JP2002234726A - Continuous producing method of calcium carbonate - Google Patents
Continuous producing method of calcium carbonateInfo
- Publication number
- JP2002234726A JP2002234726A JP2001025151A JP2001025151A JP2002234726A JP 2002234726 A JP2002234726 A JP 2002234726A JP 2001025151 A JP2001025151 A JP 2001025151A JP 2001025151 A JP2001025151 A JP 2001025151A JP 2002234726 A JP2002234726 A JP 2002234726A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- carbonation
- lime
- milk
- spindle
- 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】この発明は、石灰乳から連続
的に紡錘状炭酸カルシウムを製造する方法に係り、特に
連続式で歩留まり良く効率よく炭酸カルシウムを製造す
る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously producing spindle-shaped calcium carbonate from milk of lime, and more particularly to a continuous method for producing calcium carbonate efficiently with good yield.
【０００２】[0002]
【従来の技術】石灰乳の炭酸化反応によって合成する軽
質炭酸カルシウムは、製紙顔料、ゴム・プラスチックス
用フィラーなど幅広い用途に利用されている。特に紡錘
状炭酸カルシウムは、角柱状炭酸カルシウムに比べ摩耗
性が少ないため、例えば紙の内填用顔料として用いた場
合に抄紙ワイヤ等の摩耗を低減できることから、有用性
が高い。この紡錘状炭酸カルシウムの製造方法は、石灰
乳を入れた反応槽に炭酸ガスを吹き込みながら炭酸化す
る半回分式が一般的である。2. Description of the Related Art Light calcium carbonate synthesized by a carbonation reaction of milk of lime has been used in a wide range of applications such as papermaking pigments and fillers for rubber and plastics. In particular, spindle-shaped calcium carbonate has a low abrasion property as compared with prismatic calcium carbonate. For example, when used as a pigment for filling paper, the spindle-shaped calcium carbonate can reduce abrasion of a papermaking wire or the like, and thus has high utility. The production method of this spindle-shaped calcium carbonate is generally a semi-batch type in which carbonation is performed while blowing carbon dioxide gas into a reaction tank containing milk of lime.
【０００３】[0003]
【発明が解決しようとする課題】しかし半回分式炭酸化
では、反応が進むにつれ、炭酸化反応速度が鈍化すると
ともに紡錘状結晶以外の炭酸カルシウムが生成しやすく
なるという問題があった。また半回分式装置で大量生産
しようとすると、例えば20ｍ3以上の容量の単位装置を
数基から十数基備えなければならず、装置が大規模にな
るという問題がある。However, in semi-batch carbonation, there is a problem that as the reaction proceeds, the carbonation reaction rate slows down and calcium carbonate other than spindle-shaped crystals is easily produced. In addition, if mass production is to be performed using a semi-batch type device, several to more than ten unit devices having a capacity of, for example, 20 m 3 or more must be provided, resulting in a problem that the device becomes large-scale.
【０００４】そこで本発明は紡錘状炭酸カルシウムを効
率よく製造することができる連続製造方法を提供するこ
とを目的とする。また本発明は大規模な装置を不要と
し、大量生産に適した炭酸カルシウムの連続製造方法を
提供することを目的とする。Accordingly, an object of the present invention is to provide a continuous production method capable of producing spindle-shaped calcium carbonate efficiently. Another object of the present invention is to provide a method for continuously producing calcium carbonate which does not require a large-scale apparatus and is suitable for mass production.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
本発明者は、石灰乳の炭酸化反応について詳細な検討を
行った。その結果、1）炭酸化は、図１に示すように、
ガス吸収速度に依存するステップAと、炭酸化が生成物
(炭酸カルシウム)層内に進行するステップB(生成物層内
拡散律速ステップ)とに分けられ、ステップAの炭酸化速
度は早く、炭酸化90％近くまで進むのに対し、ステップ
Bでは反応速度が非常に鈍化し、残り10数％の炭酸化に
ステップAとほぼ時間がかかること、２）ステップBでは
炭酸化がほぼ終了しているにもかかわらず、みかけ上の
ｐHが7程度まで低下し、これによってさらにガス吸収速
度が低下すること、がわかった。Means for Solving the Problems In order to achieve the above object, the present inventors have conducted detailed studies on the carbonation reaction of lime milk. As a result, 1) carbonation, as shown in FIG.
Step A depending on gas absorption rate and carbonation is product
(Calcium carbonate) Layer B is divided into Step B (diffusion-controlled step in the product layer), and the carbonation rate in Step A is high, while the carbonation proceeds to nearly 90%.
In B, the reaction rate is extremely slowed down, and carbonation of the remaining 10% or so takes almost the same time as in step A. 2) In step B, although the carbonation is almost complete, the apparent pH is It was found that the gas absorption rate was reduced to about 7, which further reduced the gas absorption rate.
【０００６】本発明は、上記知見に基づきなされたもの
であり、反応速度の速いステップAを半回分式で行うと
ともに、生成物層内拡散律速ステップをｐHコントロー
ル下で連続式で行うことにより、反応速度を上げ、量産
性を上げて、紡錘状炭酸カルシウムを効率よく製造可能
にしたものである。The present invention has been made on the basis of the above-mentioned findings. By performing the step A having a high reaction rate in a semi-batch manner and performing the diffusion-limiting step in the product layer in a continuous manner under pH control, By increasing the reaction rate and mass productivity, spindle-shaped calcium carbonate can be produced efficiently.
【０００７】即ち、本発明の炭酸カルシウムの連続製造
方法は、石灰乳を半回分式炭酸化法で部分的に炭酸化す
るか或いは石灰乳に紡錘状炭酸カルシウム結晶(種結晶)
を混合する第1の工程と、第1の工程で部分的に炭酸化し
た或いは種結晶を混合した石灰乳に、ｐH10〜12に維持
しながら、炭酸ガスまたは炭酸化ガス含有ガスを連続的
に接触させて炭酸化する第2の工程とを含むものであ
る。That is, according to the continuous production method of calcium carbonate of the present invention, lime milk is partially carbonated by a semi-batch type carbonation method, or spindle-like calcium carbonate crystal (seed crystal) is added to lime milk.
And a lime milk partially carbonated or mixed with seed crystals in the first step, while continuously maintaining the pH at 10 to 12 with a carbon dioxide gas or a carbonation gas-containing gas. And a second step of carbonation by contact.
【０００８】第1の工程で部分的に炭酸化する場合、そ
の炭酸化開始温度を20〜60℃に保つことが好ましい。ま
た石灰乳の炭酸化率が5〜30％の範囲となるように添加
することが好ましい。[0008] In the case of partial carbonation in the first step, it is preferable to keep the carbonation start temperature at 20 to 60 ° C. Further, it is preferable to add the lime milk so that the carbonation rate is in the range of 5 to 30%.
【０００９】以下、本発明の炭酸カルシウムの製造方法
について詳述する。本発明の炭酸カルシウムの製造方法
は、半回分式で行う第1の工程と、連続式で行う第2の工
程からなり、第1の工程では、石灰乳中に紡錘状炭酸カ
ルシウム結晶が部分的に生じた状態を形成する。このた
めに石灰乳に炭酸ガス又は炭酸ガス含有ガスを吹き込み
部分的に炭酸化するか、石灰乳に種結晶として紡錘状炭
酸カルシウム結晶を混合する。Hereinafter, the method for producing calcium carbonate of the present invention will be described in detail. The method for producing calcium carbonate of the present invention comprises a first step performed by a semi-batch method and a second step performed by a continuous method.In the first step, spindle-shaped calcium carbonate crystals are partially contained in lime milk. The resulting state is formed. For this purpose, carbon dioxide gas or carbon dioxide-containing gas is blown into the lime milk to partially carbonate it, or spindle calcium calcium carbonate crystals are mixed into the lime milk as seed crystals.
【００１０】原料となる石灰乳は、生石灰を湿式消化す
ることにより得られる水性スラリーであり、消石灰粒子
濃度は好ましくは50〜150ｇ／リットル、より好ましく
は60〜120ｇ／リットルのものを用いる。[0010] The lime milk used as a raw material is an aqueous slurry obtained by wet digesting quicklime, and the slaked lime particles having a concentration of preferably 50 to 150 g / l, more preferably 60 to 120 g / l are used.
【００１１】石灰乳を部分的に炭酸化する場合には、石
灰乳を入れた容器内に炭酸ガスまたは炭酸ガス含有ガス
を吹き込む。炭酸ガス含有ガスとは、各種燃焼工程など
で排出された二酸化炭素を含有する混合ガスで、ガス中
の炭酸ガス含有量が5〜100容量％のものを用いる。具体
的には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
を用いることができる。工業的にはこのような排ガスを
利用することが好ましい。In the case where the milk of lime is partially carbonated, carbon dioxide or a gas containing carbon dioxide is blown into a container containing the milk of lime. The carbon dioxide gas-containing gas is a mixed gas containing carbon dioxide discharged in various combustion processes and the like, and has a carbon dioxide content of 5 to 100% by volume. Specifically, limestone firing exhaust gas such as limestone firing kiln exhaust gas, lime firing exhaust gas such as lime kiln exhaust gas of a pulp manufacturing plant, power generation boiler exhaust gas, refuse incineration exhaust gas, and the like can be used. It is preferable to use such exhaust gas industrially.
【００１２】吹き込み反応は、炭酸ガス量として原料1
ｋｇあたり毎分3〜20リットル、好適には5〜15リットル
の割合で吹き込みながら、数分〜30分程度行うことが好
ましい。In the blowing reaction, the raw material 1
It is preferable to perform the treatment for several minutes to 30 minutes while blowing at a rate of 3 to 20 liters per minute, preferably 5 to 15 liters per kg.
【００１３】反応開始温度は好ましくは20〜60℃とす
る。反応開始温度を20℃以上とすることにより、膠質炭
酸カルシウムの生成を抑制し、紡錘状炭酸カルシウムの
生成を促進することができる。また60℃以下とすること
により、アラゴナイト形柱状炭酸カルシウムの生成を防
止し、且つ炭酸ガスの吸収効率の低下を防止することが
できる。[0013] The reaction initiation temperature is preferably 20 to 60 ° C. By setting the reaction start temperature to 20 ° C. or higher, the formation of colloidal calcium carbonate can be suppressed, and the formation of spindle calcium carbonate can be promoted. By setting the temperature to 60 ° C. or lower, it is possible to prevent the formation of aragonite-type columnar calcium carbonate and to prevent a reduction in carbon dioxide gas absorption efficiency.
【００１４】このような条件で反応させることにより、
石灰乳は部分的に炭酸化される。反応後の炭酸化率は好
ましくは5〜30％、より好ましくは10〜20％の範囲とな
るようにする。炭酸化率が5％未満では第2の工程におい
て紡錘状炭酸カルシウムが生成しにくい。また炭酸化率
が30％を超えると、処理能力が低下する。By reacting under such conditions,
The lime milk is partially carbonated. The degree of carbonation after the reaction is preferably in the range of 5 to 30%, more preferably 10 to 20%. When the carbonation rate is less than 5%, spindle-shaped calcium carbonate is not easily generated in the second step. If the carbonation rate exceeds 30%, the processing capacity will decrease.
【００１５】第1の工程は、上述した炭酸ガスの吹き込
みによる部分炭酸化の代わりに、石灰乳に紡錘状の種結
晶を混合してもよい。この場合にも、混合後の炭酸化率
が10〜20％の範囲となるようにすることが好ましく、こ
れにより第2の工程において紡錘状炭酸カルシウムの生
成が促進される。種結晶としては、粒子の短径0.3〜0.5
μｍ、長径1〜2μｍのものが好ましい。In the first step, a spindle-shaped seed crystal may be mixed with milk of lime instead of the above partial carbonation by blowing carbon dioxide gas. Also in this case, it is preferable that the carbonation ratio after mixing is in the range of 10 to 20%, whereby the production of spindle calcium carbonate is promoted in the second step. As the seed crystal, the minor axis of the particle 0.3 to 0.5
μm and a major axis of 1-2 μm are preferred.
【００１６】第2工程は、上述した第1の工程で部分的に
炭酸化した石灰乳と炭酸ガス又は炭酸ガス含有ガスを連
続的に接触させながら、炭酸化反応を完結させる。第2
工程でも、第1の工程で用いる炭酸ガスまたは炭酸ガス
含有ガスと同様のガスを使用することができる。In the second step, the carbonation reaction is completed while continuously bringing the lime milk partially carbonated in the first step and the carbon dioxide gas or the carbon dioxide-containing gas into contact with each other. No. 2
Also in the step, the same gas as the carbon dioxide gas or the carbon dioxide-containing gas used in the first step can be used.
【００１７】第2の工程における反応は、主として、図
２に示すように表面に炭酸カルシウムが形成され内部が
水酸化カルシウムである粒子（生成物）の内部に炭酸ガ
スが浸透して炭酸化を進める生成物層内拡散律速ステッ
プであり、この生成物層内拡散律速ステップでは、炭酸
ガスのホールドアップ量を大きくしても炭酸化速度は鈍
化し、ｐHが低下する。これにより目的とする紡錘状炭
酸カルシウムが生成されにくくなる。従って、第2の工
程では、連続式で反応させてｐHをコントロールするこ
とにより、紡錘状炭酸カルシウムの生成を促進させる。The reaction in the second step mainly involves the carbonation by the permeation of carbon dioxide gas into particles (products) having calcium carbonate formed on the surface and calcium hydroxide inside as shown in FIG. This is the diffusion-controlling step in the product layer that proceeds. In this diffusion-controlling step in the product layer, even if the amount of carbon dioxide gas held up is increased, the carbonation rate slows down and the pH decreases. This makes it difficult to produce the desired spindle-shaped calcium carbonate. Therefore, in the second step, the production of spindle-shaped calcium carbonate is promoted by controlling the pH by a continuous reaction.
【００１８】即ち、第2の工程では反応槽内のｐHを10〜
12、好ましくは11〜12の範囲に制御する。ｐHを10以上
とすることにより立方体状炭酸カルシウムの生成を抑制
し、紡錘状炭酸カルシウムを選択的に生成させることが
できる。またｐHが12を超えると、粒子中に未反応の水
酸化カルシウムが残存する可能性が高くなる。That is, in the second step, the pH in the reactor is adjusted to 10 to
It is controlled in the range of 12, preferably 11 to 12. By setting the pH to 10 or more, the production of cubic calcium carbonate can be suppressed, and spindle calcium carbonate can be selectively produced. If the pH exceeds 12, the possibility that unreacted calcium hydroxide remains in the particles increases.
【００１９】反応槽内温度は、好ましくは20〜60℃とす
る。温度が20℃未満では、立方体状炭酸カルシウムが生
成される割合が高くなり、60℃を超えると炭酸ガスの吸
収効率が低下する。滞留時間は、反応槽の容量、吹込み
ガス量等によっても異なるが、通常15〜25分程度とす
る。このような条件で反応させることにより析出した炭
酸カルシウムを、反応槽からスラリーとして連続的に取
り出す。The temperature in the reaction tank is preferably 20 to 60 ° C. If the temperature is lower than 20 ° C., the rate of formation of cubic calcium carbonate increases, and if the temperature exceeds 60 ° C., the absorption efficiency of carbon dioxide decreases. The residence time varies depending on the capacity of the reaction tank, the amount of blown gas, and the like, but is usually about 15 to 25 minutes. The calcium carbonate precipitated by the reaction under such conditions is continuously taken out of the reaction tank as a slurry.
【００２０】図３にこの連続的炭酸化反応を行うのに好
適な装置の一例を示す。この装置は、攪拌機５を備え、
ガス導入管6、石灰乳供給管７および反応液溢流管８が
連結された気液混合槽１からなり、気液混合槽１下部に
連結されたガス導入管6から炭酸ガスまたは炭酸ガス含
有ガスを供給するとともに、上記第1の工程で部分的に
炭酸化された石灰乳を石灰乳供給管７から供給し、攪拌
しながら反応させて、所定の滞留時間経過後、反応液溢
流管８から溢流する反応液を回収する。FIG. 3 shows an example of an apparatus suitable for performing this continuous carbonation reaction. This device includes a stirrer 5,
It comprises a gas-liquid mixing tank 1 to which a gas introduction pipe 6, a milk of lime supply pipe 7 and a reaction liquid overflow pipe 8 are connected. While supplying the gas, the lime milk partially carbonated in the first step is supplied from the lime milk supply pipe 7 and reacted while stirring, and after a predetermined residence time has elapsed, the reaction liquid overflow pipe The reaction solution overflowing from 8 is collected.
【００２１】攪拌機５は、攪拌シャフトの下端に円形の
ディスクを固定した構造を有し、ディスクは円周部３が
ディスク面に垂直に屈曲し、その縁部に複数のピン４が
半径方向に固定されている。このような構造によって、
攪拌機５の下側からディスクに向けて吹き込まれた炭酸
ガスは細かい気泡となって混合槽内に拡散し、反応は下
から上へと進み、反応によって生じた炭酸カルシウムを
溢流スラリーとして回収することができる。The stirrer 5 has a structure in which a circular disk is fixed to the lower end of a stirring shaft. The disk has a circumferential portion 3 bent perpendicularly to the disk surface, and a plurality of pins 4 on its edge in the radial direction. Fixed. With such a structure,
The carbon dioxide gas blown from the lower side of the stirrer 5 toward the disk is dispersed as fine bubbles into the mixing tank, and the reaction proceeds from the bottom to the top, and the calcium carbonate generated by the reaction is recovered as an overflow slurry. be able to.
【００２２】スラリー中の炭酸カルシウムは、ろ別後、
必要に応じて分散、分級等の処理を行い、さらに水洗或
いは乾燥等を経て、最終製品である粉末或いは炭酸カル
シウム水性懸濁液とする。このようにして、結晶形が紡
錘形、平均短径約1〜1.5μｍ、平均長径約2〜3μｍの炭
酸カルシウムが得られる。After the calcium carbonate in the slurry is filtered off,
If necessary, dispersion, classification and the like are carried out, followed by washing with water or drying to obtain a final product, a powder or an aqueous calcium carbonate suspension. In this way, calcium carbonate having a spindle shape, an average minor axis of about 1 to 1.5 μm, and an average major axis of about 2 to 3 μm is obtained.
【００２３】以上、説明したように本発明によれば、部
分炭酸化工程と連続工程とを組み合わせることにより、
紡錘状炭酸カルシウムを量産性よく製造することができ
る。また本発明の炭酸カルシウムの製造方法によれば、
連続工程においてｐHをコントロールすることにより、
高品質の高い効率で紡錘状炭酸カルシウムを得ることが
できる。As described above, according to the present invention, by combining the partial carbonation step and the continuous step,
Spindle-shaped calcium carbonate can be produced with good mass productivity. According to the method for producing calcium carbonate of the present invention,
By controlling the pH in a continuous process,
Spindle-shaped calcium carbonate can be obtained with high quality and high efficiency.
【００２４】[0024]
【発明の実施の形態】本発明の炭酸カルシウムの製造方
法の製造フローの一実施形態を図４に示す。図４におい
て、部分炭酸化のための反応槽101、102には、生石灰を
湿式消化することにより得られた石灰乳が石灰乳槽103
から供給される。一方、石灰焼成炉104からの排ガス
（炭酸ガス含有ガス）を除塵、洗浄工程を経て反応槽10
1、102に所定時間吹き込み、部分的に炭酸化反応を進め
る。FIG. 4 shows an embodiment of the production flow of the method for producing calcium carbonate of the present invention. In FIG. 4, lime milk obtained by wet digestion of quicklime is placed in a lime milk tank 103 in reaction tanks 101 and 102 for partial carbonation.
Supplied from On the other hand, the exhaust gas (carbon dioxide gas-containing gas) from the lime sintering furnace 104 is dust-removed and subjected to a cleaning process to form
The carbonation reaction is partially advanced by blowing into 1, 102 for a predetermined time.
【００２５】この反応槽101、102の反応液は、半炭酸化
スラリー槽105に集められ、連続炭酸化槽107に供給され
る。連続炭酸化槽107には、反応槽101、102と同様に石
灰焼成炉104から炭酸ガス含有ガスが供給される。所定
の滞留時間で連続的に反応液と炭酸ガス含有ガスの反応
を進めながら、オーバーフローしたスラリーを回収す
る。このスラリーは、篩108により分級した後、品質管
理後製品化される。The reaction solutions in the reaction tanks 101 and 102 are collected in a semi-carbonated slurry tank 105 and supplied to a continuous carbonation tank 107. The continuous carbonation tank 107 is supplied with a carbon dioxide gas-containing gas from a lime sintering furnace 104 as in the case of the reaction tanks 101 and 102. The overflowed slurry is collected while the reaction between the reaction solution and the carbon dioxide-containing gas is continuously performed for a predetermined residence time. After the slurry is classified by the sieve 108, it is commercialized after quality control.
【００２６】なお、図４は本発明による炭酸カルシウム
の製造フローの一例であって、各反応槽や篩等の構成
は、図示するものに限定されず任意に変更することがで
きる。例えば図には反応槽が２槽の場合を示したが、そ
れより多くても少なくてもよい。FIG. 4 shows an example of the flow of producing calcium carbonate according to the present invention, and the constitution of each reaction tank, sieve and the like is not limited to those shown in the drawings and can be arbitrarily changed. For example, the figure shows a case where the number of reaction vessels is two, but the number may be more or less.
【００２７】[0027]
【実施例】以下、本発明の炭酸カルシウムの製造方法の
実施例を説明する。EXAMPLES Examples of the method for producing calcium carbonate of the present invention will be described below.
【００２８】[実施例１]10Ｌの消石灰スラリー（水酸化
カルシウム粒子濃度74ｇ（１モル）/Ｌ）を45℃に加熱
した後、20℃の炭酸ガスを3.7Ｌ/分の速度で13分30秒間
吹き込み、炭酸化スラリー（一次液という）を得た。こ
の一次液の炭酸ガス濃度を測定し、炭酸化率を求めたと
ころ、炭酸化率は20％であった。なお、炭酸化率は、
[（炭酸化したCa(OH)2量）÷（全Ca(OH)2量）]×100か
ら求めた。また炭酸ガス吹き込み後の液温は50℃であっ
た。Example 1 After heating 10 L of slaked lime slurry (calcium hydroxide particle concentration 74 g (1 mol) / L) to 45 ° C., carbon dioxide gas at 20 ° C. was supplied at a rate of 3.7 L / min for 13 minutes 30 minutes. The mixture was blown for 2 seconds to obtain a carbonated slurry (referred to as a primary liquid). The carbon dioxide concentration of this primary liquid was measured, and the carbonation rate was determined. The carbonation rate was 20%. The carbonation rate is
[(Carbonated Ca (OH) 2 amount) ÷ (total Ca (OH) 2 amount)] × 100. The liquid temperature after blowing carbon dioxide gas was 50 ° C.
【００２９】次に気液混合槽（内径：20ｃｍ、高さ：25
ｃｍ）内に、8ｃｍの高さまで50℃の水を入れ、この温
度に保ちつつ20℃の炭酸ガスを5Ｌ/分の速度で微細気泡
として吹き込みながら、気液混合槽内スラリーのｐＨが
10〜11の間に保持されるように上記一次液を供給した。
一次液供給後55分して、液面は20ｃｍの高さに達し、溢
流しはじめた。溢流が1Ｌになった時点で反応を停止
し、溢流をろ過し、ろ滓を140℃で1時間乾燥することに
より、60ｇの炭酸カルシウムを得た。この炭酸カルシウ
ムは、ＳＥＭ写真から長径2.5μｍ、短径1μｍの紡錘状
炭酸カルシウムであることが確認された。図５（a）に
ＳＥＭ写真を示す。Next, a gas-liquid mixing tank (inner diameter: 20 cm, height: 25
cm), water of 50 ° C. is introduced to a height of 8 cm, and while maintaining this temperature, carbon dioxide gas of 20 ° C. is blown as fine bubbles at a rate of 5 L / min.
The primary liquid was supplied so as to be maintained between 10 and 11.
55 minutes after the supply of the primary liquid, the liquid level reached a height of 20 cm and began to overflow. When the overflow reached 1 L, the reaction was stopped, the overflow was filtered, and the filter cake was dried at 140 ° C. for 1 hour to obtain 60 g of calcium carbonate. The SEM photograph confirmed that this calcium carbonate was spindle-shaped calcium carbonate having a major axis of 2.5 μm and a minor axis of 1 μm. FIG. 5A shows an SEM photograph.
【００３０】[実施例２]10ｍ3の消石灰スラリー（水酸
化カルシウム粒子濃度100ｇ/Ｌ）を50℃に加熱した後、
40℃の石灰焼成炉排ガス（炭酸ガス濃度：25体積％）を
12ｍ3/時の速度で4分12秒間吹き込み、15％の炭酸化ス
ラリー（一次液）を得た。この一次液の液温は50℃であ
った。Example 2 After heating 10 m 3 of slaked lime slurry (calcium hydroxide particle concentration 100 g / L) to 50 ° C.,
40 ° C lime kiln exhaust gas (carbon dioxide concentration: 25% by volume)
Blowing was performed at a rate of 12 m 3 / hour for 4 minutes and 12 seconds to obtain a 15% carbonated slurry (primary liquid). The liquid temperature of this primary liquid was 50 ° C.
【００３１】次に300Ｌ容量の大型気液混合槽内に、50
℃の温水50Lを入れ、上記石灰焼成炉排ガスを16ｍ3/時
の速度で微細気泡として吹き込みながら、気液混合槽内
スラリーのｐＨが11〜12の間に保持されるように上記一
次液を供給した。一次液供給後１時間17分後に250L容量
レベルで溢流し始めた。溢流した炭酸化スラリーを３時
間14分後に300Ｌろ過し、ろ滓を150℃で４時間乾燥する
ことにより、36.8kgの炭酸カルシウムを得た。この炭酸
カルシウムは、ＳＥＭ写真から長径３μｍ、短径1μｍ
の紡錘状炭酸カルシウムであることが確認された。Next, 50 liters of gas were mixed in a large 300 L gas-liquid mixing tank.
50 L of warm water at ℃, and while blowing the lime-burning furnace exhaust gas as fine bubbles at a rate of 16 m 3 / hour, the primary liquid was cooled so that the pH of the slurry in the gas-liquid mixing tank was maintained between 11 and 12. Supplied. One hour and 17 minutes after the supply of the primary liquid, it began to overflow at a 250 L volume level. After 3 hours and 14 minutes, the overflowed carbonated slurry was filtered at 300 L, and the filter cake was dried at 150 ° C. for 4 hours to obtain 36.8 kg of calcium carbonate. This calcium carbonate has a major axis of 3 μm and a minor axis of 1 μm from the SEM photograph.
Was confirmed to be spindle-shaped calcium carbonate.
【００３２】[比較例１]実施例１と同様にして一次液を
調製した。次いで気液混合槽内のスラリーのｐＨを8〜9
に保持する以外は、実施例１と同様にして、溢流から炭
酸カルシウム60ｇを回収した。但し、この場合、液面高
さ20cmで溢流し始めるのに一次液供給後80分を要した。
この炭酸カルシウムは、ＳＥＭ写真から平均辺長３μｍ
×４μｍの角柱状炭酸カルシウムであることが確認され
た。ＳＥＭ写真を図５(b)に示す。Comparative Example 1 A primary liquid was prepared in the same manner as in Example 1. Next, the pH of the slurry in the gas-liquid mixing tank was adjusted to 8 to 9
Calcium carbonate (60 g) was recovered from the overflow in the same manner as in Example 1 except that the calcium carbonate was retained. However, in this case, it took 80 minutes after the supply of the primary liquid to start overflowing at a liquid level of 20 cm.
This calcium carbonate has an average side length of 3 μm from the SEM photograph.
It was confirmed to be a square columnar calcium carbonate of × 4 μm. An SEM photograph is shown in FIG.
【００３３】[実施例３]紡錘状炭酸カルシウムのスラリ
ー（粒子濃度：100g／L）を消石灰スラリー（水酸化カ
ルシウム粒子濃度：74g／L）にCaCO3／Ca(OH)2モル比10
%になるように添加し、混合スラリーを得た。この混合
スラリーを一次液として、実施例１と同様に気液混合槽
内で炭酸ガスと反応させて、溢流から炭酸カルシウム60
ｇを回収した。この炭酸カルシウムは、ＳＥＭ写真から
長径2.5μm，短径1μmの紡錘状炭酸カルシウムであるこ
とが確認された。[Example 3] A slurry of spindle-shaped calcium carbonate (particle concentration: 100 g / L) was added to slaked lime slurry (calcium hydroxide particle concentration: 74 g / L) at a 2 molar ratio of CaCO 3 / Ca (OH) 10.
% To obtain a mixed slurry. This mixed slurry was used as a primary liquid and reacted with carbon dioxide in a gas-liquid mixing tank in the same manner as in Example 1.
g was collected. This calcium carbonate was confirmed to be spindle-shaped calcium carbonate having a major axis of 2.5 μm and a minor axis of 1 μm from a SEM photograph.
【００３４】[0034]
【発明の効果】本発明によれば、半回分式炭酸化と連続
方法とを組み合わせるとともに連続反応におけるｐＨを
高ｐＨに維持することにより、効率よく紡錘状炭酸カル
シウムを得ることができる。このような本発明の炭酸カ
ルシウムの製造方法によれば、製造時間を大幅に短縮す
ることができ、また大規模な装置を用いることなく大量
生産が可能となる。According to the present invention, a spindle-shaped calcium carbonate can be obtained efficiently by combining a semi-batch type carbonation with a continuous method and maintaining a high pH in a continuous reaction. According to the method for producing calcium carbonate of the present invention, the production time can be significantly reduced, and mass production can be performed without using a large-scale apparatus.
【図１】 石灰乳の炭酸化反応における炭酸化過程を示
す図。FIG. 1 is a diagram showing a carbonation process in a carbonation reaction of milk of lime.
【図２】 水酸化カルシウム粒子における炭酸化過程を
説明する図。FIG. 2 is a diagram illustrating a carbonation process in calcium hydroxide particles.
【図３】 連続的炭酸化反応を行うのに好適な装置の一
実施形態を示す図。FIG. 3 is a diagram showing one embodiment of an apparatus suitable for performing a continuous carbonation reaction.
【図４】 本発明の炭酸カルシウムの製造方法の一実施
形態を示すフロー図。FIG. 4 is a flowchart showing one embodiment of the method for producing calcium carbonate of the present invention.
【図５】 本発明の炭酸カルシウムの製造方法の実施例
で製造された炭酸カルシウムのＳＥＭ写真を示す図で、
（a）は実施例１の炭酸カルシウム、（ｂ）は比較例の
炭酸カルシウムである。FIG. 5 is a view showing an SEM photograph of calcium carbonate produced in an example of the method for producing calcium carbonate of the present invention,
(A) is the calcium carbonate of Example 1, and (b) is the calcium carbonate of the comparative example.
Claims (6)
化する第1の工程と、第1の工程で部分的に炭酸化した石
灰乳に、ｐH10〜12に維持しながら、炭酸ガスまたは炭
酸化ガス含有ガスを連続的に接触させて炭酸化する第2
の工程とを含む紡錘状炭酸カルシウムの連続製造方法。A first step of partially carbonating the milk of lime by a semi-batch carbonation method, and a step of maintaining a pH of 10 to 12 in the milk of partially carbonated lime in the first step; Second carbonation by continuously contacting carbon dioxide gas or gas containing carbonation gas
And a step of continuously producing spindle-shaped calcium carbonate.
を20〜60℃に保つことを特徴とする請求項1記載の炭酸
カルシウムの連続製造方法。2. The method for continuously producing calcium carbonate according to claim 1, wherein in the first step, a carbonation initiation temperature is maintained at 20 to 60 ° C.
する第1の工程と、第1の工程で紡錘状炭酸カルシウム結
晶を混合した石灰乳に、ｐH10〜12に維持しながら、炭
酸ガスまたは炭酸化ガス含有ガスを連続的に接触させて
炭酸化する第2の工程とを含む紡錘状炭酸カルシウムの
連続製造方法。3. A first step of mixing spindle-shaped calcium carbonate crystals with milk of lime, and a step of mixing carbon dioxide gas or lime milk mixed with spindle-shaped calcium carbonate crystals in the first step while maintaining the pH at 10 to 12. A second step of carbonizing by continuously contacting a carbonation gas-containing gas, thereby producing a spindle-shaped calcium carbonate.
率を5〜30％の範囲とすることを請求項１ないし３いず
れか１項記載の炭酸カルシウムの連続製造方法。4. The method for continuously producing calcium carbonate according to claim 1, wherein in the first step, the rate of carbonation of the milk of lime is in the range of 5 to 30%.
℃であることを特徴とする請求項項１ないし４いずれか
１項記載の炭酸カルシウムの連続製造方法。5. The reaction temperature in the second step is 20 to 60.
5. The continuous method for producing calcium carbonate according to claim 1, wherein the temperature is ℃.
続製造方法によって製造された紡錘状炭酸カルシウム。6. A spindle-shaped calcium carbonate produced by the continuous production method according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025151A JP4961074B2 (en) | 2001-02-01 | 2001-02-01 | Continuous production method of calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025151A JP4961074B2 (en) | 2001-02-01 | 2001-02-01 | Continuous production method of calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002234726A true JP2002234726A (en) | 2002-08-23 |
| JP4961074B2 JP4961074B2 (en) | 2012-06-27 |
Family
ID=18890190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001025151A Expired - Lifetime JP4961074B2 (en) | 2001-02-01 | 2001-02-01 | Continuous production method of calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4961074B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009091180A (en) * | 2007-10-05 | 2009-04-30 | Shiraishi Calcium Kaisha Ltd | Calcium carbonate having high rate of biologic absorption and method for producing the same |
| JP2009292666A (en) * | 2008-06-03 | 2009-12-17 | Daio Paper Corp | Production method of regeneration particle |
| WO2010106953A1 (en) * | 2009-03-17 | 2010-09-23 | アイシン精機株式会社 | Method for processing carbon dioxide gas |
| CN103539186A (en) * | 2013-09-28 | 2014-01-29 | 昆山市周市溴化锂溶液厂 | Preparation method of fusiform light calcium carbonate |
| CN115286029A (en) * | 2022-08-25 | 2022-11-04 | 广西华纳新材料股份有限公司 | Method for preparing monodisperse spindle precipitated calcium carbonate |
| CN115849424A (en) * | 2022-11-07 | 2023-03-28 | 原初科技（北京）有限公司 | Preparation device of calcium carbonate powder for carbon neutralization and use method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936025B (en) * | 2012-10-26 | 2014-05-07 | 四川中际磁业有限责任公司 | Micro and nano-grade active light calcium carbonate automated production system |
| JP7196254B1 (en) | 2021-08-20 | 2022-12-26 | 株式会社ノリタケカンパニーリミテド | Calcium carbonate production method and calcium carbonate production apparatus |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5110199A (en) * | 1974-07-16 | 1976-01-27 | Okutama Kako Kk | Heikin 3 myuuijono ritsuhotaikeitansankarushiumuno seizohoho |
| JPS5617924A (en) * | 1979-07-25 | 1981-02-20 | Maruo Calcium Kk | Manufacture of 0.1[1.0 micron calcium carbonate |
| JPS5836924A (en) * | 1981-08-28 | 1983-03-04 | Okutama Kogyo Kk | Growing method for crystal of aragonite type prismatic calcium carbonate |
| JPS5926927A (en) * | 1982-08-04 | 1984-02-13 | Okutama Kogyo Kk | Preparation of fusiform calcium carbonate crystal |
| JPH0314696A (en) * | 1988-06-10 | 1991-01-23 | Okutama Kogyo Kk | Production of paper-making pigment and agglomerated calcium carbonate |
| JPH03197318A (en) * | 1989-12-26 | 1991-08-28 | Okutama Kogyo Kk | Aggregated calcium carbonate, its production and pigment for paper making |
| JPH1111941A (en) * | 1997-06-18 | 1999-01-19 | Okutama Kogyo Kk | Production of light calcium carbonate |
-
2001
- 2001-02-01 JP JP2001025151A patent/JP4961074B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5110199A (en) * | 1974-07-16 | 1976-01-27 | Okutama Kako Kk | Heikin 3 myuuijono ritsuhotaikeitansankarushiumuno seizohoho |
| JPS5617924A (en) * | 1979-07-25 | 1981-02-20 | Maruo Calcium Kk | Manufacture of 0.1[1.0 micron calcium carbonate |
| JPS5836924A (en) * | 1981-08-28 | 1983-03-04 | Okutama Kogyo Kk | Growing method for crystal of aragonite type prismatic calcium carbonate |
| JPS5926927A (en) * | 1982-08-04 | 1984-02-13 | Okutama Kogyo Kk | Preparation of fusiform calcium carbonate crystal |
| JPH0314696A (en) * | 1988-06-10 | 1991-01-23 | Okutama Kogyo Kk | Production of paper-making pigment and agglomerated calcium carbonate |
| JPH03197318A (en) * | 1989-12-26 | 1991-08-28 | Okutama Kogyo Kk | Aggregated calcium carbonate, its production and pigment for paper making |
| JPH1111941A (en) * | 1997-06-18 | 1999-01-19 | Okutama Kogyo Kk | Production of light calcium carbonate |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009091180A (en) * | 2007-10-05 | 2009-04-30 | Shiraishi Calcium Kaisha Ltd | Calcium carbonate having high rate of biologic absorption and method for producing the same |
| JP2009292666A (en) * | 2008-06-03 | 2009-12-17 | Daio Paper Corp | Production method of regeneration particle |
| WO2010106953A1 (en) * | 2009-03-17 | 2010-09-23 | アイシン精機株式会社 | Method for processing carbon dioxide gas |
| JP2010214303A (en) * | 2009-03-17 | 2010-09-30 | Aisin Seiki Co Ltd | Method of treating carbon dioxide |
| CN103539186A (en) * | 2013-09-28 | 2014-01-29 | 昆山市周市溴化锂溶液厂 | Preparation method of fusiform light calcium carbonate |
| CN115286029A (en) * | 2022-08-25 | 2022-11-04 | 广西华纳新材料股份有限公司 | Method for preparing monodisperse spindle precipitated calcium carbonate |
| CN115286029B (en) * | 2022-08-25 | 2023-12-01 | 广西华纳新材料股份有限公司 | Method for preparing monodisperse spindle precipitated calcium carbonate |
| CN115849424A (en) * | 2022-11-07 | 2023-03-28 | 原初科技（北京）有限公司 | Preparation device of calcium carbonate powder for carbon neutralization and use method thereof |
| CN115849424B (en) * | 2022-11-07 | 2023-06-16 | 原初科技（北京）有限公司 | Preparation device of calcium carbonate powder for carbon neutralization and application method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4961074B2 (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5426982B2 (en) | Method for producing calcium carbonate | |
| KR101196041B1 (en) | Process for production of pcc | |
| US6156286A (en) | Seeding of aragonite calcium carbonate and the product thereof | |
| US20020009410A1 (en) | Precisely sized precipitated calcium carbonate (PCC) crystals of preselected crystal habit, manufactured using pressure carbonation | |
| US5342600A (en) | Precipitated calcium carbonate | |
| JP5603935B2 (en) | Method for producing calcium carbonate | |
| US20090028774A1 (en) | Carbonator and method for making calcium carbonate | |
| NZ237487A (en) | Exothermic reaction of a dissolved reactant with carbon dioxide which is injected in liquid form, the reactant being a metal oxide or hydroxide | |
| KR20050013579A (en) | Process for the production of precipitated calcium carbonates and product produced thereby | |
| JP4961074B2 (en) | Continuous production method of calcium carbonate | |
| US20030082091A1 (en) | Process for generation of precipitated calcium carbonate from calcium carbonate rich industrial by-product | |
| JP5320242B2 (en) | Method for producing calcium carbonate | |
| JPS5926927A (en) | Preparation of fusiform calcium carbonate crystal | |
| JP4157202B2 (en) | Process for producing spindle-shaped calcium carbonate | |
| EP1440037B1 (en) | Process for generation of precipitated calcium carbonate from calcium carbonate rich industrial by-product | |
| US20050089466A1 (en) | Methods and apparatus for producing precipitated calcium carbonate | |
| CN116528963A (en) | Method for producing calcium carbonate and calcium carbonate | |
| JP3924019B2 (en) | Method for producing light calcium carbonate | |
| JP4194288B2 (en) | Method for producing calcium carbonate | |
| KR20040087050A (en) | The synthesis method of cubical precipitated calcium carbonate using the limestone washing process sludge | |
| JP2002234725A (en) | Method for producing calcium carbonate of aragonite crystal system | |
| JPS62113718A (en) | Production of hexagonal complex of calcium carbonate | |
| JPH0649574B2 (en) | Method for producing fine cubic calcium carbonate | |
| KR100208370B1 (en) | Manufacturing method of calcium carbonate | |
| CN115448348B (en) | Solid morphology control agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080121 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100402 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110315 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110506 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120313 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120326 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150330 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |