JP2007145628A - Vaterite type calcium carbonate having crossed disk-like, hamburger-like or disk-like shape and its manufacture method - Google Patents
Vaterite type calcium carbonate having crossed disk-like, hamburger-like or disk-like shape and its manufacture method Download PDFInfo
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Abstract
Description
本発明は、円盤状炭酸カルシウムを基本粒子とした交差円盤状、ハンバーガー状又は円盤状形態をしたバテライト型炭酸カルシウムの製造方法に関する。さらに詳しくは、本発明は、不純物をほとんど含まない分散性のよく、粒子径が制御された円盤状炭酸カルシウムを基本粒子とした交差円盤状、ハンバーガー状又は円盤状形態をしたバテライト型炭酸カルシウムを、短時間に、しかも簡単な操作で効率よく製造する方法に関するものである。 The present invention relates to a method for producing a vaterite-type calcium carbonate having a crossed disk shape, a hamburger shape, or a disk shape with disk-shaped calcium carbonate as basic particles. More specifically, the present invention relates to a vaterite-type calcium carbonate having a discoidal shape, a hamburger shape, or a disc shape, which is made of a discoidal calcium carbonate having a good dispersibility and having a controlled particle size and containing almost no impurities. The present invention relates to a method for efficiently producing in a short time and with a simple operation.
炭酸カルシウムの工業的製造方法としては、炭酸ガス法が広く採用されているが、この製法による製造過程は、石灰石の焼成から消化・炭酸化過程及び異物除去過程と石灰石焼成排ガスの洗浄と石化乳液への導入の工程が必要であり、複雑な工程と装置が必要である。又、石灰石から混入する不純物の問題があり、用途が工業品あるいは食品までと限られている。用途を拡大するには、石灰石からの不純物を除く石灰乳の高純度化工程を経由しなければならず、そのための工程や装置の複雑化となり、製造コストが高くなる欠点がある。
一方、溶液法は不純物の混入をなくし、製造装置の簡素化ができ、製造コストの低減化が図れる利点がある。しかし、今まで提案されている溶液法で製造される炭酸カルシウムの形状はほとんどが球状形態であり、用途に限界があった。
The carbon dioxide method is widely adopted as an industrial production method for calcium carbonate. The production process by this production method includes the calcination of limestone, the digestion and carbonation process, the foreign matter removal process, the cleaning of limestone calcined exhaust gas, and the petrified emulsion. The process of introduction into the system is necessary, and complicated processes and devices are necessary. Moreover, there is a problem of impurities mixed in from limestone, and its use is limited to industrial products or foods. In order to expand the use, it is necessary to go through a process for purifying lime milk that removes impurities from limestone, which complicates the process and apparatus for that purpose and has the disadvantage of increasing manufacturing costs.
On the other hand, the solution method has the advantage of eliminating impurities, simplifying the manufacturing apparatus, and reducing the manufacturing cost. However, the shape of calcium carbonate produced by the solution method that has been proposed so far is almost spherical and has limited applications.
板状、楕円球状及び花弁状の形態をした炭酸カルシウムの製造方法としては、
板状形態をした水酸化カルシウムを高温で、炭酸ガスで炭酸化する方法(石膏石灰学会誌「石膏と石灰」No.196(以下、非特許文献1という))、の記載がある。
特開昭61−219717(以下、特許文献1という)に、「板状形態をした塩基性炭酸カルシウムを200℃以上の温度で、炭酸ガスと接触させて炭酸化し板状炭酸カルシウムを製造する方法」の記載がある。
特開平11−314915(以下、特許文献2という)に、「特定量の生石灰及び/又は消石灰と特定量の水を含有するメタノール懸濁液に炭酸ガスを導入し、炭酸化反応途中の特定時点で反応系内温度を特定の温度に調整し、炭酸化反応開始から反応系内の導電率が特定の値に到達する時間を特定化して炭酸化反応を行ない、球状又は楕円球状バテライト炭酸カルシウムの製造方法」の記載がある。
特許第3362239号(以下、特許文献3という))に「石灰乳に炭酸ガスを導入し、板状形態をした塩基性炭酸カルシウム生成条件下に有機アミン化合物を共存下で炭酸化反応をさせることにより板状炭酸カルシウムを合成する方法」が提案されている。
特開平1−108117(以下、特許文献4という)に、「カルシウムイオン溶液と炭酸イオン溶液を攪拌混合してバテライト型球状炭酸カルシウムを製造する方法」が記載されている。
特許第3376826号(以下、特許文献5という)に「縮合リン酸化合物を共存した石灰乳に炭酸ガスを導入し、板状形態をした塩基性炭酸カルシウム生成条件下に新たな縮合リン酸化合物を共存した石灰乳に炭酸ガスを導入することを繰り返し、板状構造をした塩基性炭酸カルシウムの一次粒子を球状に凝集させたものを、加熱下で炭酸ガスと接触させ炭酸化を終了させることにより、多孔質球状炭酸カルシウムを合成する方法」
As a method for producing calcium carbonate in the form of a plate, oval and petal,
There is a description of a method of carbonizing plate-like calcium hydroxide with carbon dioxide at a high temperature (“Gypsum and Lime” No. 196 (hereinafter referred to as Non-Patent Document 1)).
JP-A-61-219717 (hereinafter referred to as Patent Document 1) states that “a method of producing plate-like calcium carbonate by bringing a basic calcium carbonate in a plate-like form into contact with carbon dioxide gas at a temperature of 200 ° C. or higher. Is described.
In JP-A-11-314915 (hereinafter referred to as Patent Document 2), “a specific point in time during the carbonation reaction by introducing carbon dioxide into a methanol suspension containing a specific amount of quicklime and / or slaked lime and a specific amount of water” To adjust the temperature in the reaction system to a specific temperature, specify the time for the electrical conductivity in the reaction system to reach a specific value from the start of the carbonation reaction, and carry out the carbonation reaction. There is a description of "manufacturing method".
Patent No. 3362239 (hereinafter referred to as Patent Document 3) “Carbonating reaction is carried out in the presence of organic amine compound under the condition that carbon dioxide is introduced into lime milk to form a basic calcium carbonate in the form of a plate. Has proposed a method for synthesizing plate-like calcium carbonate.
Japanese Patent Application Laid-Open No. 1-108117 (hereinafter referred to as Patent Document 4) describes “a method of producing a vaterite spherical calcium carbonate by stirring and mixing a calcium ion solution and a carbonate ion solution”.
Patent No. 3376826 (hereinafter referred to as Patent Document 5) “Introduces carbon dioxide into lime milk coexisting with a condensed phosphate compound, and forms a new condensed phosphate compound under the basic calcium carbonate production conditions in the form of a plate. By repeatedly introducing carbon dioxide into the coexisting lime milk, and agglomerating the primary particles of basic calcium carbonate with a plate-like structure into spherical shapes, by contacting with carbon dioxide under heating, the carbonation is terminated Method for synthesizing porous spherical calcium carbonate "
しかしながら、非特許文献1と特許文献1は、固体の板状形態の水酸化カルシウムカルシウムや塩基性炭酸カルシウムを気体の炭酸ガスと接触反応させ、炭酸化させ炭酸カルシウムを生成させるため、大量の熱エネルギーを必要とし、更に炭酸化に長時間を要し、コスト高となり工業的製造に向いていない。更に、生成する炭酸カルシウムの形態が板状であり、本発明の交差円盤状、ハンバーガー状又は円盤状形態と異なる。
特許文献2の製造方法は、石灰乳に大量のアルコールを加え炭酸ガスで炭酸化する方法で、アルコールの回収に設備と費用がかかりコスト高になると同時に、石灰石由来の石灰乳中の不純物により日本薬局方や食品添加物規格には不適となり、工業的製造に向いていない。更に、生成する炭酸カルシウムの形態が球状又は楕円球状であり、本発明の交差円盤状、ハンバーガー状又は円盤状形態と異なる。
特許文献3の製造方法は、石灰乳の炭酸ガス導入時に塩基性炭酸カルシウム生成条件下で炭酸化を行い、塩基性炭酸カルシウム生成時にアミン化合物を添加するため、生成炭酸カルシウム表面にアミン化合物が吸着するため、日本薬局方や食品添加物規格に不適となり、利用範囲が限られる。更に、生成する炭酸カルシウムの形態が板状であり、本発明の交差円盤状、ハンバーガー状又は円盤状形態と異なる。
特許文献4の製造方法は、可溶性カルシウム塩と可溶性炭酸塩の反応であるが、急激に混合するためバテライト型結晶であるが、粒子形態が球状となり本発明の交差円盤状、ハンバーガー状又は円盤状形態と異なる。
特許文献5の製造方法は、縮合リン酸化合物を共存した石灰乳に炭酸ガスを導入し、板状形態をした塩基性炭酸カルシウム生成条件下に、新たな縮合リン酸化合物を共存した石灰乳を添加し炭酸ガスを導入することを2回以上繰り返し、板状構造をした塩基性炭酸カルシウムの一次粒子を球状に凝集させたものを生成させ、これを加熱下で炭酸ガスと接触させ炭酸化を終了させることにより、多孔質球状炭酸カルシウムを合成する方法である。
石灰乳を使用することから、石灰石由来の石灰乳中の不純物により日本薬局方に不適であり、塩基性球状炭酸カルシウムの炭酸化過程が固体と炭酸ガスの反応であり、反応に大量の熱エネルギーを必要とし、更に炭酸化に長時間を要し、コスト高となり工業的製造に向いていない。更に、生成する多孔質球状炭酸カルシウムの形態が板状の球状凝集体であり、本発明の交差円盤状、ハンバーガー状又は円盤状形態と異なる。
However, in Non-patent Document 1 and Patent Document 1, solid plate-like calcium calcium hydroxide or basic calcium carbonate is brought into contact with gaseous carbon dioxide to carbonate to produce calcium carbonate. It requires energy and further requires a long time for carbonation, resulting in high costs and not suitable for industrial production. Furthermore, the form of calcium carbonate to be generated is a plate shape, which is different from the crossed disk shape, the hamburger shape or the disk shape of the present invention.
The production method of Patent Document 2 is a method in which a large amount of alcohol is added to lime milk and carbonated with carbon dioxide gas. At the same time, equipment and cost are required to recover alcohol, and the cost increases. It is unsuitable for pharmacopoeia and food additive standards and is not suitable for industrial production. Furthermore, the form of calcium carbonate to be produced is spherical or elliptical spherical, and is different from the crossed disk shape, hamburger shape or disk shape of the present invention.
In the production method of Patent Document 3, carbonation is performed under basic calcium carbonate generation conditions when carbon dioxide gas is introduced into lime milk, and an amine compound is adsorbed on the surface of the generated calcium carbonate because an amine compound is added when basic calcium carbonate is generated. Therefore, it becomes unsuitable for Japanese Pharmacopoeia and food additive standards, and the range of use is limited. Furthermore, the form of calcium carbonate to be generated is a plate shape, which is different from the crossed disk shape, the hamburger shape or the disk shape of the present invention.
The production method of Patent Document 4 is a reaction of a soluble calcium salt and a soluble carbonate, but is a vaterite type crystal because of rapid mixing, but the particle form becomes spherical and the crossed disk shape, hamburger shape or disk shape of the present invention. Different from form.
In the production method of Patent Document 5, carbonic acid gas is introduced into lime milk coexisting with a condensed phosphate compound, and lime milk coexisting with a new condensed phosphate compound is produced under the basic calcium carbonate production conditions in the form of a plate. Addition and introduction of carbon dioxide gas are repeated twice or more to produce spherical aggregates of basic calcium carbonate particles having a plate-like structure, which are brought into contact with carbon dioxide gas under heating to perform carbonation. It is a method of synthesizing porous spherical calcium carbonate by finishing.
Because lime milk is used, it is unsuitable for the Japanese Pharmacopoeia due to impurities in lime milk derived from limestone, and the carbonation process of basic spherical calcium carbonate is a reaction between solid and carbon dioxide, and a large amount of thermal energy is involved in the reaction. In addition, it takes a long time for carbonation, resulting in high costs and not suitable for industrial production. Furthermore, the form of the produced porous spherical calcium carbonate is a plate-like spherical aggregate, which is different from the crossed disk shape, hamburger shape or disk shape of the present invention.
本発明は、用途が飛躍的に拡大することを目指して、工業的な利用では、今までの加工工程の改良や増量的な使い方から、板状の形態よりも分散性が向上し、物性が改善され配合効果が現れる炭酸カルシウムの形態を円盤状にすることと、粒子径を制御することを目的とし、また、この円盤状炭酸カルシウムを交差させることやハンバーガー状に積層させることにより、利用範囲を飛躍的に拡大させることを目的としている。 The present invention aims to dramatically expand the uses, and in industrial use, the dispersibility is improved and the physical properties are improved from the plate-like form due to the improvement of conventional processing steps and the increased usage. The purpose of this work is to make the shape of calcium carbonate that is improved and has a compounding effect into a disk shape and to control the particle diameter, and by using this calcium carbonate carbonate to cross and stacking in a hamburger shape, the range of use The purpose is to dramatically expand the.
さらに、炭酸化反応に大量の熱エネルギーを使用することなく、更に、アルコール等の有機溶剤を使用しないために有機溶剤の回収するための設備や運転費用も要らず、コスト高にならず安価な製造方法で工業生産に向いていること、又、添加剤としての有機アミン化合物を添加しないために、生成炭酸カルシウムに有機アミン化合物の吸着もなく、更に、原料である可溶性カルシウム塩や可溶性炭酸塩は、高純度のものが市場から容易に安価に入手可能なため、得られた炭酸カルシウムは日本薬局方や食品添加物規格に適合するものであり、可溶性のカルシウム塩と炭酸塩の水溶液を滴下反応させる、工業生産に向いている製法により、円盤状バテライト型炭酸カルシウムを合成することと、この円盤状炭酸カルシウムを交差させることやハンバンガ−状に積層させることを目的としている。
本発明は、単分散で粒子径が制御され広範囲の分野に利用できる円盤状バテライト型炭酸カルシウムを、短時間に、しかも簡単な設備と操作で効率よく、かつ経済的に製造し、さらに、この円盤状炭酸カルシウムを交差させることやハンバンガ−状に積層させることにより、さらに、利用範囲を拡大させ得る工業的に有利な方法を提供することを目的とするものである。
In addition, a large amount of heat energy is not used for the carbonation reaction, and no organic solvent such as alcohol is used. The production method is suitable for industrial production, and since no organic amine compound is added as an additive, there is no adsorption of the organic amine compound to the produced calcium carbonate. Furthermore, soluble calcium salts and soluble carbonates that are raw materials Since high-purity products are easily available at low cost from the market, the obtained calcium carbonate conforms to the Japanese Pharmacopoeia and food additive standards, and an aqueous solution of soluble calcium salt and carbonate is added dropwise. By making the reaction, a method suitable for industrial production, synthesizing disk-shaped vaterite-type calcium carbonate and crossing this disk-shaped calcium carbonate Nbanga - are intended to be laminated to form.
The present invention is a monodispersed, disk-shaped vaterite-type calcium carbonate that can be used in a wide range of fields and can be efficiently and economically produced in a short time and with simple equipment and operation. An object of the present invention is to provide an industrially advantageous method capable of further expanding the use range by crossing disk-like calcium carbonate or laminating them in a hamburger shape.
本願発明者は、鋭意研究の結果、前記課題を達成するため、溶液法の簡易さの利点を生かし、可溶性カルシウム塩に可溶性炭酸塩、あるいは可溶性炭酸塩に可溶性カルシウム塩を温度条件と滴下速度及び攪拌速度を制御して炭酸化反応を行うことにより、一次粒子としての円盤状のバテライト型炭酸カルシウムの合成方法を見出し、この反応における攪拌速度の違いにより、生成するバテライト型炭酸カルシウムの形態が、交差円盤状、ハンバーガー状又は円盤状形態に変化することを見出し、実現したものである。
本発明の可溶性カルシウム塩とは、塩化カルシウム、臭化カルシウム、ヨウ化カルシウム、硝酸カルシウム、亜硝酸カルシウム、蟻酸カルシウム、酢酸カルシウム、アスコルビン酸カルシウム、乳酸カルシウム、クエン酸カルシウム、グルコン酸カルシウムの水に可溶性のものであれば単独又は2種類以上を混合して使用しても良い。又、可溶性炭酸塩とは、炭酸ナトリウム、炭酸カリウムや炭酸アンモニウム又は炭酸水素ナトリウムの水に可溶性のものであれば単独又は2種類以上を混合しても使用しても良い。バテライト型交差円盤状、円盤状及びハンバーガー状炭酸カルシウムを製造する時、この時のそれぞれの可溶性カルシウム塩と可溶性炭酸塩の濃度は、0.1〜1モル/L、好ましくは0.3〜0.7モル/Lが良く、更に滴下時間は、0.1〜10時間、好ましくは0.5〜2時間が良い。
交差円盤状バテライト型炭酸カルシウムの製造では、反応温度は20〜65℃、好ましくは35〜55が良く、攪拌速度としては、タービン型攪拌羽根では、回転数は50〜1000rpm以下、好ましくは300〜800rpmが良い。
ハンバーガー状バテライト型炭酸カルシウムの製造では、反応温度は5〜50℃、好ましくは20〜40℃が良く、攪拌速度としては、タービン型攪拌羽根では、回転数は500〜1500rpm、好ましくは750〜1250rpmが良い。
円盤状バテライト型炭酸カルシウム製造では、反応温度は5〜50℃、好ましくは20〜45が良く、攪拌速度としては、タービン型攪拌羽根では、回転数は1200rpmを超える、好ましくは1500rpm以上が良い。
本発明のバテライト型交差円盤状、ハンバーガー状円盤状又は円盤状炭酸カルシウムの製造方法は、可溶性炭酸塩水溶液に可溶性カルシウム塩水溶液を滴下あるいは可溶性カルシウム塩水溶液に可溶性炭酸塩水溶液を滴下させることと反応温度及び攪拌条件を変化せせることを特徴とする。生成する炭酸カルシウムの粒子径は、1〜20μmで交差円盤状、ハンバーガー状又は円盤状形態をしたバテライト型炭酸カルシウムである。
As a result of diligent research, the inventor of the present application has made use of the advantage of the simplicity of the solution method in order to achieve the above-mentioned problem, and soluble carbonate in soluble calcium salt, or soluble calcium salt in soluble carbonate, temperature conditions, dropping rate and By conducting a carbonation reaction by controlling the stirring speed, a method for synthesizing discoidal vaterite-type calcium carbonate as primary particles was found, and due to the difference in the stirring speed in this reaction, the form of the produced vaterite-type calcium carbonate is It has been found and realized to change to a crossed disk shape, a hamburger shape or a disk shape.
The soluble calcium salt of the present invention includes calcium chloride, calcium bromide, calcium iodide, calcium nitrate, calcium nitrite, calcium formate, calcium acetate, calcium ascorbate, calcium lactate, calcium citrate, and calcium gluconate. If it is soluble, it may be used alone or in combination of two or more. The soluble carbonate may be used alone or in combination of two or more, as long as it is soluble in sodium carbonate, potassium carbonate, ammonium carbonate or sodium hydrogen carbonate water. When producing the vaterite-type intersecting disc-like, disc-like and hamburger-like calcium carbonate, the concentration of each soluble calcium salt and soluble carbonate at this time is 0.1-1 mol / L, preferably 0.3-0. 0.7 mol / L is good, and the dropping time is 0.1 to 10 hours, preferably 0.5 to 2 hours.
In the production of the intersecting disc-shaped vaterite type calcium carbonate, the reaction temperature is 20 to 65 ° C., preferably 35 to 55, and the stirring speed is 50 to 1000 rpm or less, preferably 300 to 300 rpm for the turbine type stirring blade. 800 rpm is good.
In the production of hamburger-like vaterite-type calcium carbonate, the reaction temperature is 5 to 50 ° C., preferably 20 to 40 ° C. The stirring speed is 500 to 1500 rpm, preferably 750 to 1250 rpm for the turbine type stirring blade. Is good.
In the production of disk-shaped vaterite type calcium carbonate, the reaction temperature is 5 to 50 ° C., preferably 20 to 45, and the stirring speed is more than 1200 rpm, preferably 1500 rpm or more for the turbine type stirring blade.
The method for producing the vaterite-type intersecting disc-shaped, hamburger-shaped disc-shaped or disc-shaped calcium carbonate according to the present invention comprises the steps of dropping a soluble calcium salt aqueous solution into a soluble carbonate aqueous solution or dropping a soluble carbonate aqueous solution into a soluble calcium salt aqueous solution. It is characterized by changing the temperature and stirring conditions. The particle size of the calcium carbonate to be produced is a vaterite type calcium carbonate having a crossed disc shape, a hamburger shape or a disc shape with 1 to 20 μm.
溶液濃度が0.1モル/L未満では、生成炭酸カルシウムの濃度が低いために、濾過・乾燥に時間を要し生産性が悪くなり工業的でない。又、溶液濃度が1モル/Lを超えると、反応が不均一となりカルサイト型立方状炭酸カルシウムの生成が多くなり、円盤状バテライト型炭酸カルシウムとカルサイト型立方状炭酸カルシウムの混合物となり、不均一反応生成物となる。更に、滴下時間が0.1時間未満では、混合反応と同様になり球状粒子の生成が多くなり不均一なものになる。又、滴下時間が6時間を超えると、カルサイト型立方状炭酸カルシウムの生成が多くなり不均一なものとなる。 When the solution concentration is less than 0.1 mol / L, since the concentration of the produced calcium carbonate is low, it takes time for filtration and drying, resulting in poor productivity and not industrial. On the other hand, when the solution concentration exceeds 1 mol / L, the reaction becomes non-uniform and the production of calcite cubic calcium carbonate increases, resulting in a mixture of disk-like vaterite calcium carbonate and calcite cubic calcium carbonate. A homogeneous reaction product is obtained. Furthermore, when the dropping time is less than 0.1 hour, it becomes the same as the mixing reaction, and the generation of spherical particles increases and becomes nonuniform. On the other hand, when the dropping time exceeds 6 hours, the production of calcite cubic calcium carbonate increases and becomes non-uniform.
本発明の炭酸カルシウムの生成温度範囲は5〜65℃であるが、それぞれの形態によりその生成温度範囲が異なり、温度範囲以外の温度での生成物の形態が少し異なる。交差円盤状では、指定の温度を超える場合、バテライト型結晶が生成せずアラゴナイト型結晶が生成し形態も柱状あるいは針状となり、指定温度未満の場合、粒子径の異なる円盤状が密に重なりハンバーガー状に似た形態となる。ハンバー状では、指定の温度未満では、楕円形の形態が生成するが、指定温度を超える場合、交差円盤状とハンバーガー状の混合物となる。円盤状では、指定温度を超える場合、カルサイト型結晶とアラゴナイト型結晶が生成が始まり、形態も立方状と柱状あるいは針状形態となり、指定温度未満の場合、カルサイト型結晶が生成し形態も立方状となる。 The production temperature range of the calcium carbonate of the present invention is 5 to 65 ° C., but the production temperature range is different depending on each form, and the product form at a temperature other than the temperature range is slightly different. In the crossed disc shape, when the specified temperature is exceeded, the vaterite type crystal is not generated and the aragonite type crystal is generated and the form is also columnar or needle-like. The shape is similar to the shape. In the hamburger shape, an elliptical shape is generated at a temperature lower than the specified temperature. However, when the temperature exceeds the specified temperature, a mixture of a crossed disk shape and a hamburger shape is formed. In the disk shape, when the specified temperature is exceeded, calcite-type crystals and aragonite-type crystals start to form, and the form also becomes cubic, columnar, or needle-like, and when the temperature is lower than the specified temperature, calcite-type crystals are formed and the form is also It becomes a cubic shape.
以上説明したように、本発明の炭酸カルシウムの製造方法は、可溶性カルシウム塩水溶液に可溶性炭酸塩水溶液を滴下あるいは可溶性炭酸塩水溶液に可溶性カルシウム塩水溶液を、一定の濃度、反応温度、滴下時間と攪拌条件で反応させるだけで、バテライト型交差円盤状、ハンバーガー状円盤状又は円盤状炭酸カルシウムを生成させる製造方法である。今まで発表されている板状又は楕円球状炭酸カルシウムの製造方法に比較して、特別な熱エネルギーが不必要であり、更にメタノール等の有機溶剤を使用しないために有機溶剤の回収費用や特別な回収装置が不必要であり、又特別な添加剤である有機アミン化合物の添加が不必要なため炭酸カルシウムの純度が高くなり、更に、生成バテライト型交差円盤状、ハンバーガー状円盤状又は円盤状炭酸カルシウムが、単分散で粒子径が制御されているため、用途が飛躍的に拡大し、広範囲な事業分野に利用が可能である。
しかも、製造装置が単純であり、操作が簡単であるため効率良く、かつ経済的に製造し得る工業的に有利なバテライト型交差円盤状、ハンバーガー状又は円盤状炭酸カルシウムの製造方法である。
As described above, the method for producing calcium carbonate according to the present invention comprises adding a soluble carbonate aqueous solution dropwise to a soluble calcium salt aqueous solution or adding a soluble calcium salt aqueous solution to a soluble carbonate aqueous solution at a certain concentration, reaction temperature, dropping time and stirring. It is a production method for producing a vaterite-type intersecting disc shape, a hamburger disc shape or a disc-like calcium carbonate only by reacting under conditions. Compared with the plate or oval spherical calcium carbonate production methods that have been announced so far, no special heat energy is required, and since organic solvents such as methanol are not used, the recovery cost of organic solvents and special The recovery equipment is unnecessary, and the addition of organic amine compound, which is a special additive, is unnecessary, so that the purity of calcium carbonate increases, and further, the produced vaterite type cross disk shape, hamburger disk shape or disk-like carbonic acid form. Since calcium is monodispersed and the particle size is controlled, the application is dramatically expanded and can be used in a wide range of business fields.
In addition, since the production apparatus is simple and the operation is simple, it is an industrially advantageous method for producing a vaterite-type crossed disk, hamburger or disk-shaped calcium carbonate that can be manufactured efficiently and economically.
本発明は、可溶性カルシウム塩水溶液あるいは可溶性炭酸塩水溶液に可溶性炭酸塩水溶液あるいは可溶性カルシウム塩水溶液を滴下し炭酸化反応を行うことを特徴とする、バテライト型交差円盤状、ハンバーガー状又は円盤状炭酸カルシウムの製造方法である。
純度の高い水溶性カルシウム塩および/またはそれらの水和物を濃度0.1〜1モル/L、好ましくは0.3〜0.7モル/Lの水溶液を作成する。別に純度の高い水溶性炭酸塩および/またはそれらの水和物を濃度0.3〜0.7モル/Lの水溶液を作成する。溶液濃度が0.1モル/L未満では、立方状炭酸カルシウムが多く生成すると同時に、炭酸カルシウムの濃度が低いために濾過・乾燥に時間を要し生産性が悪くなり工業的でない。溶液濃度が0.1モル/L未満では、生成炭酸カルシウムの濃度が低いために、濾過・乾燥に時間を要し生産性が悪くなり工業的でない。溶液濃度が1モル/Lを超えると、反応が不均一となりカルサイト型立方状炭酸カルシウムの生成が多くなり、円盤状バテライト型炭酸カルシウムとカルサイト型立方状炭酸カルシウムの混合物となり、不均一反応生成物となる。この時のカルシウムイオンと炭酸イオンのモル比は、1:1がよく、モル比が異なると、未反応のカルシウムイオンあるいは炭酸イオンが溶液中に残存し、有効資源を廃棄することになり経済的でない。
The present invention relates to a vaterite-type crossed disc, hamburger, or disc-like calcium carbonate characterized by performing a carbonation reaction by dropping a soluble carbonate aqueous solution or a soluble calcium salt aqueous solution into a soluble calcium salt aqueous solution or a soluble carbonate aqueous solution. It is a manufacturing method.
An aqueous solution of a highly pure water-soluble calcium salt and / or hydrate thereof is prepared at a concentration of 0.1 to 1 mol / L, preferably 0.3 to 0.7 mol / L. Separately, an aqueous solution having a concentration of 0.3 to 0.7 mol / L is prepared from a highly pure water-soluble carbonate and / or hydrate thereof. If the solution concentration is less than 0.1 mol / L, a large amount of cubic calcium carbonate is produced, and at the same time, the concentration of calcium carbonate is low, so that it takes time for filtration and drying, resulting in poor productivity and not industrial. When the solution concentration is less than 0.1 mol / L, since the concentration of the produced calcium carbonate is low, it takes time for filtration and drying, resulting in poor productivity and not industrial. When the solution concentration exceeds 1 mol / L, the reaction becomes heterogeneous and the production of calcite-type cubic calcium carbonate increases, resulting in a mixture of disk-like vaterite-type calcium carbonate and calcite-type cubic calcium carbonate, resulting in a heterogeneous reaction. Product. At this time, the molar ratio of calcium ions to carbonate ions is preferably 1: 1, and if the molar ratios are different, unreacted calcium ions or carbonate ions remain in the solution, and the effective resources are discarded. Not.
滴下時間を0.5〜2時間とし、滴下時間が0.1時間未満では、混合反応と同様になりバテライト型球状粒子の生成が多くなり、円盤状バテライト型炭酸カルシウムとバテライト型球状炭酸カルシウムの混合物が生成し不均一なものになる。又、滴下時間が4時間を超えるとカルサイト型立方状炭酸カルシウムの生成少しづつ多くなり、円盤状バテライト型炭酸カルシウムとカルサイト型立方状炭酸カルシウムの混合物が生成し不均一が広がってくる。滴下時間が10時間を超えると、カルサイト型立方状炭酸カルシウムの生成が主体となる。 When the dropping time is 0.5 to 2 hours and the dropping time is less than 0.1 hour, the production of the vaterite-type spherical particles increases as in the mixing reaction, and the disk-shaped vaterite-type calcium carbonate and the vaterite-type spherical calcium carbonate A mixture is formed and becomes non-uniform. When the dropping time exceeds 4 hours, the generation of calcite-type cubic calcium carbonate increases little by little, and a mixture of disk-like vaterite-type calcium carbonate and calcite-type cubic calcium carbonate is generated, resulting in spread of non-uniformity. When the dropping time exceeds 10 hours, calcite-type cubic calcium carbonate is mainly produced.
反応温度は5〜60℃の範囲でバテライト型交差円盤状、ハンバーガー状円盤状又は円盤状形態円盤状炭酸カルシウムが生成するが、交差円盤状では35〜55℃が最適であり、ハンバーガー状では15〜35℃最適であり、円盤状では30〜45℃が最適であり、生成したバテライト型交差円盤状、ハンバーガー状又は円盤状炭酸カルシウムは、粒子径1〜20μmであり、X線回析によるバテライト含有量は90%以上である。反応温度60℃以上になるとアラゴナイト型針状又は柱状炭酸カルシウムの生成が多くなり、不均一な生成物となる。20℃以下になると円盤状バテライト型炭酸カルシウムの凝集体が多くなるが、攪拌機と超音波攪拌を併用し攪拌すると反応温度20℃以下でもバテライト含有率は60%以上の分散の良い交差円盤状、ハンバーガー状円盤状又は円盤状バテライト型炭酸カルシウムが生成する。反応温度5℃未満では、円盤状バテライト型炭酸カルシウムがほとんど生成せず、冷却のための熱エネルギーを多く使用するために経済的でない。 The reaction temperature is in the range of 5 to 60 ° C., but a vaterite-type intersecting disc shape, a hamburger-like disc shape or a disc-like shape disc-like calcium carbonate is produced. ~ 35 ° C is optimal, and 30-45 ° C is optimal for discs, and the produced vaterite-type intersecting disc, hamburger or disc-like calcium carbonate has a particle size of 1 to 20 µm and is a vaterite by X-ray diffraction. The content is 90% or more. When the reaction temperature is 60 ° C. or higher, the production of aragonite needle-like or columnar calcium carbonate increases, resulting in a non-uniform product. When the temperature is 20 ° C. or less, agglomerates of disk-like vaterite-type calcium carbonate increase. However, when agitator and ultrasonic stirring are used in combination, the content of the vaterite is 60% or more with good dispersion even when the reaction temperature is 20 ° C. or less. A hamburger disk or disk-shaped vaterite-type calcium carbonate is produced. When the reaction temperature is less than 5 ° C., almost no discoidal vaterite-type calcium carbonate is generated, and it is not economical because a large amount of heat energy is used for cooling.
水に難溶性若しくは不溶性のカルシウム塩又は炭酸塩の使用や、カルシウム塩あるいは炭酸塩のどちらか一方を可溶性塩でもう一方を難溶性塩あるいは不溶性塩を使っても反応はうまく行かず、バテライト型交差円盤状、ハンバーガー状又は円盤状炭酸カルシウムは生成しない。
以下、本発明の実施例及び比較例により説明するが、本発明はこれらにより何ら限定されるものではない。
The use of calcium salts or carbonates that are sparingly or insoluble in water, or the use of either calcium salts or carbonates with soluble salts and the other with sparingly soluble or insoluble salts, the reaction does not go well. Crossed disk, hamburger or disk calcium carbonate is not produced.
Hereinafter, although an example and a comparative example of the present invention explain, the present invention is not limited at all by these.
試薬特級の塩化カルシウム5.55gを50℃の温水100mlで溶解する。試薬特級の炭酸ナトリウム5.30gを100mlで溶解し、この溶液を、塩化カルシウム溶液をタービン型攪拌機で500rpmで撹拌し、撹拌しながら1時間で連続に滴下した。滴下を終了した後、ろ過・水洗し、その後110℃で12時間乾燥した。この乾燥固形物の粉末X回折結果を図1に示した、このスペクトルを解析した結果、バテライトの含有率が97%であった。走査電子顕微鏡観察の結果を図2に示す。写真から基本粒子径5〜15μmの円盤状結晶の結晶が5〜20個交差状に結合成長した交差円盤状炭酸カルシウムであった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。 Reagent-grade calcium chloride 5.55 g is dissolved in 100 ml of warm water at 50 ° C. Reagent-grade sodium carbonate (5.30 g) was dissolved in 100 ml, and this solution was continuously added dropwise over 1 hour while stirring the calcium chloride solution with a turbine-type stirrer at 500 rpm. After completion of dropping, the mixture was filtered and washed with water, and then dried at 110 ° C. for 12 hours. The powder X diffraction result of this dry solid was shown in FIG. 1. As a result of analyzing this spectrum, the content of vaterite was 97%. The results of observation with a scanning electron microscope are shown in FIG. From the photograph, it was crossed disk-like calcium carbonate in which 5 to 20 crystals of disk-like crystals having a basic particle diameter of 5 to 15 μm were bonded and grown in a crossing manner. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
試薬特級の塩化カルシウム2水和物7.36gを40℃の温水200mlで溶解する。試薬特級の炭酸ナトリウム5.30gを100mlで溶解し、この溶液を、塩化カルシウム溶液をタービン型攪拌機で1000rpmで撹拌し、撹拌しながら1時間で連続に滴下した。滴下を終了した後、ろ過し、水洗し、その後110℃で12時間乾燥した。この乾燥固形物の粉末X回折測定スペクトルを解析した結果、バテライトの含有率が96%であった。走査電子顕微鏡観察の結果を図3から粒子径8〜12μmの円盤状結晶がハンバーガー状に重なったハンバーガー状炭酸カルシウムであった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。 7.36 g of reagent-grade calcium chloride dihydrate is dissolved in 200 ml of warm water at 40 ° C. Reagent-grade sodium carbonate (5.30 g) was dissolved in 100 ml, and this solution was continuously added dropwise over 1 hour while stirring the calcium chloride solution at 1000 rpm with a turbine-type stirrer. After completion of dropping, the mixture was filtered, washed with water, and then dried at 110 ° C. for 12 hours. As a result of analyzing the powder X-ray diffraction measurement spectrum of this dry solid, the content of vaterite was 96%. As a result of observation with a scanning electron microscope, it was a hamburger-like calcium carbonate in which disk-like crystals having a particle diameter of 8 to 12 μm overlapped in a hamburger shape from FIG. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
試薬特級の塩化カルシウム2水和物7.36gを40℃の温水200mlで溶解する。試薬特級の炭酸ナトリウム5.30gを100mlで溶解し、この溶液を、塩化カルシウム溶液をタービン型攪拌機で3000rpmで撹拌し、撹拌しながら1時間で連続に滴下した。滴下を終了した後、ろ過し、水洗し、その後110℃で12時間乾燥した。この乾燥固形物の粉末X回折測定スペクトルを解析した結果、バテライトの含有率が92%であった。走査電子顕微鏡観察の結果を図4に示す。写真から粒子径5〜10μmの円盤状結晶であった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。
〔比較例1〕
7.36 g of reagent-grade calcium chloride dihydrate is dissolved in 200 ml of warm water at 40 ° C. Reagent-grade sodium carbonate (5.30 g) was dissolved in 100 ml, and this solution was continuously added dropwise over 1 hour while stirring the calcium chloride solution with a turbine-type stirrer at 3000 rpm. After completion of dropping, the mixture was filtered, washed with water, and then dried at 110 ° C. for 12 hours. As a result of analyzing the powder X-ray diffraction measurement spectrum of this dry solid, the content of vaterite was 92%. The results of scanning electron microscope observation are shown in FIG. From the photograph, it was a disk-like crystal having a particle diameter of 5 to 10 μm. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
[Comparative Example 1]
塩化カルシウム溶液に炭酸ナトリウム溶液を1分以内で攪拌混合する以外は、実施例2と同様にした。得られた乾燥固形物の粉末X回折スペクトルを解析した結果、バテライトの含有率は90%であった。走査電子顕微鏡観察の結果を図5に示す。粒子径は2〜4μmの球状型バテライトと立方状のカルサイトであった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。
〔比較例2〕
The same procedure as in Example 2 was repeated, except that the sodium carbonate solution was mixed with the calcium chloride solution within 1 minute. As a result of analyzing the powder X diffraction spectrum of the obtained dry solid, the content of vaterite was 90%. The results of observation with a scanning electron microscope are shown in FIG. The particle size was 2-4 μm spherical vaterite and cubic calcite. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
[Comparative Example 2]
反応温度を15℃で行った以外は、実施例3と同様にした。得られた乾燥固形物の粉末X回折スペクトルを解析した結果、バテライトの含有率は92%であった。走査電子顕微鏡観察の結果、その結果、粒子径は一次粒子径の1〜10μmの円盤状形態がランダムにに凝集し、分散性の悪い円盤状炭酸カルシウの凝集体であった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。 Example 3 was repeated except that the reaction temperature was 15 ° C. As a result of analyzing the powder X diffraction spectrum of the obtained dry solid, the content of vaterite was 92%. As a result of observation with a scanning electron microscope, as a result, a disc-like form having a primary particle size of 1 to 10 μm was agglomerated at random, resulting in a disc-like calcium carbonate aggregate having poor dispersibility. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
塩化カルシウム2水和物3.68gと硝酸カルシウム4水和物5.90gを40℃の温水200mlで溶解した以外は、実施例1と同様に行なった。得られた乾燥固形物の粉末X回折を測定した結果を図、バテライトの含有率は94%であった。走査電子顕微鏡観察の結果、粒子径は3〜6μmの交差円盤状形態であった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。 The same procedure as in Example 1 was conducted except that 3.68 g of calcium chloride dihydrate and 5.90 g of calcium nitrate tetrahydrate were dissolved in 200 ml of warm water at 40 ° C. The result of having measured the powder X diffraction of the obtained dry solid substance is a figure, and the content rate of vaterite was 94%. As a result of observation with a scanning electron microscope, the particle diameter was a crossed disk shape of 3 to 6 μm. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
試薬特級の塩化カルシウム2水和物11.04gを55℃の温水200mlで溶解する。試薬特級の炭酸ナトリウム10.37gを100mlで溶解し、この溶液を、塩化カルシウム溶液をタービン型攪拌機で700rpmで撹拌しながら1時間で連続に滴下した。滴下を終了した後、ろ過し、水洗し、その後110℃で12時間乾燥した。この乾燥固形物の粉末X回折を測定した結果、バテライトの含有率が90%であった。走査電子顕微鏡観察の結果、基本粒子径4〜8μmの円盤状結晶の結晶が5〜20個交差状に結合成長した交差円盤状炭酸カルシウムであった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。
〔比較例3〕
Dissolve 11.04 g of reagent grade calcium chloride dihydrate in 200 ml of warm water at 55 ° C. Reagent-grade sodium carbonate (10.37 g) was dissolved in 100 ml, and this solution was continuously added dropwise over 1 hour while stirring the calcium chloride solution with a turbine-type stirrer at 700 rpm. After completion of dropping, the mixture was filtered, washed with water, and then dried at 110 ° C. for 12 hours. As a result of measuring the powder X diffraction of this dry solid, the content rate of the vaterite was 90%. As a result of observation with a scanning electron microscope, it was found to be intersecting disc-like calcium carbonate in which 5 to 20 disc-like crystals having a basic particle diameter of 4 to 8 μm were bonded and grown in an intersecting manner. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
[Comparative Example 3]
反応温度を70℃にした以外は実施例1と同様に行なった。得られた乾燥固形物の粉末X回折を測定した結果、バテライトが主体であり、少量のバテライトとカルサイトが認められ混合物であり、アラゴナイトの含有率は91%で、走査電子顕微鏡観察の結果、粒子径は1〜10μmの針状・柱状・立方状の混合物であった。 The same procedure as in Example 1 was performed except that the reaction temperature was 70 ° C. As a result of measuring the powder X diffraction of the obtained dry solid, vaterite is the main component, a small amount of vaterite and calcite are recognized, and the content of aragonite is 91%. As a result of observation with a scanning electron microscope, The particle size was a mixture of needles, columns, and cubes having a size of 1 to 10 μm.
試薬特級の塩化カルシウム2水和物10.30gを35℃の温水200mlで溶解する。試薬特級の炭酸ナトリウム7.42gを100mlで溶解し、この溶液を、塩化カルシウム溶液をタービン型攪拌機で1500rpmで撹拌し、撹拌しながら3時間で連続に滴下した。滴下を終了した後、ろ過し、水洗し、その後110℃で12時間乾燥した。この乾燥固形物の粉末X回折測定スペクトルを解析した結果、バテライトの含有率が92%であった。走査電子顕微鏡観察の結果を図3から粒子径5〜8μmの円盤状結晶がハンバーガー状に重なったハンバーガー状炭酸カルシウムであった。化学分析の結果99.9%以上の炭酸カルシウム含有量であった。
10.30 g of reagent-grade calcium chloride dihydrate is dissolved in 200 ml of warm water at 35 ° C. 7.42 g of reagent-grade sodium carbonate was dissolved in 100 ml, and this solution was continuously added dropwise over 3 hours while stirring the calcium chloride solution with a turbine-type stirrer at 1500 rpm. After completion of dropping, the mixture was filtered, washed with water, and then dried at 110 ° C. for 12 hours. As a result of analyzing the powder X-ray diffraction measurement spectrum of this dry solid, the content of vaterite was 92%. As a result of observation with a scanning electron microscope, it was a hamburger-like calcium carbonate in which disk-like crystals having a particle diameter of 5 to 8 μm overlapped in a hamburger shape from FIG. As a result of chemical analysis, the content of calcium carbonate was 99.9% or more.
Claims (5)
反応温度は5〜50℃、回転数は500〜1500rpmの反応条件であるハンバーガー状バテライト型炭酸カルシウムの製造方法、
反応温度は5〜50℃、回転数は1200〜5000rpmの反応条件である円盤状バテライト型炭酸カルシウム製造方法。
The method for producing a crossed disk-shaped vaterite-type calcium carbonate, wherein changing the stirring state according to any one of claims 2 to 4 is a reaction condition of a reaction temperature of 20 to 65 ° C and a rotation speed of 50 to 1000 rpm. ,
A reaction temperature of 5 to 50 ° C. and a rotational speed of 500 to 1500 rpm.
A method for producing a disk-shaped vaterite-type calcium carbonate having a reaction temperature of 5 to 50 ° C. and a rotation speed of 1200 to 5000 rpm.
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JP2007277036A (en) * | 2006-04-05 | 2007-10-25 | Hokkaido Kyodo Sekkai Kk | Vaterite-type spherical calcium carbonate and method for producing the same |
JP2009067605A (en) * | 2007-09-10 | 2009-04-02 | Oita Univ | Method for producing aragonite type calcium carbonate with hexagonal plate form |
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JP2011126740A (en) * | 2009-12-17 | 2011-06-30 | Taiheiyo Cement Corp | Method for producing vaterite type calcium carbonate |
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