of carbon dioxide gas of 10 L / min / kg CaO. The product was found to be needle-like calcium carbonate having an average major axis of 3.5 μm and an average minor axis of 0.3 μm and having an aragonite crystal content of 87%. Table 1 shows the experimental conditions and results. [Example 3] Carrying out lime milk at a ratio of 20% by weight as quicklime concentration, blowing carbon dioxide gas at a flow rate of 2 L / min / kg CaO, and performing a carbonation reaction at a temperature of 75 ° C It carried out like Example 1. The product was found to be columnar calcium carbonate having an average major axis of 9.0 μm and an average minor axis of 0.5 μm and having an aragonite crystal content of 99%. Table 1 shows the experimental conditions and results. Comparative Example 1 Example 2 except that water was used for preparing lime milk.
The same was done. At this time, it was confirmed that the reaction product was mixed calcium carbonate having a sea urchin-like and granular shape with an aragonite crystal content of 59%. Table 1 shows the experimental conditions and results. [Comparative Example 2] The same procedure as in Example 3 was carried out except that water was used for the preparation of lime milk at a temperature of 50 ° C. The reaction product at this time was confirmed to be calcium carbonate having a aragonite crystal content of 41% and a mixture of granular and columnar shapes. Table 1 shows the experimental conditions and results.
【００２０】［比較例３］石灰乳の調製に0.5mol/L-NaO
Hと0.8mol/L-Na2CO3の混合溶液を用いて生石灰濃度とし
て20重量％になる割合で石灰乳を調製し、炭酸ガス流量
を4L/min/kg CaO、温度を75℃とした以外は実施例1と同
様に行った。この時の反応生成物は、アラゴナイト結晶
含有率36%で塊状と針状の混合した炭酸カルシウムであ
ることが認められた。実験条件および結果を表１に示
す。Comparative Example 3 For preparing lime milk, 0.5 mol / L-NaO was used.
Using a mixed solution of H and 0.8 mol / L-Na 2 CO 3 , lime milk was prepared at a ratio of quick lime concentration of 20% by weight, the carbon dioxide gas flow rate was 4 L / min / kg CaO, and the temperature was 75 ° C. Other than that, it carried out similarly to Example 1. The reaction product at this time was found to be a mixture of massive and acicular calcium carbonate with an aragonite crystal content of 36%. Table 1 shows the experimental conditions and results.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】実施例１〜3に示す如く、本発明による
炭酸カルシウムはアラゴナイト結晶の針状、柱状、イガ
グリ状の炭酸カルシウムであった。さらに、本法は炭酸
ガスの流量を高めた場合でも高アラゴナイト含有である
アラゴナイト結晶系炭酸カルシウムを製造することがで
きた。As shown in Examples 1 to 3, the calcium carbonate according to the present invention was aragonite crystal needle-like, column-like, or wiggly-like calcium carbonate. Further, this method was able to produce aragonite crystalline calcium carbonate having a high aragonite content even when the flow rate of carbon dioxide gas was increased.
【図１】 実施例１で得られた針状炭酸カルシウムの結
晶粒子構造を示す走査型電子顕微鏡写真である。FIG. 1 is a scanning electron micrograph showing the crystal particle structure of acicular calcium carbonate obtained in Example 1.
【図２】 実施例１で得られた生成物についてのＸ線回
折の結果を示す図である。FIG. 2 is a view showing a result of X-ray diffraction of a product obtained in Example 1.
【図３】 実施例２で得られた針状炭酸カルシウムの結
晶粒子構造を示す走査型電子顕微鏡写真である。FIG. 3 is a scanning electron micrograph showing the crystal particle structure of acicular calcium carbonate obtained in Example 2.
【図４】 比較例１で得られた粒状と柱状炭酸カルシウ
ムの結晶粒子構造を示す走査型電子顕微鏡写真である。FIG. 4 is a scanning electron micrograph showing a crystal particle structure of granular and columnar calcium carbonate obtained in Comparative Example 1.
【図５】 比較例１で得られた生成物についてのＸ線回
折の結果を示す図である。FIG. 5 is a view showing the result of X-ray diffraction of the product obtained in Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 南里 泰徳 山口県岩国市飯田町２丁目８番１号 日本 製紙株式会社岩国技術研究所内 Ｆターム(参考） 4G076 AA16 AB06 AB09 BA34 BB03 BD02 BD06 CA29 DA02 DA15 4L055 AG10 AG12 AG16 AG94 AH01 AH02 EA20 EA25 EA32 FA30 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasunori Minamisato 2-8-1, Iida-cho, Iwakuni-shi, Yamaguchi Japan F-term in Iwakuni Technical Research Laboratory, Japan 4G076 AA16 AB06 AB09 BA34 BB03 BD02 BD06 CA29 DA02 DA15 4L055 AG10 AG12 AG16 AG94 AH01 AH02 EA20 EA25 EA32 FA30
Claims (1)
スを導入することによって紙、ゴム、プラスチック等の
各種素材の充填材・顔料として有用なアラゴナイト結晶
系炭酸カルシウムを製造する方法であって、水酸化カル
シウム濃度が生石灰換算で5〜30重量％、好ましくは5〜
20重量％になるように、水酸化カルシウム1 molに対し
て0.25 mol以下、好ましくは0.1mol以下、より好ましく
は0.01mol以下の炭酸イオンを含む水酸化物イオン濃度
で0.01〜2M、好ましくは0.1〜1Mのアルカリ水溶液を添
加し、攪拌しながら調製した水酸化カルシウムの水性懸
濁液に、炭酸ガスを0.5〜10L/min/kg CaOの範囲で添加
し、反応温度20〜80℃にて炭酸化を行うことによりな
る、前記アラゴナイト結晶系炭酸カルシウムの製造方
法。1. A method for producing aragonite crystalline calcium carbonate useful as a filler / pigment for various materials such as paper, rubber and plastic by introducing carbon dioxide gas into an aqueous suspension of calcium hydroxide. The calcium hydroxide concentration is 5 to 30% by weight in terms of quicklime, preferably 5 to
The concentration of hydroxide ion containing carbonate ion of 0.25 mol or less, preferably 0.1 mol or less, more preferably 0.01 mol or less with respect to 1 mol of calcium hydroxide is 0.01 to 2 M, preferably 0.1 to 2% by weight. ~ 1M aqueous alkali solution is added, and to the aqueous suspension of calcium hydroxide prepared with stirring, carbon dioxide gas is added in a range of 0.5 ~ 10L / min / kg CaO, and carbon dioxide is added at a reaction temperature of 20 ~ 80 ° C. A method for producing the aragonite crystalline calcium carbonate, comprising:
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