JPH09309724A - Production of precipitated calcium carbonate - Google Patents
Production of precipitated calcium carbonateInfo
- Publication number
- JPH09309724A JPH09309724A JP12600996A JP12600996A JPH09309724A JP H09309724 A JPH09309724 A JP H09309724A JP 12600996 A JP12600996 A JP 12600996A JP 12600996 A JP12600996 A JP 12600996A JP H09309724 A JPH09309724 A JP H09309724A
- Authority
- JP
- Japan
- Prior art keywords
- water
- calcium carbonate
- calcium
- carbon dioxide
- aqueous suspension
- 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.)
- Granted
Links
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、軽質炭酸カルシウ
ムの製造方法に関するものである。さらに詳しくいえ
ば、本発明は、酸化カルシウムを原料とし、種晶を用い
て軽質炭酸カルシウムの粒径を制御する方法の改良に関
するものである。TECHNICAL FIELD The present invention relates to a method for producing light calcium carbonate. More specifically, the present invention relates to an improvement in a method of controlling the particle size of light calcium carbonate by using calcium oxide as a raw material and using seed crystals.
【０００２】[0002]
【従来の技術】従来、炭酸カルシウムは工業的には石灰
石を焼成して得た生石灰を原料に用いて、これを水と反
応させて消石灰水性スラリーを調製し、これを二酸化炭
素と反応させることにより軽質炭酸カルシウムとして製
造され、０．１μｍ以下の膠質粒子から数μｍ〜数十μ
ｍの粗大粒子までの種々の粒径のものや、紡錘状、角
状、柱状、針状、球状などの種々の形態のものが生産さ
れている。2. Description of the Related Art Conventionally, calcium carbonate is industrially prepared by using quicklime obtained by firing limestone as a raw material, reacting it with water to prepare an aqueous slaked lime slurry, and reacting it with carbon dioxide. Manufactured as light calcium carbonate by a few μm to several tens of μ from colloidal particles of 0.1 μm or less.
Various particle sizes up to coarse particles of m, and various forms such as spindle shape, angular shape, columnar shape, needle shape, and spherical shape are produced.
【０００３】この粒径の制御については、工業的には種
晶添加法が知られており、例えば、粒径０．０１〜０．
０９μｍの極微細種晶を炭酸化反応の途中で添加し、立
方体状炭酸カルシウムを製造する方法（特公平３−１９
１６５号公報）、カルシウム塩の水溶液に炭酸カルシウ
ム種晶を特定比で加えたのち、二酸化炭素を導入するこ
とにより、種晶表面に析出する炭酸カルシウムの量を調
整して平均粒径を制御する方法（特開昭６３−２３０５
２０号公報）、一部炭酸化された膠質粒子状水酸化カル
シウム水性懸濁液を所定割合で炭酸化率が所定値になる
までに添加して均一で分散性が良好な所定紡錘状炭酸カ
ルシウムを製造する方法（特公平８−１８８２７号公
報）、この方法を酸化カルシウムの湿式消化後液体サイ
クロン処理して調製した水酸化カルシウム水性懸濁液を
原料に用いて行う方法（特開平６−５６４２２号公報）
などが提案されている。For controlling the grain size, a seed crystal addition method is industrially known. For example, the grain size of 0.01 to 0.
A method for producing cubic calcium carbonate by adding ultrafine seed crystals of 09 μm during the carbonation reaction (Japanese Patent Publication No. 3-19).
No. 165), calcium carbonate seed crystals are added to an aqueous solution of calcium salt at a specific ratio, and then carbon dioxide is introduced to adjust the amount of calcium carbonate precipitated on the seed crystal surface to control the average particle diameter. Method (JP-A-63-2305
No. 20), a predetermined spindle-shaped calcium carbonate having a uniform and good dispersibility by adding a partially carbonated colloidal particulate calcium hydroxide aqueous suspension at a predetermined ratio until the carbonation rate reaches a predetermined value. (Japanese Patent Publication No. 8-18827), a method of using this method as a raw material, which is an aqueous suspension of calcium hydroxide prepared by wet cyclodigestion of calcium oxide and then subjecting to hydrocyclone treatment (JP-A-6-56422). Issue)
Have been proposed.
【０００４】しかしながら、これらの方法では、種晶を
生成させる反応を別に行わねばならないため煩雑とな
り、また反応器やタンク等の新たな設備が必要となるな
どの問題を生じるのを免れない。However, these methods are unavoidable in that the reaction for forming seed crystals must be carried out separately, which is complicated and requires new equipment such as a reactor and a tank.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、このような
種晶を用いて粒径を制御する従来法の欠点を克服し、操
作を簡便にして効率よく工業的に炭酸カルシウムを製造
する方法を提供することを目的としてなされたものであ
る。DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the conventional method of controlling the particle size by using such seed crystals, simplifies the operation, and efficiently and industrially produces calcium carbonate. It is made for the purpose of providing.
【０００６】[0006]
【課題を解決するための手段】本発明者は、前記の好ま
しい特徴を有する炭酸カルシウムの工業的製法を開発す
るために種々研究を重ねた結果、所定炭酸化反応で生成
される炭酸カルシウム水性スラリーの脱水やろ過で生じ
る分離水やろ水を、消化用の水の全部あるいは一部に用
いることにより、その目的を達成しうることを見出し、
この知見に基づいて本発明を完成するに至った。The present inventor has conducted various studies to develop an industrial production method of calcium carbonate having the above-mentioned preferable characteristics, and as a result, an aqueous calcium carbonate slurry produced by a predetermined carbonation reaction. It was found that the purpose can be achieved by using the separated water or the filtered water produced by the dehydration or filtration of the whole or part of the water for digestion,
Based on this finding, the present invention has been completed.
【０００７】すなわち、本発明は、酸化カルシウムに水
を加え湿式消化させて水酸化カルシウム水性懸濁液を調
製し、次いでこの水性懸濁液に二酸化炭素又は二酸化炭
素含有ガスを吹き込み炭酸化することにより軽質炭酸カ
ルシウムを製造するに当り、消化用の水として、水酸化
カルシウム水性懸濁液の炭酸化反応で生成される炭酸カ
ルシウム水性スラリーの分離脱水処理により得られる分
離水及び該スラリーのろ過処理により得られるろ水の中
から選ばれた少なくとも１種あるいはそれを混入させた
水を用いることを特徴とする軽質炭酸カルシウムの製造
方法を提供するものである。That is, according to the present invention, water is added to calcium oxide for wet digestion to prepare a calcium hydroxide aqueous suspension, and then carbon dioxide or a carbon dioxide-containing gas is blown into the aqueous suspension for carbonation. In producing light calcium carbonate by means of water, as water for digestion, separated water obtained by separation and dehydration treatment of calcium carbonate aqueous slurry produced by carbonation reaction of calcium hydroxide aqueous suspension, and filtration treatment of the slurry The present invention provides a method for producing light calcium carbonate, which comprises using at least one selected from the filtered water obtained in step 1 or water mixed with it.
【０００８】[0008]
【発明の実施の形態】本発明方法においては、酸化カル
シウムを所定の水で湿式消化させて水酸化カルシウム水
性懸濁液を調製し、次いでこの水性懸濁液に二酸化炭素
やそれを含有するガスを吹き込み炭酸化することにより
軽質炭酸カルシウムが製造される。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, calcium oxide is wet-digested with predetermined water to prepare a calcium hydroxide aqueous suspension, and then carbon dioxide or a gas containing the same is added to the aqueous suspension. Light calcium carbonate is produced by blowing and carbonating.
【０００９】この所定の消化用の水は、水酸化カルシウ
ム水性懸濁液の炭酸化反応で生成される炭酸カルシウム
水性スラリーの分離脱水処理により得られる分離水及び
該スラリーのろ過処理により得られるろ水の中から選ば
れた少なくとも１種あるいはそれを混入させた水であ
る。この分離脱水処理としては、遠心分離処理や沈降分
離処理が好適に用いられ、その他、浮上分離処理も用い
られる。遠心分離処理は、通常、適当な装置、例えば遠
心沈降機、遠心ろ過機、遠心分離機、遠心傾瀉機（デカ
ンター）、遠心清澄機（クラリファイヤー）などを用い
て行われる。ろ過処理として好適には加圧又は真空下に
行う加圧ろ過処理又は真空ろ過処理が行われ、加圧ろ過
処理はフィルタープレスやベルトプレスによるのが、ま
た真空ろ過処理はオリバーフィルターやドラムフィルタ
ーによるのが好ましい。上記消化用の水には、炭酸カル
シウムが含有されており、その濃度は０．０５〜１０ｇ
／リットル、中でも０．１〜７ｇ／リットルの範囲に調
整するのが好ましい。また、消化用の水は導電率が０．
２〜１０ｍＳ／ｃｍであるものが好ましい。上記分離水
やろ水を水に混入させる場合、この水としては通常、工
業用水、井戸水、地下水などが用いられる。The predetermined water for digestion is separated water obtained by separating and dehydrating the calcium carbonate aqueous slurry produced by the carbonation reaction of the calcium hydroxide aqueous suspension, and filtered by the filtration treatment of the slurry. It is at least one selected from water or water containing it. As the separation / dehydration treatment, centrifugal separation treatment or sedimentation separation treatment is preferably used, and in addition, floating separation treatment is also used. Centrifugation treatment is usually performed using an appropriate device, for example, a centrifugal settler, a centrifugal filter, a centrifuge, a centrifugal decanter (decanter), a centrifugal clarifier (clarifier), or the like. The filtration treatment is preferably a pressure filtration treatment or a vacuum filtration treatment performed under pressure or vacuum. The pressure filtration treatment is performed by a filter press or a belt press, and the vacuum filtration treatment is performed by an oliver filter or a drum filter. Is preferred. The water for digestion contains calcium carbonate, and its concentration is 0.05 to 10 g.
/ Liter, preferably 0.1 to 7 g / liter. Also, water for digestion has a conductivity of 0.
It is preferably 2 to 10 mS / cm. When the separated water or filtered water is mixed with water, industrial water, well water, ground water, etc. are usually used.
【００１０】本発明方法において、この生石灰の水によ
る湿式消化は、濃度５０〜１５０ｇ‐ＣａＯ／リットル
好ましくは６０〜１２０ｇ‐ＣａＯ／リットル、消化水
温度２０〜９０℃好ましくは３０〜７０℃及び平均滞留
時間６０分以内好ましくは３〜３０分という消化条件下
で行うことが必要である。この条件の範囲を逸脱すると
所期の効果が得られない。すなわち、この濃度が高すぎ
ると生成する消石灰水性スラリーの粘度が上昇し、残さ
が増大するし、また低すぎても効率的でなくなる。消化
水温度が９０℃より高いと生成する消石灰水性スラリー
の粘度が上昇し、熱経済的にもよくないし、また２０℃
より低いと消化に時間がかかり、効率的でなくなる。平
均滞留時間が長すぎると消石灰の粒径の幅が大きくな
り、炭酸カルシウムの粒度分布のばらつきや不揃いの原
因となる。また、湿式消化は連続湿式型のスレーカーを
用いて行うのが好ましい。In the method of the present invention, the wet digestion of quicklime with water has a concentration of 50 to 150 g-CaO / liter, preferably 60 to 120 g-CaO / liter, a digestion water temperature of 20 to 90 ° C., preferably 30 to 70 ° C. and an average. It is necessary to carry out the reaction under a digestion condition of a residence time of 60 minutes or less, preferably 3 to 30 minutes. If the range of this condition is exceeded, the desired effect cannot be obtained. That is, if this concentration is too high, the viscosity of the slaked lime aqueous slurry produced increases, and the residue increases, and if it is too low, it becomes inefficient. When the digestion water temperature is higher than 90 ° C, the viscosity of the slaked lime aqueous slurry formed increases, which is not good in terms of thermo-economical condition, and 20 ° C
Lower levels will take longer to digest and are less efficient. If the average residence time is too long, the range of particle size of slaked lime becomes large, which causes variation or unevenness in the particle size distribution of calcium carbonate. The wet digestion is preferably performed using a continuous wet type breaker.
【００１１】このような湿式消化により消石灰水性スラ
リーが調製される。本発明方法においては、この水性ス
ラリーに二酸化炭素を吹き込み炭酸化することにより軽
質炭酸カルシウムを製造することができる。この炭酸化
反応は通常用いられる方法で行われ、好ましくは消石灰
濃度５０〜２００ｇ／リットル、中でも６０〜１５０ｇ
／リットルの消石灰水性スラリーに、二酸化炭素濃度５
〜４０容量％、中でも１０〜３５容量％の二酸化炭素含
有ガスを消石灰１ｋｇ当り標準状態で毎分１〜１２リッ
トル、中でも３〜１０リットルになる割合で反応開始温
度３０〜７０℃、中でも３５〜６０℃で吹き込む方法が
用いられる。A slaked lime aqueous slurry is prepared by such wet digestion. In the method of the present invention, light calcium carbonate can be produced by blowing carbon dioxide into this aqueous slurry for carbonation. This carbonation reaction is carried out by a commonly used method, preferably a slaked lime concentration of 50 to 200 g / liter, and particularly 60 to 150 g.
/ Liter of slaked lime aqueous slurry, carbon dioxide concentration 5
-40% by volume, especially 10-35% by volume of carbon dioxide-containing gas per kg of slaked lime in a standard state of 1 to 12 liters per minute, particularly 3 to 10 liters at a reaction initiation temperature of 30 to 70 ° C., particularly 35 to 35 liters. A method of blowing at 60 ° C. is used.
【００１２】本発明方法においては、炭酸化反応に二酸
化炭素又は二酸化炭素含有ガスが用いられるが、工業的
には二酸化炭素含有ガスが好ましい。二酸化炭素含有ガ
スとして好適には、二酸化炭素を含有する混合ガス、例
えば石灰石焼成キルン排ガスなどの石灰石焼成排ガス、
パルプ製造プラントの石灰キルン排ガスなどの石灰焼成
排ガス、発電ボイラー排ガス、ゴミ焼却排ガスなどが用
いられる。In the method of the present invention, carbon dioxide or a carbon dioxide-containing gas is used in the carbonation reaction, but the carbon dioxide-containing gas is industrially preferable. Suitably as carbon dioxide-containing gas, mixed gas containing carbon dioxide, for example limestone firing exhaust gas such as limestone firing kiln exhaust gas,
Lime firing exhaust gas such as lime kiln exhaust gas from a pulp manufacturing plant, power generation boiler exhaust gas, and waste incineration exhaust gas are used.
【００１３】二酸化炭素含有ガスとして上記各種排ガス
を用いる場合には、排ガス中に石灰石、石灰、硫黄酸化
物、未燃焼カーボン等のダストが含まれているので、ダ
ストを、バグフィルター、電気集塵機、湿式スクラバー
あるいはそれらの組合せで除塵して排ガスを浄化するよ
うにする。上記排ガスは、乾性ガスであってもよいし、
また湿性ガスであってもよく、乾性ガスの場合には前以
てバグフィルターや電気集塵機である程度浄化したの
ち、さらに湿式スクラバーで所望程度まで浄化するのが
好ましく、また湿性ガスの場合には多段の湿式スクラバ
ーで所望程度まで浄化するかあるいは前以て湿式電気集
塵機である程度浄化したのち、さらに湿式スクラバーで
所望程度まで浄化するのが好ましい。When the above-mentioned various exhaust gases are used as the carbon dioxide-containing gas, the exhaust gases contain dust such as limestone, lime, sulfur oxides and unburned carbon. Use a wet scrubber or a combination of them to remove dust and purify the exhaust gas. The exhaust gas may be a dry gas,
It may be moist gas. In the case of dry gas, it is preferable to purify to some extent with a bag filter or an electrostatic precipitator in advance, and then to a desired degree with a wet scrubber. It is preferable to purify to a desired degree with the wet scrubber or to some degree with a wet electrostatic precipitator, and then to a desired degree with a wet scrubber.
【００１４】本発明方法においては、必要に応じ、本発
明の目的をそこなわない範囲で、従来の種晶添加法を若
干併用することができる。In the method of the present invention, a conventional seed crystal addition method may be used in combination, if necessary, within a range not impairing the object of the present invention.
【００１５】本発明方法で得られる軽質炭酸カルシウム
としては、好ましくはカルサイトであり、さらには粒子
形状が紡錘状又は偏三角面体状（ｓｃａｌｅｎｏｈｅｄ
ｒａｌ）であるものがよい。The light calcium carbonate obtained by the method of the present invention is preferably calcite, and the particle shape is spindle-shaped or scalenohedron-shaped.
ral) is preferable.
【００１６】[0016]
【実施例】次に、実施例により本発明をさらに詳細に説
明する。各例に用いた酸化カルシウムは、天然産石灰石
をＣサイズに粒度調整し、ベッケンバッハ炉で焼成した
ＪＩＳ特号相当品の酸化カルシウムを篩分けし、粒分を
ジョークラッシャーで粉砕したものである。Next, the present invention will be described in more detail with reference to examples. The calcium oxide used in each example is obtained by adjusting the particle size of natural limestone to C size, sieving the calcium oxide of JIS special product equivalent to that baked in a Beckenbach furnace, and crushing the particles with a jaw crusher. .
【００１７】比較例 １０００リットルの容器に東京都西多摩郡瑞穂町の導電
率０．１ｍＳ／ｃｍの水道水を６００リットル入れ、６
０℃に調整した。撹拌機を用い５００ｒｐｍでかきまぜ
ながら、生石灰４２ｋｇを加え、３０分後に３２５メッ
シュ篩でろ過し、８５ｇ／リットルの濃度の水酸化カル
シウム水性スラリーを得た。このスラリー３００リット
ルを半回分式反応器に仕込み、５０℃に調整したのち、
この反応器中のスラリーに、０．５ｇ／Ｎｍ3のダスト
濃度をバグフィルターで０．００５ｇ／Ｎｍ3に、さら
に湿式スクラバーで０．００３ｇ／Ｎｍ3に減少させて
除塵することによって浄化した、二酸化炭素濃度３０容
量％のベッケンバッハ型石灰焼成炉排ガスを、水酸化カ
ルシウム１ｋｇ当り１００容量％二酸化炭素換算で５Ｎ
リットル／分の割合で吹き込み、炭酸化率が１００％に
なるまで反応させて炭酸カルシウム水性懸濁液を得た。
このものを３２５メッシュ篩でろ過して得た炭酸カルシ
ウムは、ＳＥＭ写真（倍率×１００００）よりデジマチ
ックノギスで粒径を測定したところ、平均長径４．１μ
ｍ、平均短径１．５μｍの紡錘状粒子であった。Comparative Example 600 liters of tap water having conductivity of 0.1 mS / cm from Mizuho-cho, Nishitama-gun, Tokyo was placed in a container of 1000 liters.
The temperature was adjusted to 0 ° C. While stirring at 500 rpm with a stirrer, 42 kg of quick lime was added, and after 30 minutes, filtration was performed with a 325 mesh sieve to obtain a calcium hydroxide aqueous slurry having a concentration of 85 g / liter. After charging 300 liters of this slurry into a semi-batch type reactor and adjusting the temperature to 50 ° C.,
The slurry in the reactor was clean the dust concentration of 0.5 g / Nm 3 to 0.005 g / Nm 3 with a bag filter, by dedusting by further reduced in wet scrubber to 0.003 g / Nm 3, Exhaust gas from a Beckenbach-type lime calcination furnace with a carbon dioxide concentration of 30% by volume was converted to 100% by volume of carbon dioxide per kg of calcium hydroxide, and converted to 5N.
It was blown in at a rate of 1 / min and reacted until the carbonation rate reached 100% to obtain a calcium carbonate aqueous suspension.
The calcium carbonate obtained by filtering this through a 325-mesh sieve was measured with a Digimatic caliper from SEM photographs (magnification: 10,000) to find that the average major axis was 4.1 μm.
m, and an average minor axis of 1.5 μm.
【００１８】実施例１ 比較例と同様にして得られた炭酸カルシウム水性懸濁液
をフィルタープレスを用いてろ過し、含水率４０重量％
の炭酸カルシウムケーキと炭酸カルシウム濃度５ｇ／リ
ットル、導電率１．５ｍＳ／ｃｍのろ過水を得た。この
ろ過水２００リットルを３００リットルの容器に入れ、
６０℃に調整した。撹拌機を用い５００ｒｐｍでかきま
ぜながら、生石灰１４ｋｇを加え、３０分後に３２５メ
ッシュ篩でろ過し、８５ｇ／リットルの濃度の水酸化カ
ルシウム水性スラリーを得た。このスラリー２００リッ
トルを半回分式反応器に仕込み、５０℃に調整したの
ち、この反応器中のスラリーに、比較例と同様に浄化し
た二酸化炭素濃度３０容量％のベッケンバッハ型石灰焼
成炉排ガスを、水酸化カルシウム１ｋｇ当り１００容量
％二酸化炭素換算で５Ｎリットル／分の割合で吹き込
み、炭酸化率が１００％になるまで反応させて炭酸カル
シウム水性懸濁液を得た。このものを３２５メッシュ篩
でろ過して得た炭酸カルシウムは、ＳＥＭ写真（倍率×
３０００）よりデジマチックノギスで粒径を測定したと
ころ、平均長径２．６μｍ、平均短径０．８μｍの紡錘
状粒子であった。Example 1 An aqueous calcium carbonate suspension obtained in the same manner as in Comparative Example was filtered using a filter press to give a water content of 40% by weight.
To obtain filtered water having a calcium carbonate concentration of 5 g / liter and an electric conductivity of 1.5 mS / cm. Put 200 liters of this filtered water in a 300 liter container,
The temperature was adjusted to 60 ° C. While stirring at 500 rpm with a stirrer, 14 kg of quick lime was added, and 30 minutes later, the mixture was filtered through a 325 mesh sieve to obtain a calcium hydroxide aqueous slurry having a concentration of 85 g / liter. 200 liters of this slurry was charged into a semi-batch type reactor and adjusted to 50 ° C., and then the Beckenbach type lime calcination furnace exhaust gas with a carbon dioxide concentration of 30% by volume purified in the same manner as in the comparative example was added to the slurry in this reactor. Then, it was blown at a rate of 5 N liter / min in terms of 100 volume% carbon dioxide per 1 kg of calcium hydroxide and reacted until the carbonation rate reached 100% to obtain a calcium carbonate aqueous suspension. The calcium carbonate obtained by filtering this through a 325 mesh sieve was a SEM photograph (magnification ×
The particle size was measured with a Digimatic caliper from 3000) to find that the particles were spindle-shaped particles having an average major axis of 2.6 μm and an average minor axis of 0.8 μm.
【００１９】実施例２ 実施例１と同様にして得られた炭酸カルシウム水性懸濁
液をフィルタープレスを用いてろ過し、含水率４０重量
％の炭酸カルシウムケーキと炭酸カルシウム濃度６ｇ／
リットル、導電率１．７ｍＳ／ｃｍのろ過水を得た。こ
のろ過水４０リットルを６０リットルの容器に入れ、６
０℃に調整した。撹拌機を用い５００ｒｐｍでかきまぜ
ながら、生石灰２．８ｋｇを加え、３０分後に３２５メ
ッシュ篩でろ過し、８５ｇ／リットルの濃度の水酸化カ
ルシウム水性スラリーを得た。このスラリー３０リット
ルを半回分式反応器に仕込み、５０℃に調整したのち、
この反応器中のスラリーに、比較例と同様に浄化した二
酸化炭素濃度３０容量％のベッケンバッハ型石灰焼成炉
排ガスを、水酸化カルシウム１ｋｇ当り１００容量％二
酸化炭素換算で５Ｎｍ3／ｈｒの割合で吹き込み、炭酸
化率が１００％になるまで反応させて炭酸カルシウム水
性懸濁液を得た。このものを３２５メッシュ篩でろ過し
て得た炭酸カルシウムは、ＳＥＭ写真（倍率×１０００
０）よりデジマチックノギスで粒径を測定したところ、
平均長径２．５μｍ、平均短径０．７μｍの紡錘状粒子
であった。Example 2 An aqueous calcium carbonate suspension obtained in the same manner as in Example 1 was filtered using a filter press to give a calcium carbonate cake having a water content of 40% by weight and a calcium carbonate concentration of 6 g /
Filtrate water having a liter and an electric conductivity of 1.7 mS / cm was obtained. Put 40 liters of this filtered water in a 60 liter container,
The temperature was adjusted to 0 ° C. While stirring at 500 rpm with a stirrer, 2.8 kg of quick lime was added, and after 30 minutes, the mixture was filtered through a 325 mesh sieve to obtain a calcium hydroxide aqueous slurry having a concentration of 85 g / liter. After charging 30 liters of this slurry into a semi-batch type reactor and adjusting the temperature to 50 ° C.,
Beckenbach-type lime calcination furnace exhaust gas having a carbon dioxide concentration of 30% by volume, which had been purified in the same manner as in the comparative example, was added to the slurry in this reactor at a rate of 5 Nm 3 / hr in terms of 100% by volume of carbon dioxide per 1 kg of calcium hydroxide. It was blown in and reacted until the carbonation rate reached 100% to obtain a calcium carbonate aqueous suspension. Calcium carbonate obtained by filtering this through a 325 mesh sieve was a SEM photograph (magnification × 1000
From 0), the particle size was measured with a Digimatic caliper,
The spindle-shaped particles had an average major axis of 2.5 μm and an average minor axis of 0.7 μm.
【００２０】実施例３ 実施例２の容器に入れたろ過水４０リットルに代えて、
実施例２と同様にして得られたろ過水３０リットルと前
記水道水１０リットルを消化水として用いた以外は、実
施例２と同様にして消化、炭酸化反応を行い、３２５メ
ッシュ篩いでろ過して得た炭酸カルシウムは、ＳＥＭ写
真（倍率×１００００）よりデジマチックノギスで粒径
を測定したところ、平均長径２．８μｍ、平均短径０．
８μｍの紡錘状粒子であった。Example 3 Instead of 40 liters of filtered water contained in the container of Example 2,
Digestion and carbonation were carried out in the same manner as in Example 2 except that 30 liters of filtered water obtained in the same manner as in Example 2 and 10 liters of tap water were used as digestion water, and filtered through a 325 mesh sieve. The particle diameter of the obtained calcium carbonate was measured with a Digimatic caliper from an SEM photograph (magnification: 10000). The average major axis was 2.8 μm, and the average minor axis was 0.2 μm.
It was a spindle-shaped particle of 8 μm.
【００２１】実施例４ ろ過水と水道水の使用量をそれぞれ２０リットルに変え
た以外は、実施例２と同様にして消化、炭酸化反応を行
い、３２５メッシュ篩いでろ過して得た炭酸カルシウム
は、ＳＥＭ写真（倍率×１００００）よりデジマチック
ノギスで粒径を測定したところ、平均長径３．０μｍ、
平均短径０．９μｍの紡錘状粒子であった。Example 4 Calcium carbonate obtained by digesting and carbonating in the same manner as in Example 2 except that the amounts of filtered water and tap water used were changed to 20 liters, respectively, and filtered through a 325 mesh sieve. Is the average major axis 3.0 μm
It was a spindle-shaped particle having an average short diameter of 0.9 μm.
【００２２】実施例５ ろ過水と水道水の使用量をそれぞれ１０リットルと３０
リットルに変えた以外は、実施例２と同様にして消化、
炭酸化反応を行い、３２５メッシュ篩いでろ過して得た
炭酸カルシウムは、ＳＥＭ写真（倍率×１００００）よ
りデジマチックノギスで粒径を測定したところ、平均長
径３．３μｍ、平均短径１．０μｍの紡錘状粒子であっ
た。Example 5 The amounts of filtered water and tap water used were 10 liter and 30 respectively.
Digested in the same manner as in Example 2 except that the liter was changed to
The calcium carbonate obtained by carrying out a carbonation reaction and filtering through a 325 mesh sieve was measured for its particle diameter with a Digimatic caliper from an SEM photograph (magnification: 10000). The average major axis was 3.3 μm and the average minor axis was 1.0 μm. It was a spindle-shaped particle of.
【００２３】実施例６ 比較例と同様にして調製された水酸化カルシウム水性懸
濁液を３０ｇ／リットルに濃度調整したものを３０リッ
トル半回分式反応器に仕込み、１５℃に温度調節し、比
較例と同様にして調製された二酸化炭素含有排ガスを、
水酸化カルシウム１ｋｇ当り１００容量％二酸化炭素換
算で８Ｎリットル／分の割合で吹き込んで炭酸化反応を
行い、炭酸化率３５％のところで反応を停止し、一次炭
酸化水酸化カルシウム水性スラリーを得た。比較例と同
様にして得られた炭酸カルシウム水性懸濁液をオリバー
フィルターを用いてろ過して得た炭酸カルシウム濃度５
ｇ／リットル、導電率１．３ｍＳ／ｃｍのろ過水と工業
用水を３：１の割合で混合し、４０℃に調整したものを
消化水として用い、連続式湿式消化方式のスレーカーに
おいて、生石灰と共に定量供給を行い、スレーカーで未
消化残さを除去し、８０ｇ／リットル濃度の水酸化カル
シウム水性スラリーを得た。この水酸化カルシウム水性
スラリー３０リットルと上記一次炭酸化水酸化カルシウ
ム水性スラリー０．８リットルを反応器で混合し、比較
例と同様にして炭酸化反応させて炭酸カルシウム水性懸
濁液を得た。このものを３２５メッシュ篩でろ過して得
た炭酸カルシウムは、ＳＥＭ写真（倍率×１００００）
よりデジマチックノギスで粒径を測定したところ、平均
長径１．５μｍ、平均短径０．４μｍの紡錘状粒子であ
った。Example 6 A calcium hydroxide aqueous suspension prepared in the same manner as in the comparative example, the concentration of which was adjusted to 30 g / liter, was charged into a 30 liter semi-batch type reactor and the temperature was adjusted to 15 ° C. A carbon dioxide-containing exhaust gas prepared in the same manner as in the example,
A carbonation reaction was carried out by blowing at a rate of 8 N liters / minute in terms of 100 vol% carbon dioxide per 1 kg of calcium hydroxide, and the reaction was stopped at a carbonation rate of 35% to obtain a primary carbonated calcium hydroxide aqueous slurry. . A calcium carbonate aqueous suspension obtained in the same manner as in Comparative Example was filtered using an Oliver filter to obtain a calcium carbonate concentration of 5
g / l, filtered water having conductivity of 1.3 mS / cm and industrial water were mixed at a ratio of 3: 1 and adjusted to 40 ° C. and used as digestion water. In a continuous wet digestion type slaker, along with quicklime A fixed amount was supplied and the undigested residue was removed with a slaker to obtain a calcium hydroxide aqueous slurry having a concentration of 80 g / liter. 30 liters of this calcium hydroxide aqueous slurry and 0.8 liter of the above-mentioned primary carbonated calcium hydroxide aqueous slurry were mixed in a reactor and subjected to carbonation reaction in the same manner as in Comparative Example to obtain a calcium carbonate aqueous suspension. Calcium carbonate obtained by filtering this through a 325 mesh sieve is a SEM photograph (magnification x 10000)
When the particle size was measured with a Digimatic caliper, the particles were spindle-shaped particles having an average major axis of 1.5 μm and an average minor axis of 0.4 μm.
【００２４】実施例７ 比較例と同様にして得られた炭酸カルシウム水性懸濁液
をスクリュウデカンターを用いてろ過して得た炭酸カル
シウム濃度４ｇ／リットル、導電率１．０ｍＳ／ｃｍの
ろ過水と工業用水を３：１の割合で混合し、４０℃に調
整したものを消化水として用い、連続式湿式消化方式の
スレーカーにおいて、生石灰と共に定量供給を行い、ス
レーカーで未消化残さを除去し、３２５メッシュ篩でろ
過を行い、次いで公称カットポイントが１０μｍの２液
分離型の液体サイクロン（Ｔ−１０：大石機械製）にか
け、トップから吐出された６０ｇ／リットル濃度の水酸
化カルシウム水性スラリーを得た。この水酸化カルシウ
ム水性スラリー３０リットルと実施例６と同様にして得
られた一次炭酸化水酸化カルシウム水性スラリー１．２
リットルを反応器で混合し、比較例と同様にして炭酸化
反応させて炭酸カルシウム水性懸濁液を得た。このもの
を３２５メッシュ篩でろ過して得た炭酸カルシウムは、
ＳＥＭ写真（倍率×１００００）よりデジマチックノギ
スで粒径を測定したところ、平均長径０．８μｍ、平均
短径０．２μｍの紡錘状粒子であった。Example 7 An aqueous suspension of calcium carbonate obtained in the same manner as in Comparative Example was filtered with a screw decanter to obtain filtered water having a calcium carbonate concentration of 4 g / liter and an electric conductivity of 1.0 mS / cm. Industrial water was mixed at a ratio of 3: 1 and adjusted to 40 ° C. was used as digestion water, and in a continuous wet digestion system slaker, fixed amount was supplied together with quick lime, and an undigested residue was removed with a slaker. The mixture was filtered through a mesh sieve and then applied to a two-liquid separation type liquid cyclone (T-10: made by Oishi Machine Co., Ltd.) having a nominal cut point of 10 μm to obtain a 60 g / l concentration calcium hydroxide aqueous slurry discharged from the top. . 30 liters of this calcium hydroxide aqueous slurry and 1.2 of the primary carbonated calcium hydroxide aqueous slurry obtained in the same manner as in Example 6
The liters were mixed in a reactor and subjected to a carbonation reaction in the same manner as in Comparative Example to obtain a calcium carbonate aqueous suspension. The calcium carbonate obtained by filtering this through a 325 mesh sieve is
When the particle size was measured with a Digimatic caliper from an SEM photograph (magnification: 10,000), the particles were spindle-shaped particles having an average major axis of 0.8 μm and an average minor axis of 0.2 μm.
【００２５】応用例 実施例２〜６及び比較例で得た炭酸カルシウム水性スラ
リーをフィルタープレスでろ過して固形分が４０重量％
の炭酸カルシウムケーキとしたのち、適量の水を加えて
炭酸カルシウム含量が４００ｇ／リットル（固形分３２
重量％）の炭酸カルシウムスラリーを作製した。このス
ラリーを適当に希釈し、これを広葉樹クラフトパルプ
（３５０ｃｓｆ）と針葉樹クラフトパルプ（４５０ｃｓ
ｆ）を重量比７：３で混合したパルプ原料１００重量部
に配合し、さらに紙力増強剤としてカチオン化デンプン
０．５重量部、中性サイズ剤としてのアルキルケテンダ
イマー０．２重量部、歩留まり向上剤としてのポリアク
リルアミド０．０２重量部を添加し、填料添加率をパル
プに対し１５％とし、坪量４０ｇ／ｍ２で角型シートマ
シンを用いた手抄きにより、炭酸カルシウム内填紙を得
た。このものの物性を表１に示す。Application Examples The calcium carbonate aqueous slurries obtained in Examples 2 to 6 and Comparative Example were filtered with a filter press to obtain a solid content of 40% by weight.
After making the calcium carbonate cake, add an appropriate amount of water to give a calcium carbonate content of 400 g / liter (solid content 32
% By weight) calcium carbonate slurry was prepared. This slurry is appropriately diluted, and this is diluted with hardwood kraft pulp (350csf) and softwood kraft pulp (450cs).
f) was mixed with 100 parts by weight of a pulp raw material mixed at a weight ratio of 7: 3, 0.5 part by weight of cationized starch as a paper-strengthening agent, 0.2 part by weight of alkyl ketene dimer as a neutral sizing agent, Add 0.02 part by weight of polyacrylamide as a yield improver, make the filler addition rate 15% with respect to pulp, and add calcium carbonate by hand making with a square sheet machine at a basis weight of 40 g / m 2. Got the paper. The physical properties of this product are shown in Table 1.
【００２６】なお、表中の各物性は次のようにして測定
した。 （１）歩留り：ＪＩＳ Ｐ ８１２９により測定。 （２）灰分 ：ＪＩＳ Ｐ ８１２８により測定。 （３）白色度：ＪＩＳ Ｐ ８１２３により測定。 （４）不透明度：ＪＩＳ Ｐ ８１３６により測定。 （５）引張強度：ＪＩＳ Ｐ ８１１３により測定。The physical properties in the table were measured as follows. (1) Yield: Measured according to JIS P8129. (2) Ash: Measured according to JIS P8128. (3) Whiteness: Measured according to JIS P8123. (4) Opacity: Measured according to JIS P 8136. (5) Tensile strength: Measured according to JIS P 8113.
【００２７】[0027]
【表１】 [Table 1]
【００２８】これより、実施例で得られた炭酸カルシウ
ムはいずれも比較例のそれに比べ白色度や不透明度に優
れていることが分る。From the above, it can be seen that the calcium carbonates obtained in the examples are superior in whiteness and opacity to those of the comparative examples.
【００２９】[0029]
【発明の効果】本発明方法によれば、従来の種晶添加法
に比べ、種晶を生成させる反応を別に行わなくてすむた
め操作が簡便であり、水の使用量を節減でき、また反応
器やタンク等の新たな設備を要しないためコストダウン
を図れる上に、均一で分散性良好な軽質炭酸カルシウ
ム、特にカルサイト系の、さらに好適には紡錘状又は偏
三角面体状（ｓｃａｌｅｎｏｈｅｄｒａｌ）の軽質炭酸
カルシウムを得ることができる。この軽質炭酸カルシウ
ムは分散性が高いため、高濃度スラリー化して紙の内填
あるいは塗工に供すると、高い不透明性や隠蔽性を与え
るし、またさらに適当な表面改質剤で表面処理が施され
たものは、ゴムや樹脂の充填材として優れた機械特性を
与えるという利点もある。EFFECTS OF THE INVENTION According to the method of the present invention, as compared with the conventional seed crystal addition method, the reaction for forming the seed crystal does not have to be performed separately, so that the operation is simple and the amount of water used can be reduced. Costs can be reduced because new equipment such as vessels and tanks is not required, and light calcium carbonate that is uniform and has good dispersibility, particularly calcite-based, and more preferably spindle-shaped or scalenehedron-shaped (scalenohedral) Light calcium carbonate can be obtained. Since this light calcium carbonate has high dispersibility, when it is made into a high-concentration slurry and used for filling the paper or coating it, it provides high opacity and hiding power, and is further surface-treated with a suitable surface modifier. The obtained product also has an advantage of giving excellent mechanical properties as a filler of rubber or resin.
Claims (4)
て水酸化カルシウム水性懸濁液を調製し、次いでこの水
性懸濁液に二酸化炭素又は二酸化炭素含有ガスを吹き込
み炭酸化することにより軽質炭酸カルシウムを製造する
に当り、消化用の水として、水酸化カルシウム水性懸濁
液の炭酸化反応で生成される炭酸カルシウム水性スラリ
ーの分離脱水処理により得られる分離水及び該スラリー
のろ過処理により得られるろ水の中から選ばれた少なく
とも１種あるいはそれを混入させた水を用いることを特
徴とする軽質炭酸カルシウムの製造方法。1. Light calcium carbonate prepared by adding water to calcium oxide and subjecting it to wet digestion to prepare a calcium hydroxide aqueous suspension, and then carbon dioxide by blowing carbon dioxide or a carbon dioxide-containing gas into the aqueous suspension. In the production of water, as water for digestion, separated water obtained by separation and dehydration treatment of an aqueous calcium carbonate slurry produced by a carbonation reaction of an aqueous suspension of calcium hydroxide and a filter obtained by filtration treatment of the slurry. A method for producing light calcium carbonate, characterized by using at least one selected from water or water mixed with it.
〜１０ｇ／リットルの濃度で含有する請求項１記載の方
法。2. The water for digestion contains 0.05% calcium carbonate.
The method according to claim 1, which is contained at a concentration of 10 to 10 g / liter.
ｃｍを有する請求項１又は２記載の方法。3. The water for digestion has a conductivity of 0.2 to 10 mS /
A method according to claim 1 or 2 having cm.
離処理であり、ろ過処理が加圧ろ過処理又は真空ろ過処
理である請求項１、２又は３記載の方法。4. The method according to claim 1, 2 or 3, wherein the separation dehydration treatment is a centrifugal separation treatment or a sedimentation separation treatment, and the filtration treatment is a pressure filtration treatment or a vacuum filtration treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12600996A JP3924019B2 (en) | 1996-05-21 | 1996-05-21 | Method for producing light calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12600996A JP3924019B2 (en) | 1996-05-21 | 1996-05-21 | Method for producing light calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09309724A true JPH09309724A (en) | 1997-12-02 |
| JP3924019B2 JP3924019B2 (en) | 2007-06-06 |
Family
ID=14924478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12600996A Expired - Fee Related JP3924019B2 (en) | 1996-05-21 | 1996-05-21 | Method for producing light calcium carbonate |
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| Country | Link |
|---|---|
| JP (1) | JP3924019B2 (en) |
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| JP2010222220A (en) * | 2009-03-25 | 2010-10-07 | Taiheiyo Cement Corp | Method for manufacturing high-purity calcium carbonate |
| JP2011073891A (en) * | 2009-09-29 | 2011-04-14 | Nippon Paper Industries Co Ltd | Method for producing calcium carbonate |
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| CN114620753A (en) * | 2021-11-29 | 2022-06-14 | 浙江天石纳米科技股份有限公司 | Low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat |
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1996
- 1996-05-21 JP JP12600996A patent/JP3924019B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101435991B1 (en) * | 2007-07-20 | 2014-09-04 | 유피엠-케이메네 오와이제이 | Use of carbon dioxide generated in manufacturing synthetic hydrocarbon chains |
| JP2010222220A (en) * | 2009-03-25 | 2010-10-07 | Taiheiyo Cement Corp | Method for manufacturing high-purity calcium carbonate |
| JP2011073891A (en) * | 2009-09-29 | 2011-04-14 | Nippon Paper Industries Co Ltd | Method for producing calcium carbonate |
| CN105217673A (en) * | 2015-10-21 | 2016-01-06 | 常山县南方碳酸钙有限公司 | A kind of preparation method of high thixotropic silicone adhesive special-purpose nanometer activated Calcium carbonate |
| CN114349036A (en) * | 2021-11-01 | 2022-04-15 | 山东宇信纳米科技有限公司 | Preparation method of nano calcium carbonate for MS glue |
| CN114349036B (en) * | 2021-11-01 | 2023-11-24 | 山东宇信纳米科技有限公司 | Preparation method of nano calcium carbonate for MS glue |
| CN114620753A (en) * | 2021-11-29 | 2022-06-14 | 浙江天石纳米科技股份有限公司 | Low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat |
| CN114620753B (en) * | 2021-11-29 | 2023-08-18 | 浙江天石纳米科技股份有限公司 | Low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat |
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