JP2005154158A - Porous granular basic magnesium carbonate and its producing method - Google Patents
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本発明は、多孔質粒状塩基性炭酸マグネシウムに関するものであり、特に、食品や飲料のマグネシウム補強剤としての使用に適した粒子サイズへの粉砕もしくは解砕が容易な多孔質粒状塩基性炭酸マグネシウムに関するものである。 The present invention relates to porous granular basic magnesium carbonate, and more particularly to porous granular basic magnesium carbonate that can be easily pulverized or crushed to a particle size suitable for use as a magnesium reinforcing agent for foods and beverages. Is.
近年、食品や飲料のマグネシウム補強剤として、塩基性炭酸マグネシウムを用いることが検討されている。食品や飲料に添加される塩基性炭酸マグネシウムは、食品や飲料の食感を損なわないように、粒子サイズが小さい方が好ましい。一般に平均粒子径で、食品では３μｍ以下、飲料では０．５μｍ以下であることが好ましいといわれている。 In recent years, the use of basic magnesium carbonate as a magnesium reinforcing agent for foods and beverages has been studied. The basic magnesium carbonate added to foods and beverages preferably has a smaller particle size so as not to impair the texture of foods and beverages. In general, it is said that the average particle size is preferably 3 μm or less for foods and 0.5 μm or less for beverages.
例えば、特許文献１には、平均体積粒子が０．１〜０．５μｍの範囲にある塩基性炭酸マグネシウムが分散されているマグネシウムの補強飲料もしくはペースト状食品が開示されている。また、特許文献２には、カルシウム素材と平均体積粒子が０．１〜０．５μｍの範囲にある塩基性炭酸マグネシウムとが分散されているカルシウムとマグネシウムの補強飲料もしくはペースト状食品が開示されている。これらの特許文献１、２には、上記粒子サイズの塩基性炭酸マグネシウムは、水酸化マグネシウム懸濁液に、炭酸ガスを接触させて、水酸化マグネシウムの炭酸化反応により炭酸マグネシウムを生成し、次いで炭酸マグネシウムを分解熟成して塩基性炭酸マグネシウムに転化することによって製造された塩基性炭酸マグネシウム（二次粒子）を、ビーズミルを用いた湿式粉砕法によって粉砕することによって得られると記載されている。 For example, Patent Literature 1 discloses a magnesium-reinforced beverage or pasty food in which basic magnesium carbonate having an average volume particle in the range of 0.1 to 0.5 μm is dispersed. Patent Document 2 discloses a calcium and magnesium reinforced beverage or pasty food in which a calcium material and basic magnesium carbonate having an average volume particle in the range of 0.1 to 0.5 μm are dispersed. Yes. In these patent documents 1 and 2, the basic magnesium carbonate having the above particle size is produced by bringing a magnesium hydroxide suspension into contact with carbon dioxide gas to produce magnesium carbonate by a carbonation reaction of magnesium hydroxide, It is described that basic magnesium carbonate (secondary particles) produced by decomposing and aging magnesium carbonate and converting it to basic magnesium carbonate is obtained by pulverization by a wet pulverization method using a bead mill.
上記の水酸化マグネシウムの炭酸化反応を利用して、塩基性炭酸マグネシウムを合成する方法は、工業的に広く行われている。この水酸化マグネシウムの炭酸化反応により得られる塩基性炭酸マグネシウム（二次粒子）は、一般に鱗片状の一次粒子が球状に凝集してなる多孔質粒子である。 A method for synthesizing basic magnesium carbonate by utilizing the above-mentioned carbonation reaction of magnesium hydroxide is widely performed industrially. Basic magnesium carbonate (secondary particles) obtained by the carbonation reaction of magnesium hydroxide is generally porous particles formed by agglomerating flaky primary particles into a spherical shape.
例えば、特許文献３には、塩基性炭酸マグネシウム出発懸濁液に、水酸化マグネシウム懸濁液を添加しながら、炭酸ガスを吹き込んで炭酸化反応を行なう多孔質球状塩基性炭酸マグネシウムの製造方法が開示されている。この特許文献の実施例１では、鱗片状の一次粒子が多孔質に凝集した、１５μｍ程度の均一な粒子径をもつ球状体であって、見掛比重０．２５ｇ／ｃｃ、吸油量１７０ｍＬ／１００ｇで、水５００ｍＬに粉末１００ｇを懸濁させた際の粘度が２００ｃｐｓの多孔質球状塩基性炭酸マグネシウムが得られている。
また、この特許文献の記載によれば、上述の方法によって製造される多孔質球状塩基性炭酸マグネシウムは、水、有機溶媒あるいはポリマー等への分散性に優れ、塗料、化粧料、紙あるいはポリマー等の充填剤及び薬剤のキャリアー、芳香剤の担体等の広い用途に好適に使用できるとされている。
Further, according to the description of this patent document, the porous spherical basic magnesium carbonate produced by the above-described method is excellent in dispersibility in water, an organic solvent, a polymer or the like, such as a paint, a cosmetic, paper or a polymer. It is said that it can be suitably used for a wide range of applications, such as fillers and drug carriers, and fragrance carriers.
上述の水酸化マグネシウムの炭酸化反応を利用して多孔質粒状塩基性炭酸マグネシウムを製造する場合、水性媒体中の多孔質粒状塩基性炭酸マグネシウムの粒子サイズを小さくすると（特に、平均粒子径で３μｍ以下にすると）、後工程であるろ過工程でのろ過効率が低下するため、多孔質粒状塩基性炭酸マグネシウムの生産性が低下する傾向にある。また、粒子サイズの小さい多孔質粒状塩基性炭酸マグネシウムは、乾燥時に、固結しやすいという問題がある。これらの理由から、水酸化マグネシウムの炭酸化反応を利用して製造された多孔質粒状塩基性炭酸マグネシウムは、平均粒子径で１０μｍ以上であることが多い。 When producing the porous granular basic magnesium carbonate using the above-mentioned carbonation reaction of magnesium hydroxide, the particle size of the porous granular basic magnesium carbonate in the aqueous medium is reduced (particularly, the average particle diameter is 3 μm). If it is set below), the filtration efficiency in the subsequent filtration step is lowered, so the productivity of the porous granular basic magnesium carbonate tends to be lowered. In addition, porous granular basic magnesium carbonate having a small particle size has a problem that it tends to solidify during drying. For these reasons, the porous granular basic magnesium carbonate produced by utilizing the carbonation reaction of magnesium hydroxide often has an average particle diameter of 10 μm or more.
上記のような粒子サイズの大きい多孔質粒状塩基性炭酸マグネシウムを食品や飲料のマグネシウム補強剤として用いるためには、その粒子サイズを予め使用目的に応じたサイズに粉砕もしくは解砕することが必要とある。しかしながら、本発明者の検討によると、水酸化マグネシウム懸濁液中の水酸化マグネシウム（一次粒子）は、緻密な凝集体（二次粒子）を形成し易いため、水酸化マグネシウムの炭酸化反応を利用して製造した多孔質粒状塩基性炭酸マグネシウムは、一次粒子の緻密な凝集体となる傾向にあり、食品や飲料のマグネシウム補強剤としての使用に適した粒子サイズにまで粉砕もしくは解砕するのは容易ではない。
従って、本発明の課題は、食品や飲料のマグネシウム補強剤としての使用に適した粒子サイズへの粉砕もしくは解砕が容易な塩基性炭酸マグネシウム及びその製造方法を提供することにある。
In order to use porous granular basic magnesium carbonate having a large particle size as described above as a magnesium reinforcing agent for foods and beverages, it is necessary to pulverize or crush the particle size to a size according to the purpose of use in advance. is there. However, according to the study by the present inventor, magnesium hydroxide (primary particles) in the magnesium hydroxide suspension tends to form dense aggregates (secondary particles), and therefore, the carbonation reaction of magnesium hydroxide is not performed. Porous granular basic magnesium carbonate produced by use tends to be a dense aggregate of primary particles, and is pulverized or crushed to a particle size suitable for use as a magnesium reinforcing agent in foods and beverages. Is not easy.
Accordingly, an object of the present invention is to provide basic magnesium carbonate that can be easily pulverized or pulverized into a particle size suitable for use as a magnesium reinforcing agent in foods and beverages, and a method for producing the same.
本発明者は、一次粒子の平均粒子径が０．０１〜０．５μｍの範囲にある酸化マグネシウム粉末の懸濁液に炭酸ガスを接触させることにより、比表面積が１０〜１００ｍ2／ｇの範囲にあり、平均粒子径が１０〜８０μｍの範囲にあって、直径が１０〜３００ｎｍの細孔（以下、このサイズの細孔をマクロ細孔ということもある）の総容積が０．２〜１．０ｍＬ／ｇの範囲にある多孔質粒状塩基性炭酸マグネシウムを得ることができ、さらに、この多孔質粒状塩基性炭酸マグネシウムが、上記の水酸化マグネシウムの炭酸化反応を利用して得られた多孔質粒状塩基性炭酸マグネシウムと比べて粉砕性もしくは解砕性に優れることを見い出して、本発明に到達した。 The inventor of the present invention has a specific surface area of 10 to 100 m 2 / g by bringing carbon dioxide gas into contact with a suspension of magnesium oxide powder having an average primary particle diameter of 0.01 to 0.5 μm. The total volume of pores having an average particle diameter of 10 to 80 μm and a diameter of 10 to 300 nm (hereinafter, pores of this size may be referred to as macropores) is 0.2 to 1 A porous granular basic magnesium carbonate in a range of 0.0 mL / g can be obtained, and the porous granular basic magnesium carbonate is obtained by using the above-mentioned carbonation reaction of magnesium hydroxide. The present inventors have found that it is excellent in pulverization property or pulverization property compared with granular granular magnesium carbonate, and has reached the present invention.
従って、本発明は、一次粒子が凝集してなる多孔質粒状塩基性炭酸マグネシウムであって、比表面積が１０〜１００ｍ2／ｇの範囲にあり、平均粒子径が１０〜８０μｍの範囲にあって、直径が１０〜３００ｎｍの細孔（マクロ細孔）の総容積が０．２〜１．０ｍＬ／ｇの範囲にあることを特徴とする多孔質粒状塩基性炭酸マグネシウムにある。 Accordingly, the present invention is a porous granular basic magnesium carbonate in which primary particles are aggregated, having a specific surface area in the range of 10 to 100 m 2 / g and an average particle diameter in the range of 10 to 80 μm. In the porous granular basic magnesium carbonate, the total volume of pores (macropores) having a diameter of 10 to 300 nm is in the range of 0.2 to 1.0 mL / g.
本発明の多孔質粒状塩基性炭酸マグネシウムの好ましい態様を下記に示す。
（１）マクロ細孔の総容積が全細孔の総容積の８０％以上を占める。
（２）粒子径が５μｍ未満の多孔質粒子を１０体積％以上含まない。
The preferable aspect of the porous granular basic magnesium carbonate of this invention is shown below.
(1) The total volume of macropores occupies 80% or more of the total volume of all pores.
(2) Does not contain 10% by volume or more of porous particles having a particle diameter of less than 5 μm.
本発明の多孔質粒状塩基性炭酸マグネシウムは、一次粒子の平均粒子径が０．０１〜０．５μｍの範囲にある酸化マグネシウム粉末を、水性媒体中で炭酸ガスに接触させることによって製造することができる。 The porous granular basic magnesium carbonate of the present invention can be produced by contacting magnesium oxide powder having an average primary particle diameter in the range of 0.01 to 0.5 μm with carbon dioxide gas in an aqueous medium. it can.
本発明の多孔質粒状塩基性炭酸マグネシウムは、マクロ細孔の総容積が大きく、一次粒子が粗に凝集した多孔質粒子であるので、容易に粉砕もしくは解砕することができる。従って、本発明の多孔質粒状塩基性炭酸マグネシウムは、食品や飲料のマグネシウム補強剤の原料として有利に使用することができる。
また、本発明の製造方法では、酸化マグネシウム粉末を水性媒体中で炭酸ガスに接触させるので、酸化マグネシウムの水和反応による水酸化マグネシウムの生成と、その生成した水酸化マグネシウムの炭酸化反応とが同時に進行する。すなわち、水酸化マグネシウムが緻密な凝集体を形成する前に水酸化マグネシウムの炭酸化反応が進行する。従って、本発明の製造方法より、マクロ細孔の総容積の大きい多孔質粒状塩基性炭酸マグネシウムを工業的に有利に製造することができる。
Since the porous granular basic magnesium carbonate of the present invention is a porous particle in which the total volume of macropores is large and primary particles are coarsely aggregated, it can be easily pulverized or crushed. Therefore, the porous granular basic magnesium carbonate of the present invention can be advantageously used as a raw material for a magnesium reinforcing agent for foods and beverages.
Further, in the production method of the present invention, the magnesium oxide powder is brought into contact with carbon dioxide gas in an aqueous medium. Therefore, the production of magnesium hydroxide by the hydration reaction of magnesium oxide and the carbonation reaction of the produced magnesium hydroxide are performed. Progress at the same time. That is, the carbonate reaction of magnesium hydroxide proceeds before magnesium hydroxide forms a dense aggregate. Therefore, the porous granular basic magnesium carbonate having a large total volume of macropores can be industrially advantageously produced by the production method of the present invention.
本発明の多孔質粒状塩基性炭酸マグネシウムは、一次粒子が凝集してなる多孔質粒状塩基性炭酸マグネシウムであって、比表面積が１０〜１００ｍ2／ｇの範囲にあり、平均粒子径が１０〜８０μｍの範囲にあって、直径が１０〜３００ｎｍの細孔（マクロ細孔）の総容積が０．２〜１．０ｍＬ／ｇの範囲にあることを特徴とする。上記マクロ細孔の総容積は、全細孔の総容積の８０体積％以上（特に、８５〜９９体積％の範囲）を占めることが好ましい。 The porous granular basic magnesium carbonate of the present invention is a porous granular basic magnesium carbonate formed by aggregation of primary particles, having a specific surface area in the range of 10 to 100 m 2 / g, and an average particle diameter of 10 to 10. The total volume of pores (macropores) having a diameter of 10 to 300 nm in a range of 80 μm is in a range of 0.2 to 1.0 mL / g. The total volume of the macropores preferably occupies 80% by volume or more (particularly in the range of 85 to 99% by volume) of the total volume of all the pores.
さらに本発明の多孔質粒状塩基性炭酸マグネシウムは、粒子径が５μｍ未満の多孔質粒子を１０体積％以上含まないことが好ましい。また、ハンドリング性（流動性）の指標として、安息角が５０度以下、特に、２０〜４０度の範囲にあることが好ましい。 Furthermore, it is preferable that the porous granular basic magnesium carbonate of the present invention does not contain 10% by volume or more of porous particles having a particle diameter of less than 5 μm. Further, as an index of handling property (fluidity), it is preferable that the angle of repose is 50 degrees or less, particularly 20 to 40 degrees.
本発明の多孔質粒状塩基性炭酸マグネシウムは、例えば、水などの適当な溶媒に分散させた状態で超音波振動を付与することにより、あるいはボールミルを用いた湿式粉砕法により、食品や飲料のマグネシウム補強剤として有用な粒子サイズとすることができる。 The porous granular basic magnesium carbonate of the present invention can be obtained by applying ultrasonic vibrations in a state dispersed in a suitable solvent such as water, or by wet pulverization using a ball mill. The particle size can be useful as a reinforcing agent.
上記の多孔質粒状塩基性炭酸マグネシウムは、一次粒子の平均粒子径が０．０１〜０．５μｍにある酸化マグネシウム粉末を、水性媒体中で炭酸ガスに接触させることにより有利に製造することができる。なお、酸化マグネシウム粉末の一次粒子の平均粒子径は、Ｘ線粉末法により求めた結晶子サイズを意味する。 The porous granular basic magnesium carbonate can be advantageously produced by bringing a magnesium oxide powder having an average primary particle diameter of 0.01 to 0.5 μm into contact with carbon dioxide gas in an aqueous medium. . In addition, the average particle diameter of the primary particle of magnesium oxide powder means the crystallite size calculated | required by the X-ray powder method.
酸化マグネシウム粉末の一次粒子は、二次粒子を形成していてもよい。二次粒子のサイズは、平均粒子径で１〜３μｍの範囲にあることが好ましい。酸化マグネシウム粉末は、水酸化マグネシウムや炭酸マグネシウムなどのマグネシウム化合物を、１２００℃以下の温度で焼成して製造した仮焼酸化マグネシウム粉末であることが好ましい。 The primary particles of the magnesium oxide powder may form secondary particles. The size of the secondary particles is preferably in the range of 1 to 3 μm in terms of average particle diameter. The magnesium oxide powder is preferably a calcined magnesium oxide powder produced by firing a magnesium compound such as magnesium hydroxide or magnesium carbonate at a temperature of 1200 ° C. or lower.
水性媒体には、９０℃以下、特に６０〜８０℃の温水を用いることが好ましい。水性媒体の温度が低くなると、酸化マグネシウムの水和速度が遅くなったり、また水酸化マグネシウムの炭酸化反応によって生成した炭酸マグネシウムからの塩基性炭酸マグネシウムへの転化速度が遅くなる傾向にある。水性媒体中の酸化マグネシウム濃度は、１〜２０質量％の範囲にあることが好ましい。 As the aqueous medium, it is preferable to use hot water of 90 ° C. or less, particularly 60 to 80 ° C. When the temperature of the aqueous medium is lowered, the hydration rate of magnesium oxide tends to be slow, and the conversion rate of magnesium carbonate produced by the carbonate reaction of magnesium hydroxide to basic magnesium carbonate tends to be slow. The magnesium oxide concentration in the aqueous medium is preferably in the range of 1 to 20% by mass.
炭酸ガスの供給（水性媒体への吹き込み）は、酸化マグネシウムの水和反応により生成した水酸化マグネシウムが水性媒体中にて緻密な凝集体を形成しないように、酸化マグネシウム粉末を水性媒体に投入する前もしくは投入後直ちに行なうことが好ましい。炭酸ガスは、ＣＯ2濃度で２０〜１００容量％の範囲にあることが好ましい。炭酸ガスの流量は、酸化マグネシウム粉末１ｋｇあたり、５〜３０Ｌ／分の範囲にあることが好ましい。炭酸ガスの供給は、水性媒体中に炭酸ガスが十分に分散するように、水性媒体を攪拌しながら行なうことが好ましい。攪拌は、生成した塩基性炭酸マグネシウムの多孔質粒子に衝撃を与えないように緩やかに行なうことが好ましい。 The supply of carbon dioxide gas (blowing into the aqueous medium) is performed by introducing magnesium oxide powder into the aqueous medium so that the magnesium hydroxide produced by the hydration reaction of magnesium oxide does not form a dense aggregate in the aqueous medium. It is preferable to carry out it immediately before or immediately after charging. The carbon dioxide gas is preferably in the range of 20 to 100% by volume in terms of CO 2 concentration. The flow rate of carbon dioxide gas is preferably in the range of 5 to 30 L / min per kg of magnesium oxide powder. The carbon dioxide gas is preferably supplied while stirring the aqueous medium so that the carbon dioxide gas is sufficiently dispersed in the aqueous medium. The stirring is preferably performed gently so as not to give an impact to the produced porous particles of basic magnesium carbonate.
上記の方法により得られた多孔質粒状塩基性炭酸マグネシウムは、ろ過し、乾燥することによって、回収することができる。 The porous granular basic magnesium carbonate obtained by the above method can be recovered by filtration and drying.
以下、実施例により本発明を詳細に説明する。なお、下記の実施例及び比較例において得られた多孔質粒状塩基性炭酸マグネシウムの比表面積、マクロ細孔の総容積、全細孔総容積に対するマクロ細孔総容積の占有率、平均粒子径、粒子径が５μｍ未満の多孔質粒子含有率、超音波粉砕処理の平均粒子径及び安息角は下記の方法により測定した。 Hereinafter, the present invention will be described in detail by way of examples. The specific surface area of the porous granular basic magnesium carbonate obtained in the following Examples and Comparative Examples, the total volume of macropores, the occupation ratio of the total macropore volume to the total total pore volume, the average particle diameter, The content of porous particles having a particle diameter of less than 5 μm, the average particle diameter of the ultrasonic grinding treatment, and the angle of repose were measured by the following methods.
（１）比表面積：試料を１２０℃で３時間真空乾燥した後、ユアサアイオニクス（株）製、Ａｕｔｏｓｏｒｂ−ＭＰ３を用いて、ＢＥＴ法により測定した。
（２）マクロ細孔の総容積及びマクロ細孔の総容積占有率：試料を１２０℃で３時間真空乾燥した後、ユアサアイオニクス（株）製、Ａｕｔｏｓｏｒｂ−ＭＰ３を用いて、窒素吸着法により測定した。減圧度合いを変化させることによって、細孔径ごとに総容積を測定して、マクロ細孔の総容積とマクロ細孔の総容積占有率とを算出した。
（３）平均粒子径及び５μｍ未満の多孔質粒子含有率：試料５ｇを水５０ｇが入った１００ｍＬビーカに投入し、試料が均一に分散するまでガラス棒でゆっくりかき混ぜた後、レーザ回折式粒度分布測定装置（日機装（株）製、ＭｉｃｒｏｔａｃＸ１００）を用いて、平均粒子径及び５μｍ未満の多孔質粒子含有率を測定した。
（４）超音波粉砕処理後の平均粒子径：試料５ｇを水５０ｇが入った１００ｍＬビーカに投入し、超音波振動子（日本精機（株）製、ＵＳ−３００）を用いて電流値３００μＡの条件下にて１０分間超音波粉砕処理を行なった後、レーザ回折式粒度分布測定装置を用いて平均粒子径を測定した。
（５）安息角：ホソカワミクロン（株）製、パウダーテスターを用いて測定した。
(1) Specific surface area: The sample was vacuum-dried at 120 ° C. for 3 hours and then measured by BET method using Autosorb-MP3 manufactured by Yuasa Ionics Co., Ltd.
(2) Total volume of macropores and total volume occupancy of macropores: After the sample was vacuum-dried at 120 ° C. for 3 hours, it was subjected to nitrogen adsorption method using Autosorb-MP3 manufactured by Yuasa Ionics Co., Ltd. It was measured. By changing the degree of decompression, the total volume was measured for each pore diameter, and the total volume of the macropores and the total volume occupation ratio of the macropores were calculated.
(3) Average particle diameter and porous particle content of less than 5 μm: 5 g of a sample is put into a 100 mL beaker containing 50 g of water, and stirred slowly with a glass rod until the sample is uniformly dispersed, and then laser diffraction particle size distribution Using a measuring device (Nikkiso Co., Ltd., Microtac X100), the average particle size and the content of porous particles less than 5 μm were measured.
(4) Average particle size after ultrasonic pulverization treatment: 5 g of sample was put into a 100 mL beaker containing 50 g of water, and the current value was 300 μA using an ultrasonic vibrator (Nippon Seiki Co., Ltd., US-300). After ultrasonic pulverization for 10 minutes under the conditions, the average particle size was measured using a laser diffraction particle size distribution analyzer.
(5) Angle of repose: Measured using a powder tester manufactured by Hosokawa Micron Corporation.
［実施例１］
水酸化マグネシウム（関東化学（株）製、鹿１級）を電気炉に入れ、室温から４５０℃まで４５分間、４５０℃から７００℃まで５０分間、７００℃から９５０℃まで８０分間の昇温条件で昇温した後、９５０℃にて１時間保持して酸化マグネシウム粉末を得た。得られた酸化マグネシウム粉末の一次粒子の平均粒子径をＸ線粉末法により測定したところ、その値は０．０４μｍであった。また、酸化マグネシウム粉末をエタノールに分散させた後、レーザ回折式粒度分布測定装置（日機装（株）製、ＭｉｃｒｏｔａｃＸ１００）を用いて、二次粒子の平均粒子径を測定したところ、その値は２．６μｍであった。
上記の酸化マグネシウム粉末１ｋｇを７０℃の温水２０ｋｇが入った攪拌機付き反応槽に入れ、ＣＯ2濃度２５容量％の炭酸ガスを１０．５Ｌ／分の流量にて吹き込みながら５時間攪拌した。反応生成物を吸引ろ過した後、エタノール洗浄し、１２０℃の温度にて２４時間乾燥した。乾燥後、反応生成物の組成を分析したところ、塩基性炭酸マグネシウムであることが確認された。また、粒子形状を電子顕微鏡を用いて観察したところ、鱗片状の一次粒子が凝集した球状の多孔質粒子であることが確認された。
得られた多孔質粒状塩基性炭酸マグネシウムの比表面積、マクロ細孔の総容積、マクロ細孔の総容積占有率、平均粒子径及び５μｍ未満の多孔質粒子含有率を表１に、超音波粉砕処理後の平均粒子径及び安息角を表２に示す。
[Example 1]
Magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd., deer grade 1) is placed in an electric furnace, and the temperature is raised from room temperature to 450 ° C for 45 minutes, from 450 ° C to 700 ° C for 50 minutes, and from 700 ° C to 950 ° C for 80 minutes. And then held at 950 ° C. for 1 hour to obtain a magnesium oxide powder. When the average particle diameter of the primary particles of the obtained magnesium oxide powder was measured by the X-ray powder method, the value was 0.04 μm. In addition, after dispersing the magnesium oxide powder in ethanol, the average particle diameter of the secondary particles was measured using a laser diffraction particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtac X100). It was 6 μm.
1 kg of the above magnesium oxide powder was placed in a reaction vessel equipped with a stirrer containing 20 kg of hot water at 70 ° C., and stirred for 5 hours while blowing carbon dioxide gas having a CO 2 concentration of 25% by volume at a flow rate of 10.5 L / min. The reaction product was filtered with suction, washed with ethanol, and dried at a temperature of 120 ° C. for 24 hours. After drying, the composition of the reaction product was analyzed and confirmed to be basic magnesium carbonate. Moreover, when the particle shape was observed using an electron microscope, it was confirmed that the particles were spherical porous particles in which the scaly primary particles were aggregated.
Table 1 shows the specific surface area of the obtained porous granular basic magnesium carbonate, the total volume of macropores, the total volume occupancy of macropores, the average particle diameter, and the content of porous particles less than 5 μm. Table 2 shows the average particle diameter and angle of repose after treatment.
［実施例２］
水酸化マグネシウム（関東化学（株）製、鹿１級）を電気炉に入れ、室温から４５０℃まで４５分間、４５０℃から７００℃まで５０分間、７００℃から７５０℃まで１０分間の昇温条件で昇温した後、７５０℃にて１時間保持して酸化マグネシウム粉末を得た。得られた酸化マグネシウム粉末の一次粒子の平均粒子径をＸ線粉末法により測定したところ、その値は０．０２μｍであった。また、酸化マグネシウム粉末をエタノールに分散させた後、レーザ回折式粒度分布測定装置（日機装（株）製、ＭｉｃｒｏｔａｃＸ１００）を用いて、二次粒子の平均粒子径を測定したところ、その値は２．１μｍであった。
上記の酸化マグネシウム粉末１ｋｇを６０℃の温水２０ｋｇが入った攪拌機付き反応槽に入れ、ＣＯ2濃度１００容量％の炭酸ガスを１０．５Ｌ／分の流量にて吹き込みながら５時間攪拌した。反応生成物を吸引ろ過した後、エタノール洗浄し、１２０℃の温度にて２４時間乾燥した。乾燥後、反応生成物の組成を分析したところ、塩基性炭酸マグネシウムであることが確認された。また、粒子形状を電子顕微鏡を用いて観察したところ、鱗片状の一次粒子が凝集した球状の多孔質粒子であることが確認された。
得られた多孔質粒状塩基性炭酸マグネシウムの比表面積、マクロ細孔の総容積、マクロ細孔の総容積占有率、平均粒子径及び５μｍ未満の多孔質粒子含有率を表１に、超音波粉砕処理後の平均粒子径及び安息角を表２に示す。
[Example 2]
Magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd., deer grade 1) is placed in an electric furnace, and the temperature is raised from room temperature to 450 ° C for 45 minutes, from 450 ° C to 700 ° C for 50 minutes, and from 700 ° C to 750 ° C for 10 minutes. And then kept at 750 ° C. for 1 hour to obtain a magnesium oxide powder. When the average particle diameter of the primary particles of the obtained magnesium oxide powder was measured by the X-ray powder method, the value was 0.02 μm. In addition, after dispersing the magnesium oxide powder in ethanol, the average particle diameter of the secondary particles was measured using a laser diffraction particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtac X100). It was 1 μm.
1 kg of the above magnesium oxide powder was placed in a reaction vessel equipped with a stirrer containing 20 kg of hot water at 60 ° C., and stirred for 5 hours while blowing CO 2 gas of 100% by volume at a flow rate of 10.5 L / min. The reaction product was filtered with suction, washed with ethanol, and dried at a temperature of 120 ° C. for 24 hours. After drying, the composition of the reaction product was analyzed and confirmed to be basic magnesium carbonate. Moreover, when the particle shape was observed using an electron microscope, it was confirmed that the particles were spherical porous particles in which the scaly primary particles were aggregated.
Table 1 shows the specific surface area of the obtained porous granular basic magnesium carbonate, the total volume of macropores, the total volume occupancy of macropores, the average particle diameter, and the content of porous particles less than 5 μm. Table 2 shows the average particle diameter and angle of repose after treatment.
［比較例１］
水酸化マグネシウム（関東化学（株）製、鹿１級）１．４５ｋｇを７０℃の温水２０ｋｇが入った攪拌機付き反応槽に入れ、ＣＯ2濃度２５容量％の炭酸ガスを１０．５Ｌ／分の流量にて吹き込みながら５時間攪拌した。
反応生成物を吸引ろ過した後、エタノール洗浄し、１２０℃の温度にて２４時間乾燥した。乾燥後、反応生成物の組成を分析したところ、塩基性炭酸マグネシウムであることが確認された。また、粒子形状を電子顕微鏡を用いて観察したところ、鱗片状の一次粒子が凝集した球状の多孔質粒子であることが確認された。
得られた多孔質粒状塩基性炭酸マグネシウムの比表面積、マクロ細孔の総容積、マクロ細孔の総容積占有率、平均粒子径及び５μｍ未満の多孔質粒子含有率を表１に、超音波粉砕処理後の平均粒子径及び安息角を表２に示す。
[Comparative Example 1]
1.45 kg of magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd., deer grade 1) is placed in a reactor equipped with a stirrer containing 20 kg of hot water at 70 ° C., and carbon dioxide with a CO 2 concentration of 25% by volume is 10.5 L / min. The mixture was stirred for 5 hours while blowing at a flow rate.
The reaction product was filtered with suction, washed with ethanol, and dried at a temperature of 120 ° C. for 24 hours. After drying, the composition of the reaction product was analyzed and confirmed to be basic magnesium carbonate. Moreover, when the particle shape was observed using an electron microscope, it was confirmed that the particles were spherical porous particles in which the scaly primary particles were aggregated.
Table 1 shows the specific surface area of the obtained porous granular basic magnesium carbonate, the total volume of macropores, the total volume occupancy of macropores, the average particle diameter, and the content of porous particles less than 5 μm. Table 2 shows the average particle diameter and angle of repose after treatment.
［比較例２］
前記の特許文献３（特開昭６３−８９４１８号公報）の実施例１の記載に従って、下記の方法により多孔質粒状塩基性炭酸マグネシウムを製造した。
水酸化マグネシウム（関東化学（株）製、鹿１級）を炭酸化して得た濃度３０ｇＭｇＯ／Ｌの塩基性炭酸マグネシウム出発懸濁液１０Ｌを６０℃に保持して反応槽に入れ、これに濃度３０ｇＭｇＯ／Ｌの水酸化マグネシウム懸濁液を１０Ｌ／時間の速度で添加しながら、ＣＯ2濃度２５容量％の炭酸ガスを１０．５Ｌ／分の流量にて吹き込んだ。反応槽内の懸濁液量が５０Ｌになるまで水酸化マグネシウム懸濁液を添加し、添加終了後３０分間さらに炭酸ガスを吹き込んだ。反応生成物を吸引ろ過した後、エタノール洗浄し、１２０℃の温度にて２４時間乾燥した。乾燥後、反応生成物の組成を分析したところ、塩基性炭酸マグネシウムであることが確認された。また、粒子形状を電子顕微鏡を用いて観察したところ、鱗片状の一次粒子が凝集した球状の多孔質粒子であることが確認された。
得られた多孔質粒状塩基性炭酸マグネシウムの比表面積、マクロ細孔の総容積、マクロ細孔の総容積占有率、平均粒子径及び５μｍ未満の多孔質粒子含有率を表１に、超音波粉砕処理後の平均粒子径及び安息角を表２に示す。
[Comparative Example 2]
Porous granular basic magnesium carbonate was produced by the following method according to the description in Example 1 of Patent Document 3 (Japanese Patent Laid-Open No. 63-89418).
10 L of basic magnesium carbonate starting suspension having a concentration of 30 g MgO / L obtained by carbonation of magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd., deer grade 1) was kept at 60 ° C. and placed in a reaction vessel. While adding a magnesium hydroxide suspension of 30 g MgO / L at a rate of 10 L / hour, carbon dioxide gas having a CO 2 concentration of 25 vol% was blown at a flow rate of 10.5 L / min. Magnesium hydroxide suspension was added until the amount of suspension in the reaction vessel reached 50 L, and carbon dioxide gas was blown for 30 minutes after the addition was completed. The reaction product was filtered with suction, washed with ethanol, and dried at a temperature of 120 ° C. for 24 hours. After drying, the composition of the reaction product was analyzed and confirmed to be basic magnesium carbonate. Moreover, when the particle shape was observed using an electron microscope, it was confirmed that the particles were spherical porous particles in which the scaly primary particles were aggregated.
Table 1 shows the specific surface area of the obtained porous granular basic magnesium carbonate, the total volume of macropores, the total volume occupancy of macropores, the average particle diameter, and the content of porous particles less than 5 μm. Table 2 shows the average particle diameter and angle of repose after treatment.
表１
────────────────────────────────────────
比表面積 マクロ細孔の マクロ細孔の 平均粒子径 ５μｍ未満の多孔
総容積 総容積占有率 質粒子含有率
（ｍ2／ｇ） （ｍＬ／ｇ） （体積％） （μｍ） （体積％）
────────────────────────────────────────
実施例１ ５１．８ ０．４６２５ ９１ ４３ ３
実施例２ ４１．１ ０．３３３７ ８６ ３２ ５
────────────────────────────────────────
比較例１ １９．７ ０．１７４６ ５４ ９．１ ３２
比較例２ ２３．０ ０．１８９４ ５５ １８ １７
────────────────────────────────────────
Table 1
────────────────────────────────────────
Specific surface area Macropores Macropores Average particle size Pore with less than 5μm
Total volume Total volume share Mass particle content
(M 2 / g) (mL / g) (volume%) (μm) (volume%)
────────────────────────────────────────
Example 1 51.8 0.4625 91 43 3
Example 2 41.1 0.3337 86 32 5
────────────────────────────────────────
Comparative Example 1 19.7 0.1746 54 9.1 32
Comparative Example 2 23.0 0.1894 55 18 17
────────────────────────────────────────
表２
────────────────────────────────────────
超音波粉砕処理の平均粒子径（μｍ） 安息角（度）
────────────────────────────────────────
実施例１ ２．８ ３６
実施例２ ２．５ ３８
────────────────────────────────────────
比較例１ ８．８ ５５
比較例２ １４ ４５
────────────────────────────────────────
Table 2
────────────────────────────────────────
Average particle size of ultrasonic grinding (μm) Angle of repose (degrees)
────────────────────────────────────────
Example 1 2.8 36
Example 2 2.5 38
────────────────────────────────────────
Comparative Example 1 8.8 55
Comparative Example 2 14 45
────────────────────────────────────────
表１及び表２に示した結果から、マクロ細孔の容積が０．２ｍＬ／ｇ以上の塩基性炭酸マグネシウム（実施例１、実施例２）は、マクロ細孔の容積が０．２ｍＬ／ｇよりも小さいもの（比較例１、比較例２）と比べて、超音波粉砕処理後の平均粒子径が小さいことがわかる。 From the results shown in Tables 1 and 2, basic magnesium carbonate (Example 1, Example 2) having a macropore volume of 0.2 mL / g or more has a macropore volume of 0.2 mL / g. It can be seen that the average particle size after the ultrasonic pulverization treatment is smaller than those smaller than those (Comparative Example 1 and Comparative Example 2).
Claims (4)
2. The porous granular basic magnesium carbonate according to claim 1, wherein a magnesium oxide powder having an average primary particle diameter of 0.01 to 0.5 μm is brought into contact with carbon dioxide gas in an aqueous medium. Manufacturing method.
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| JP2007254193A (en) * | 2006-03-22 | 2007-10-04 | Ube Material Industries Ltd | Anhydrous magnesium carbonate powder and its manufacturing method |
| JP2009234829A (en) * | 2008-03-26 | 2009-10-15 | Bio Coke Lab Co Ltd | Method and apparatus for recycling magnesium hydroxide |
| JP2013510206A (en) * | 2009-11-03 | 2013-03-21 | オムヤ・デイベロツプメント・アー・ゲー | Precipitated magnesium carbonate |
| WO2014009802A2 (en) * | 2012-07-13 | 2014-01-16 | Calix Limited | Production of magnesium carbonate |
| JP2016508104A (en) * | 2012-12-06 | 2016-03-17 | ディスルプチベ マテリアルズ アクティエボラーグ | Anhydrous, amorphous and porous magnesium carbonate and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007254193A (en) * | 2006-03-22 | 2007-10-04 | Ube Material Industries Ltd | Anhydrous magnesium carbonate powder and its manufacturing method |
| JP2009234829A (en) * | 2008-03-26 | 2009-10-15 | Bio Coke Lab Co Ltd | Method and apparatus for recycling magnesium hydroxide |
| JP2013510206A (en) * | 2009-11-03 | 2013-03-21 | オムヤ・デイベロツプメント・アー・ゲー | Precipitated magnesium carbonate |
| WO2014009802A2 (en) * | 2012-07-13 | 2014-01-16 | Calix Limited | Production of magnesium carbonate |
| WO2014009802A3 (en) * | 2012-07-13 | 2014-03-06 | Calix Limited | Production of magnesium carbonate |
| JP2016508104A (en) * | 2012-12-06 | 2016-03-17 | ディスルプチベ マテリアルズ アクティエボラーグ | Anhydrous, amorphous and porous magnesium carbonate and process for producing the same |
| US10508041B2 (en) | 2012-12-06 | 2019-12-17 | Disruptive Materials Ab | Anhydrous, amorphous and porous magnesium carbonates and methods of production thereof |
| US11155469B2 (en) | 2012-12-06 | 2021-10-26 | Disruptive Materials Operations Ab | Mesoporous composite comprising anhydrous, amorphous magnesium carbonate and calcium carbonate, and methods of production thereof |
| WO2019044121A1 (en) * | 2017-08-28 | 2019-03-07 | 神島化学工業株式会社 | Highly dispersed basic magnesium carbonate powder, and method for producing same |
| JP2019038724A (en) * | 2017-08-28 | 2019-03-14 | 神島化学工業株式会社 | Highly-dispersible basic magnesium carbonate powder and production method thereof |
| JP2021133318A (en) * | 2020-02-27 | 2021-09-13 | 株式会社ジョンクェルコンサルティング | Method for treating carbon dioxide, and water dispersion used therein |
| JP2021171706A (en) * | 2020-04-24 | 2021-11-01 | 株式会社ジョンクェルコンサルティング | Carbon dioxide treatment method, and water dispersion used in the same |
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