JP4248350B2 - Method for producing calcite-type calcium carbonate - Google Patents
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Description
本発明は、光学材料の原料として有用な炭酸カルシウム、特に粒子径の大きいカルサイト型炭酸カルシウムの製造方法に関するものである。 The present invention relates to a method for producing calcium carbonate useful as a raw material for optical materials, particularly calcite-type calcium carbonate having a large particle size.
炭酸カルシウムは、ゴム、プラスチック、顔料、製紙、蛍光体、歯磨粉、食品、光学ガラスやフッ化カルシウム等の原料として種々の用途に用いられている。これらに使用される炭酸カルシウムに要求される品質は用途によってさまざまである。光学ガラス用としては鉄等の遷移金属が少なく粒子径が大きく嵩密度の高い品質が要求される。特に、カルサイト型炭酸カルシウムの形状は、立方形状、紡錘形状（両先端のとがった形）等があり、大きな立方形状のものが得られない。 Calcium carbonate is used in various applications as a raw material for rubber, plastic, pigment, papermaking, phosphor, toothpaste, food, optical glass, calcium fluoride, and the like. The quality required for the calcium carbonate used for these varies depending on the application. For optical glass, a quality with a small transition metal such as iron, a large particle diameter and a high bulk density is required. In particular, the shape of calcite-type calcium carbonate includes a cubic shape, a spindle shape (a shape with sharp tips at both ends), and a large cubic shape cannot be obtained.
しかしながら、炭酸ガスと水酸化カルシウムとの気液反応で得られる炭酸カルシウムの製造方法においては、平均粒子径１０μｍ以下の小さな粒子は得られやすいが、４０μｍ以上の粒子のそろった大きなカルサイト型炭酸カルシウムを得ることは難しい（特許文献１〜３）。また、炭酸アンモニウム溶液を仕込みとしてカルシウム塩溶液を添加して反応させる方法では、平均粒子径２０μｍ以下のカルサイト型炭酸カルシウムしか得られない。一方、大きな粒子が得られ易い高い反応温度では、アラゴナイト型炭酸カルシウムが生成しやすく、平均粒子径が４０μｍ以上のカルサイト型炭酸カルシウムは得られない。又、カルシウム塩溶液と炭酸アンモニウム溶液を別々の供給口から同時に添加して反応させる方法では、微細なカルサイト型炭酸カルシウムが集合した球状の凝集晶に成り易く、凝集結晶の少ない立方形状の炭酸カルシウムは得られない。
本発明者らは、 これら従来技術の問題点に鑑み鋭意検討の結果、限られた反応方法において、限られた反応温度、スラリー濃度、晶出速度で反応させることにより、かかる目的を達成することができることを見いだし本発明に到達したものである。 As a result of intensive studies in view of the problems of these prior arts, the present inventors achieve this object by reacting at a limited reaction temperature, slurry concentration, and crystallization rate in a limited reaction method. The present invention has been found out.
すなわち本発明は、カルシウム塩溶液と炭酸アンモニウム溶液との反応による炭酸カルシウムの製造において、２０〜７５℃の温度範囲でカルシウム塩溶液に炭酸アンモニウム溶液を０．０５〜４０ｍｏｌ／ｈ／ｍｏｌ・カルシウム塩の範囲の添加速度で添加し、スラリー濃度を５〜１３重量％に維持することを特徴とする平均粒子径４０μｍ以上の立方形状のカルサイト型炭酸カルシウムの製造方法を提供するものである。
That is, the present invention relates to the production of calcium carbonate by the reaction of a calcium salt solution and an ammonium carbonate solution, and 0.05 to 40 mol / h / mol · calcium salt of the ammonium carbonate solution into the calcium salt solution at a temperature range of 20 to 75 ° C. Thus, a method for producing cubic calcite-type calcium carbonate having an average particle diameter of 40 μm or more is provided, which is added at an addition rate in the range of 5 to 13% by weight.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は、カルシウム塩溶液に炭酸アンモニウム溶液を添加して反応させる方法である。本発明で用いるカルシウム塩としては、塩化カルシウム、硝酸カルシウムである。 The present invention is a method of reacting a calcium salt solution by adding an ammonium carbonate solution. The calcium salt used in the present invention is calcium chloride or calcium nitrate.
本発明のカルシウム塩溶液に炭酸アンモニウム溶液を添加して反応させる方法においては、先にバテライト型炭酸カルシウムが生成した後、徐々にカルサイト型炭酸カルシウムに転移生成する。本発明の限られた条件を外れた場合には、平均粒子径が４０μｍ以上の立方形状のカルサイト型炭酸カルシウムを得ることは難しく、また極度に生産性が低下する。 In the method of adding an ammonium carbonate solution to the calcium salt solution of the present invention and reacting it, vaterite-type calcium carbonate is first produced and then gradually transferred to calcite-type calcium carbonate. When the conditions of the present invention are not satisfied, it is difficult to obtain cubic calcite-type calcium carbonate having an average particle diameter of 40 μm or more, and the productivity is extremely lowered.
本発明において、反応は、２０〜７５℃の温度範囲で実施するのが好ましく、最適には、３５〜６５℃の範囲が好ましい。反応温度が、２０℃より低いと、バテライト結晶晶出時の部分的なゲル化が大きくカルサイト型炭酸カルシウムの結晶核の発生量が多くなり、平均粒子径は４０μｍより小さくなり好ましくない。又、反応温度が７５℃より高いと晶出したバテライト型炭酸カルシウムからカルサイト型炭酸カルシウムへの転移速度が速く、カルサイト型炭酸カルシウムの結晶核の発生量が多くなり、平均粒子径は４０μｍより小さくなり好ましくない。 In the present invention, the reaction is preferably carried out in the temperature range of 20 to 75 ° C, and most preferably in the range of 35 to 65 ° C. When the reaction temperature is lower than 20 ° C., partial gelation at the time of crystallization of the vaterite crystal is large, and the amount of crystal nuclei of calcite-type calcium carbonate is increased, and the average particle size is less than 40 μm. Also, when the reaction temperature is higher than 75 ° C., the rate of transition from crystallized vaterite-type calcium carbonate to calcite-type calcium carbonate is high, the amount of crystal nuclei of calcite-type calcium carbonate is increased, and the average particle size is 40 μm. It becomes smaller and is not preferable.
一方、炭酸アンモニウム溶液の添加速度とは、カルシウム塩１ｍｏｌに対し炭酸アンモニウムを１時間当たりに添加するｍｏｌ数で表すものであり、０．０５〜４０ｍｏｌ／ｈ／ｍｏｌ・カルシウム塩の範囲で添加するのが好ましい。添加速度が、０．０５ｍｏｌ／ｈ／ｍｏｌ・カルシウム塩より遅いと極度に生産性が低下するため現実的でない。又、反応槽内では十分な混合拡散が行われていることが必要であり、混合拡散が悪いと平均粒子径が４０μｍ以上のカルサイト型炭酸カルシウムは得られない。また、添加速度が、４０ｍｏｌ／ｈ／ｍｏｌ・カルシウム塩を超えると平均粒子径が４０μｍより小さくなり好ましくない。 On the other hand, the addition rate of the ammonium carbonate solution is expressed as the number of moles of ammonium carbonate added per hour with respect to 1 mol of calcium salt, and is added in the range of 0.05 to 40 mol / h / mol · calcium salt. Is preferred. If the addition rate is slower than 0.05 mol / h / mol · calcium salt, the productivity is extremely lowered, which is not realistic. In addition, it is necessary that sufficient mixing and diffusion is performed in the reaction vessel. If the mixing and diffusion is poor, a calcite-type calcium carbonate having an average particle size of 40 μm or more cannot be obtained. On the other hand, when the addition rate exceeds 40 mol / h / mol · calcium salt, the average particle size is less than 40 μm, which is not preferable.
また、本発明において、反応時のスラリーを５〜１３重量％に維持することが必要である。より最適には、６〜１１重量％に維持することが好ましい。スラリー濃度が、１３重量％以上になると炭酸アンモニウムの溶液の添加時混合拡散が悪化し、結晶晶出時の部分的なゲル化が大きくなるため、カルサイト型炭酸カルシウムの結晶核の発生量が多く平均粒子径は４０μｍより小さくなる。一方、スラリー濃度が５重量％未満の場合は、極度に生産性が低下するため現実的でない。 In the present invention, it is necessary to maintain the slurry during the reaction at 5 to 13% by weight. More preferably, it is preferably maintained at 6 to 11% by weight. When the slurry concentration is 13% by weight or more, mixing and diffusion at the time of addition of the ammonium carbonate solution deteriorates and partial gelation at the time of crystal crystallization increases, so the amount of crystal nuclei of calcite-type calcium carbonate generated In many cases, the average particle size is smaller than 40 μm. On the other hand, when the slurry concentration is less than 5% by weight, the productivity is extremely lowered, which is not realistic.
本発明の方法により、平均粒子径４０μｍ以上の立方形状のカルサイト型炭酸カルシウムを容易に得ることを可能にした。 By the method of the present invention, cubic calcite calcium carbonate having an average particle diameter of 40 μm or more can be easily obtained.
以下、本発明を実施例により詳細に説明するが、かかる実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not limited to this Example.
実施例１
１４重量％塩化カルシウム（０．７６４ｍｏｌ）溶液６０５．２ｇを１Ｌビーカーに仕込み撹拌しながら３０℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム溶液２４４．８ｇ（０．７６４ｍｏｌ）を、４時間で添加した。この時の炭酸アンモニウム添加速度は、０．２５ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ２である。また、最終スラリー濃度は９重量％であった。
Example 1
605.2 g of a 14 wt% calcium chloride (0.764 mol) solution was charged into a 1 L beaker and kept warm at 30 ° C. with stirring. To this charged solution, 244.8 g (0.764 mol) of a 30 wt% ammonium carbonate solution was added in 4 hours. The addition rate of ammonium carbonate at this time is 0.25 mol / h / mol · CaCl 2 . The final slurry concentration was 9% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定した結果、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。 As a result of measuring the crystal form of the produced calcium carbonate with an X-ray diffractometer, it was confirmed that the total amount of calcium carbonate was transferred to calcite type calcium carbonate. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours.
得られたカルサイト型炭酸カルシウムを粒度分布測定装置（セイシン企業製,レーザーマイクロンサイザーＰＲＯ―７０００Ｓ）にて測定した結果、平均粒子径は５１μｍであった。 As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring apparatus (manufactured by Seishin Enterprise, Laser Micron Sizer PRO-7000S), the average particle size was 51 μm.
実施例２
塩化カルシウムの水溶液を１Ｌビーカーに仕込み撹拌しながら６５℃に加温保持して反応を行なった以外は実施例１と同様の操作を行なった。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は４１μｍであった。
Example 2
The same operation as in Example 1 was carried out except that an aqueous solution of calcium chloride was charged in a 1 L beaker and kept warm at 65 ° C. while stirring and reacted. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring device, the average particle size was 41 μm.
実施例３
２１．６重量％塩化カルシウム（１．０１９ｍｏｌ）溶液５２３．６ｇを１Ｌビーカーに仕込み撹拌しながら５５℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム溶液３２６．４ｇ（１．０１９ｍｏｌ）を、１０時間で添加した。この時の炭酸アンモニウム添加速度は、０．１ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ２である。また、最終スラリー濃度は１２重量％であった。
Example 3
523.6 g of a 21.6 wt% calcium chloride (1.019 mol) solution was charged into a 1 L beaker and kept warm at 55 ° C. with stirring. 306.4 g (1.019 mol) of a 30 wt% ammonium carbonate solution was added to the charged solution over 10 hours. The addition rate of ammonium carbonate at this time is 0.1 mol / h / mol · CaCl 2 . The final slurry concentration was 12% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は４５μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring device, the average particle size was 45 μm.
実施例４
１４重量％塩化カルシウム（０．７６４ｍｏｌ）溶液６０５．２ｇを１Ｌビーカーに仕込み撹拌しながら５５℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム溶液２４４．８ｇ（０．７６４ｍｏｌ）を、２分で添加した。この時の炭酸アンモニウムの添加速度は、３０ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ2である。また、最終スラリー濃度は９重量％であった。
Example 4
605.2 g of a 14 wt% calcium chloride (0.764 mol) solution was charged into a 1 L beaker and kept warm at 55 ° C. with stirring. To this charged solution, 244.8 g (0.764 mol) of a 30 wt% ammonium carbonate solution was added in 2 minutes. The addition rate of ammonium carbonate at this time is 30 mol / h / mol · CaCl 2 . The final slurry concentration was 9% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は４３μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring device, the average particle size was 43 μm.
実施例５
１４重量％塩化カルシウム（８０９．１ｍｏｌ）溶液６４０．９ｋｇを１ｍ３のＰＴＦＥ製反応槽に仕込み撹拌しながら４０℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム水溶液２５９．１ｋｇ（８０９．１ｍｏｌ）を、１４時間で添加した。この時の炭酸アンモニウムの添加速度は、０．０７ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ2である。また、最終スラリー濃度は９重量％であった。
Example 5
A 14 wt% calcium chloride (809.1 mol) solution (640.9 kg) was charged into a 1 m 3 PTFE reaction vessel and kept warm at 40 ° C. with stirring. To this charged solution, 259.1 kg (809.1 mol) of a 30 wt% ammonium carbonate aqueous solution was added over 14 hours. The addition rate of ammonium carbonate at this time is 0.07 mol / h / mol · CaCl 2 . The final slurry concentration was 9% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は５３μｍであった。 After measuring the crystal form of the generated calcium carbonate with an X-ray diffractometer and confirming that all of the calcium carbonate has been transferred to the calcite type calcium carbonate, the slurry containing the generated calcium carbonate is washed with filtered water, and the resulting precipitate is obtained. Was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring device, the average particle size was 53 μm.
実施例６
２４重量％硝酸カルシウム（０．７６４ｍｏｌ）溶液５２３．６ｇを１Ｌビーカーに仕込み撹拌しながら５５℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム溶液２４４．８ｇ（０．７６４ｍｏｌ）を、８時間で添加した。この時の炭酸アンモニウムの添加速度は、０．１２５ｍｏｌ／ｈ／ｍｏｌ・Ｃａ(ＮＯ３)２である。また、最終スラリー濃度は９重量％であった。
Example 6
523.6 g of a 24 wt% calcium nitrate (0.764 mol) solution was charged into a 1 L beaker and kept warm at 55 ° C. with stirring. To this charged solution, 244.8 g (0.764 mol) of a 30 wt% ammonium carbonate solution was added over 8 hours. The addition rate of ammonium carbonate at this time is 0.125 mol / h / mol · Ca (NO 3 ) 2 . The final slurry concentration was 9% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は４９μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring device, the average particle size was 49 μm.
比較例１
８重量％炭酸アンモニウム溶液６１５ｇ（０．５０９ｍｏｌ）を１Ｌビーカーに仕込み撹拌しながら５０℃に加温保持した。この仕込み液に２４重量％塩化カルシウム（０．５０９ｍｏｌ）溶液２３５．４ｇを、３０分で添加した。この時の塩化カルシウムの添加速度は、２ｍｏｌ／ｈ／ｍｏｌ・（ＮＨ４）２ＣＯ３である。また、最終スラリー濃度は６重量％であった。
Comparative Example 1
615 g (0.509 mol) of an 8 wt% ammonium carbonate solution was charged into a 1 L beaker and kept warm at 50 ° C. with stirring. 235.4 g of a 24 wt% calcium chloride (0.509 mol) solution was added to the charged solution in 30 minutes. The addition rate of calcium chloride at this time is 2 mol / h / mol · (NH 4 ) 2 CO 3 . The final slurry concentration was 6% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は１２μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite-type calcium carbonate with a particle size distribution analyzer, the average particle size was 12 μm.
比較例２
８重量％炭酸アンモニウム水溶液６１５ｇ（０．５０９ｍｏｌ）を１Ｌビーカーに仕込み撹拌しながら５０℃に加温保持した。この仕込み液に２４重量％塩化カルシウム溶液２３５．４ｇ（０．５０９ｍｏｌ）を、６時間で添加した。この時の塩化カルシウムの添加速度は、０．１７ｍｏｌ／ｈ／ｍｏｌ・（ＮＨ４）２ＣＯ３である。また、最終スラリー濃度は６重量％であった。
Comparative Example 2
615 g (0.509 mol) of 8 wt% ammonium carbonate aqueous solution was charged into a 1 L beaker and kept warm at 50 ° C. with stirring. 235.4 g (0.509 mol) of a 24 wt% calcium chloride solution was added to this charged solution over 6 hours. The addition rate of calcium chloride at this time is 0.17 mol / h / mol · (NH 4 ) 2 CO 3 . The final slurry concentration was 6% by weight.
生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。炭酸カルシウムの結晶型をＸ線回折装置で測定した結果、アラゴナイト型炭酸カルシウムとカルサイト型炭酸カルシウムが混在していた。 The produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the crystal form of calcium carbonate with an X-ray diffractometer, aragonite-type calcium carbonate and calcite-type calcium carbonate were mixed.
比較例３
比較例２と同様の操作を行ない生成した針状のアラゴナイト型炭酸カルシウムを含むスラリーがカルサイト型炭酸カルシウムに全量転移するまで３０時間熟成を行なった。生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は１８μｍであった。
Comparative Example 3
The same operation as in Comparative Example 2 was performed, and aging was performed for 30 hours until the entire slurry containing acicular aragonite-type calcium carbonate was transferred to calcite-type calcium carbonate. The produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite-type calcium carbonate with a particle size distribution analyzer, the average particle size was 18 μm.
比較例４
イオン交換水４５１．６ｇを１Ｌビーカーに仕込み撹拌しながら４０℃に加温保持した。この仕込み水に２４重量％塩化カルシウム溶液２３５．４ｇ（０．５０９ｍｏｌ）と３０重量％炭酸アンモニウム溶液１６３ｇ（０．５０９ｍｏｌ）を、ＣＯ２／Ｃａモル比１になるようにそれぞれ０．１２７ｍｏｌ／ｈの速度で別々の供給口から同時に添加を行ない５０℃を保持した。最終スラリー濃度は６重量％であった。
Comparative Example 4
451.6 g of ion-exchanged water was charged into a 1 L beaker and kept warm at 40 ° C. with stirring. In this charged water, 235.4 g (0.509 mol) of a 24 wt% calcium chloride solution and 163 g (0.509 mol) of a 30 wt% ammonium carbonate solution were each 0.127 mol / h so that the CO 2 / Ca molar ratio was 1. Were added simultaneously from separate feed ports at a rate of 50 ° C. and maintained at 50 ° C. The final slurry concentration was 6% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、スラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。尚、生成した炭酸カルシウムを顕微鏡確認したところ微細な結晶が集合した球状の凝集晶であった。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は３８μｍの凝集晶であった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the slurry was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. In addition, when the produced calcium carbonate was microscopically confirmed, it was a spherical aggregated crystal in which fine crystals were assembled. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring apparatus, it was an aggregated crystal having an average particle size of 38 μm.
比較例５
６．６重量％塩化カルシウム溶液７１４ｇ（０．４２５ｍｏｌ）を１Ｌビーカーに仕込み撹拌しながら１５℃に保持した。この仕込み液に３０重量％炭酸アンモニウム溶液１３６ｇ（０．４２５ｍｏｌ）を、４時間で添加した。この時の炭酸アンモニウムの添加速度は、０．２５ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ２である。また、最終スラリー濃度は５重量％であった。
Comparative Example 5
714 g (0.425 mol) of a 6.6 wt% calcium chloride solution was charged into a 1 L beaker and kept at 15 ° C. with stirring. To this charged solution, 136 g (0.425 mol) of a 30 wt% ammonium carbonate solution was added in 4 hours. The addition rate of ammonium carbonate at this time is 0.25 mol / h / mol · CaCl 2 . The final slurry concentration was 5% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は３５μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite-type calcium carbonate with a particle size distribution analyzer, the average particle size was 35 μm.
比較例６
塩化カルシウムの水溶液を１Ｌビーカーに仕込み撹拌しながら８０℃に加温保持して反応を行なった以外は比較例５と同様の操作を行なった。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は３０μｍであった。
Comparative Example 6
The same operation as in Comparative Example 5 was carried out except that an aqueous solution of calcium chloride was charged into a 1 L beaker and heated and maintained at 80 ° C. while stirring. As a result of measuring the obtained calcite type calcium carbonate with a particle size distribution measuring device, the average particle size was 30 μm.
比較例７
２８重量％塩化カルシウム溶液４６９．２ｇ（１．１８９ｍｏｌ）を１Ｌビーカーに仕込み撹拌しながら５５℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム溶液３８０．８ｇ（１．１８９ｍｏｌ）を、４時間で添加した。この時の炭酸アンモニウムの添加速度は、０．２５ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ２である。また、最終スラリー濃度は１４重量％であった。
Comparative Example 7
469.2 g (1.189 mol) of 28 wt% calcium chloride solution was charged into a 1 L beaker and kept warm at 55 ° C. with stirring. To this charging solution, 380.8 g (1.189 mol) of 30 wt% ammonium carbonate solution was added in 4 hours. The addition rate of ammonium carbonate at this time is 0.25 mol / h / mol · CaCl 2 . The final slurry concentration was 14% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は２０μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite-type calcium carbonate with a particle size distribution analyzer, the average particle size was 20 μm.
比較例８
１４重量％塩化カルシウム溶液６８８．９ｇ（０．５０９ｍｏｌ）を１Ｌビーカーに仕込み撹拌しながら５５℃に加温保持した。この仕込み液に３０重量％炭酸アンモニウム溶液１６３．０ｇ（０．５０９ｍｏｌ）を、１分で添加した。この時の炭酸アンモニウムの添加速度は、６０ｍｏｌ／ｈ／ｍｏｌ・ＣａＣｌ２である。最終スラリー濃度は６重量％であった。
Comparative Example 8
688.9 g (0.509 mol) of 14 wt% calcium chloride solution was charged into a 1 L beaker and kept warm at 55 ° C. with stirring. To this charging solution, 163.0 g (0.509 mol) of a 30 wt% ammonium carbonate solution was added in 1 minute. The addition rate of ammonium carbonate at this time is 60 mol / h / mol · CaCl 2 . The final slurry concentration was 6% by weight.
生成した炭酸カルシウムの結晶型をＸ線回折装置で測定し、カルサイト型炭酸カルシウムに全量転移しているのを確認した。その後、生成した炭酸カルシウムを含むスラリーを濾過水洗し、得られた沈殿物を１００℃で１０時間乾燥した。得られたカルサイト型炭酸カルシウムを粒度分布測定装置にて測定した結果、平均粒子径は２０μｍであった。 The crystal form of the generated calcium carbonate was measured with an X-ray diffractometer, and it was confirmed that the total amount of calcite type calcium carbonate had been transferred. Thereafter, the produced slurry containing calcium carbonate was washed with filtered water, and the resulting precipitate was dried at 100 ° C. for 10 hours. As a result of measuring the obtained calcite-type calcium carbonate with a particle size distribution analyzer, the average particle size was 20 μm.
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