JP5615146B2 - Method for transforming fibrous asbestos into cubic calcium carbonate - Google Patents
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- JP5615146B2 JP5615146B2 JP2010265035A JP2010265035A JP5615146B2 JP 5615146 B2 JP5615146 B2 JP 5615146B2 JP 2010265035 A JP2010265035 A JP 2010265035A JP 2010265035 A JP2010265035 A JP 2010265035A JP 5615146 B2 JP5615146 B2 JP 5615146B2
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Description
本発明は、繊維状の石綿を立方状の炭酸カルシウムに変形させる方法に関するものであって、より詳しくは、透角閃石を炭酸カルシウムに結晶化させて石綿の繊維状結晶を完全に除去する、石綿を用いた立方状の炭酸カルシウムの製造方法に関する。 The present invention relates to a method for transforming fibrous asbestos into cubic calcium carbonate, and more specifically, crystallizing amphibole into calcium carbonate to completely remove fibrous crystals of asbestos. The present invention relates to a method for producing cubic calcium carbonate using asbestos.
石綿類の鉱物は、自然界から産出される長尺の柱状、針状、および繊維状の結晶を有する６種のケイ酸塩鉱物であって、蛇紋石族（ｓｅｒｐｅｎｔｉｎｅ ｇｒｏｕｐ）と角閃石族（ａｍｐｉｂｏｌｅ ｇｒｏｕｐ）の２種類の鉱物群に分けられる。特に、角閃石の一種である透角閃石は、ＳｉＯ４の四面体が２つあるいは３つの角を共有結合して構成された二重鎖（ｄｏｕｂｌｅ ｃｈａｉｎ）を骨格にした結晶構造からなる。この際、二重鎖は、ＳｉＯ４の６個の四面体により環状を形成し、これらが繰り返してｃ軸に沿って鎖が長く配列される構造を有するが、このような配列形態は透角閃石を繊維状の変種をなすようにする。 Asbestos minerals are six kinds of silicate minerals having long columnar, needle-like, and fibrous crystals produced from the natural world. group) and divided into two mineral groups. In particular, transilopite, a kind of amphibole, has a crystal structure with a double chain composed of two or three corners of SiO 4 tetrahedrons covalently bonded. At this time, the double chain forms a ring with six tetrahedrons of SiO 4 and has a structure in which the chain is repeatedly arranged along the c-axis repeatedly. Try to make the fluorite a fibrous variant.
石綿（ａｓｂｅｓｔｏｓ）は、本来岩石中にある、繊維状のケイ酸塩鉱物であって、微細な大きさの繊維に容易に割れて糸を抽出することや、布を作ることが可能である。さらに、物理的に強靭で、化学的に酸とアルカリに対して非活性であり、電気と熱に対する絶縁性が高い。 Asbestos is a fibrous silicate mineral that is originally found in rocks, and can be easily broken into fine sized fibers to extract yarns and fabrics. Furthermore, it is physically tough, chemically inert to acids and alkalis, and has high insulation against electricity and heat.
石綿は、羽毛と絹のような感触を感じさせ、火に焼けず、腐食することもないため、従来、家庭用品、建築断熱材、自動車ブレーキライニング、また各種産業工程の材料として、その用途が３０００種類を超えるほど広範囲に用いられてきたが、石綿が呼吸器に吸入される場合、肺ガンなどの病気を起こすという事実が２０世紀半ばに始めて知られ、各種規制策が施行されてきた。しかし、既に長い間、石綿は各種素材として用いられたので、われらの生活環境に他の鉱物質と共に広範囲に分散されており、その濃度を減らすことが非常に難しい。 Asbestos feels like feathers and silk, does not burn to fire, and does not corrode, so it has traditionally been used as a material for household products, building insulation, automobile brake lining, and various industrial processes. It has been widely used to exceed 3000 types, but when asbestos is inhaled into the respiratory tract, the fact that it causes diseases such as lung cancer was first known in the middle of the 20th century, and various regulatory measures have been implemented. However, since asbestos has already been used as a material for many years, it is widely dispersed in our living environment along with other minerals, and it is very difficult to reduce its concentration.
一方、あらゆる石綿鉱物が危険なものではなく、繊維状に形成されている石綿だけ危険である。石綿ホコリは、呼吸器を通して吸入されて健康上の問題を引き起こすが、石綿ホコリを吸入したとして必ずしも病気が発生するものではない。 On the other hand, not all asbestos minerals are dangerous, only asbestos formed in a fibrous form is dangerous. Asbestos dust is inhaled through the respiratory tract and causes health problems, but asbestos dust is inhaled, it does not necessarily cause illness.
長さが５μｍ以上で、直径が２μｍ以下であり、その比（ａｓｐｅｃｔ ｒａｔｉｏ）が５：１以上である石綿ホコリが主に肺組織に沈着して病気を起こすと知られている。通常、職業上の理由で石綿ホコリの吸入量が多く、また吸入期間も長い場合に肺ガンにかかる確率が高いが、それも石綿を吸入してから２０〜４０年後に発病すると知られている。石綿による病気としては、石綿肺、肺ガン、中皮腫、胸膜肥厚などがある。 It is known that asbestos dust having a length of 5 μm or more and a diameter of 2 μm or less and an aspect ratio of 5: 1 or more mainly deposits on lung tissue and causes disease. Usually, for occupational reasons, the inhalation amount of asbestos dust is large, and when the inhalation period is long, the probability of getting lung cancer is high, but it is also known that the disease will occur 20 to 40 years after inhalation of asbestos. . Asbestos-related diseases include asbestosis, lung cancer, mesothelioma, and pleural thickening.
人体に対する石綿の毒性は、石綿鉱物の種類、粒子の大きさ、化学組成、表面特徴、耐久性などに関連がある。温石綿のように肺に含まれている体液に溶解される石綿は毒性が低く、透角閃石のように溶解性が低く、耐久性が大きい石綿は毒性が最も高い。韓国内で産出される透角閃石は、臨床実験の結果、毒性が非常に高いと報告されている。 The toxicity of asbestos to the human body is related to the type of asbestos mineral, particle size, chemical composition, surface characteristics, and durability. Asbestos that dissolves in body fluids contained in the lung, such as warm asbestos, has low toxicity, and asbestos that has low solubility and high durability, such as amphibole, has the highest toxicity. The amphibole produced in Korea is reported to be very toxic as a result of clinical experiments.
また、二酸化炭素は、温室ガスの中、最も多く排出されており、二酸化炭素の低減のために、安定した二酸化炭素の貯蔵技術が求められている。 Carbon dioxide is emitted most in greenhouse gases, and stable carbon dioxide storage technology is required to reduce carbon dioxide.
そのため、本発明者らは、上述した問題を解決しようと研究を重ねた結果、透角閃石にＣＯ２ガスを注入して炭酸塩鉱物を水熱反応させる場合、ＣＯ２の低減効果だけでなく、繊維状の透角閃石が立方状の方解石に転移することにより、２つの有害環境問題を同時に解決できることを確認し、本発明を完成した。 Therefore, as a result of repeated studies to solve the above-described problems, the present inventors have not only reduced the CO 2 reduction effect when the carbonate mineral is hydrothermally reacted by injecting CO 2 gas into the amphibole. It was confirmed that the two harmful environmental problems could be solved simultaneously by transferring the fibrous amphibole into cubic calcite, and the present invention was completed.
本発明の目的は、石綿の有害性を除去する方法であって、より詳しくは、有害な石綿の一種である透角閃石をＣＯ２ガスと反応させて炭酸カルシウムに結晶化することにより、石綿の繊維状結晶を完全に除去する、石綿を用いた立方状の炭酸カルシウムの製造方法を提供することにある。 An object of the present invention is a method for removing the harmfulness of asbestos, and more specifically, asbestos is obtained by reacting a hornblende, which is a kind of harmful asbestos, with CO 2 gas and crystallizing it into calcium carbonate. It is an object of the present invention to provide a method for producing cubic calcium carbonate using asbestos that completely removes the fibrous crystals.
本発明は、二酸化炭素の存在下で、透角閃石粉末およびアルカリ溶液の混合物を反応させて製造する、石綿を用いた立方状の炭酸カルシウムの製造方法を提供する。 The present invention provides a method for producing cubic calcium carbonate using asbestos, which is produced by reacting a mixture of amphibole powder and an alkaline solution in the presence of carbon dioxide.
本発明の製造方法は、高温高圧の反応容器内の二酸化炭素の存在下で、直接炭酸化過程を介して立方状の炭酸カルシウムを製造することを特徴とする。 The production method of the present invention is characterized in that cubic calcium carbonate is produced through a direct carbonation process in the presence of carbon dioxide in a high-temperature and high-pressure reaction vessel.
より詳しくは、本発明の製造方法は、ｐＨが１０〜１４の水溶液において、透角閃石粉末を３〜２０ｂａｒの二酸化炭素のガス分圧下で、２５０〜４００℃の反応温度および３０〜２００ｂａｒの反応圧力により製造することを特徴とする。 More specifically, in the production method of the present invention, in an aqueous solution having a pH of 10 to 14, the amphibole powder is subjected to a reaction temperature of 250 to 400 ° C. and a reaction of 30 to 200 bar under a gas partial pressure of 3 to 20 bar of carbon dioxide. It is manufactured by pressure.
以下、本発明を詳細に説明する。
本発明は、
ａ）粉砕された透角閃石粉末にアルカリ溶液を添加して混合物を製造した後、二酸化炭素を注入するステップと、
ｂ）二酸化炭素の存在下で、前記混合物を炭酸化反応させて炭酸カルシウムが含まれたスラリーを製造するステップと、
ｃ）前記製造されたスラリーから形態が変形された炭酸カルシウムを含む固体を得るステップと、
を含む、石綿を用いた立方状の炭酸カルシウムの製造方法を提供する。図１を参照する。
Hereinafter, the present invention will be described in detail.
The present invention
a) adding an alkaline solution to the pulverized amphibole powder to produce a mixture, and then injecting carbon dioxide;
b) carbonating the mixture in the presence of carbon dioxide to produce a slurry containing calcium carbonate;
c) obtaining a solid containing calcium carbonate having a deformed form from the produced slurry;
And a method for producing cubic calcium carbonate using asbestos. Please refer to FIG.
透角閃石の理想的な化学式は、Ｃａ２Ｍｇ５Ｓｉ８Ｏ２２（ＯＨ）２であり、５４．９％のＳｉＯ２、１２．３％のＣａＯ、１６．１％のＭｇＯ、１０．６１％のＦｅＯの化学組成を有する。 The ideal chemical formula for amphibole is Ca 2 Mg 5 Si 8 O 22 (OH) 2 , 54.9% SiO 2 , 12.3% CaO, 16.1% MgO, 10.61. % Chemical composition of FeO.
本発明は、前記透角閃石を二酸化炭素（ＣＯ２）と反応させ、方解石（ｃａｌｃｉｔｅ）およびマグネサイト（ｍａｇｎｅｃｉｔｅ）などの炭酸塩鉱物を生成させるものであって、前記ステップａ）の透角閃石粉末は粒子の大きさが３０μｍ以下であることを特徴とする。 The present invention is to react the amphibole with carbon dioxide (CO 2 ) to produce carbonate minerals such as calcite and magnesite, and the amphibole of the step a). The powder has a particle size of 30 μm or less.
より詳しくは、前記透角閃石粉末の粒子サイズは３０μｍ以下であり、粉末の粒子サイズが３０μｍを超える場合、炭酸化反応による立方状の炭酸カルシウムに転移しにくいだけでなく、結晶性が低下して純粋な炭酸カルシウムを製造しにくいという問題がある。すなわち、粒子サイズが３０μｍを超えると、反応性が減少することにより効率が大きく低下するだけでなく、石綿の形態を完全に変形させることができないため、毒性の低減および除去が容易でないという問題がある。 More specifically, the amphibole powder has a particle size of 30 μm or less, and when the particle size of the powder exceeds 30 μm, not only is it difficult to transfer to cubic calcium carbonate by the carbonation reaction, but also the crystallinity decreases. There is a problem that it is difficult to produce pure calcium carbonate. That is, when the particle size exceeds 30 μm, not only the efficiency is greatly reduced due to the decrease in reactivity, but also the form of asbestos cannot be completely deformed, and thus the problem that toxicity reduction and removal is not easy. is there.
本発明において、前記ステップａ）のアルカリ溶液は、ｐＨが１０〜１４であることを特徴とし、より詳しくは、蒸溜水に酢酸またはアンモニア水を添加してｐＨを１０〜１４にしてアルカリ度を調節したアルカリ溶液２００重量部に対して、粉砕された透角閃石粉末１〜１０重量部を混合して使用する。 In the present invention, the alkaline solution of step a) is characterized in that the pH is 10 to 14, more specifically, acetic acid or ammonia water is added to distilled water to adjust the pH to 10 to 14, thereby increasing the alkalinity. 1 to 10 parts by weight of pulverized amphibole powder is mixed with 200 parts by weight of the adjusted alkaline solution.
前記アルカリ溶液のｐＨが１０未満であるか、１４を超える場合は、炭酸化反応中、ｐＨ条件の悪化により炭酸カルシウムの再結晶化が困難となり、炭酸カルシウムの回収率を低減させるため、好ましくない。 If the pH of the alkaline solution is less than 10 or exceeds 14, it is not preferable because during the carbonation reaction, recrystallization of calcium carbonate becomes difficult due to deterioration of pH conditions, and the recovery rate of calcium carbonate is reduced. .
本発明において、前記ステップｂ）の炭酸化反応は、直接炭酸化反応であり、同一の反応器内の透角閃石から抽出された金属イオン（Ｃａ２＋、Ｍｇ２＋）と二酸化炭素ガスとの水熱反応により炭酸塩鉱物を製造することを特徴とする。 In the present invention, the carbonation reaction in the step b) is a direct carbonation reaction, and water of metal ions (Ca 2+ , Mg 2+ ) and carbon dioxide gas extracted from the hornblende in the same reactor. A carbonate mineral is produced by a thermal reaction.
より詳しくは、前記ステップｂ）の炭酸化反応は、３〜２０ｂａｒの二酸化炭素のガス分圧下で、２５０〜４００℃の反応温度および３０〜２００ｂａｒの反応圧力で行われるものであって、前記反応条件を全て満たす反応器内で製造されることにより、結晶性に優れた高純度の炭酸カルシウムを得ることができる。 More specifically, the carbonation reaction of step b) is performed under a gas partial pressure of 3 to 20 bar carbon dioxide at a reaction temperature of 250 to 400 ° C. and a reaction pressure of 30 to 200 bar. By producing in a reactor that satisfies all the conditions, high-purity calcium carbonate excellent in crystallinity can be obtained.
二酸化炭素ガスの注入量が３ｂａｒ未満または２０ｂａｒを超えて注入される場合、炭酸化反応中、ｐＨの低下により炭酸カルシウムの再結晶化が困難となるため、炭酸カルシウムの回収率が減少する問題がある。 When the injection amount of carbon dioxide gas is less than 3 bar or more than 20 bar, it is difficult to recrystallize calcium carbonate due to a decrease in pH during the carbonation reaction, and thus the recovery rate of calcium carbonate is reduced. is there.
また、反応温度が２５０℃未満または４００℃を超えて炭酸化反応させる場合、同一の反応器内で透角閃石と二酸化炭素との反応が不安定になって炭酸化反応が阻害されるため、炭酸カルシウムの製造が困難である。 In addition, when the carbonation reaction is performed at a reaction temperature of less than 250 ° C. or more than 400 ° C., the reaction between hornblende and carbon dioxide becomes unstable in the same reactor and the carbonation reaction is inhibited. It is difficult to produce calcium carbonate.
本発明において、前記ステップｃ）は、製造されたスラリーから固体を分離して乾燥した後、粉砕して製造することができる。この際、全ての繊維状石綿が球状、立方状などに変形されるため、もはや石綿ではなく、単純に方解石を含む環境に無害な粉末であるといえる。 In the present invention, the step c) may be produced by separating and drying the solid from the produced slurry and then pulverizing it. At this time, since all the fibrous asbestos is deformed into a spherical shape, a cubic shape or the like, it can be said that it is no longer asbestos but simply a harmless powder containing calcite.
前記スラリーから固体を分離するための分離手段としては、遠心分離機またはプレスフィルタなどを用いることができるが、これに限定されることはなく、固体と液体を分離する方法であれば何れも可能である。 As a separation means for separating the solid from the slurry, a centrifuge or a press filter can be used, but is not limited thereto, and any method can be used as long as it is a method for separating the solid and the liquid. It is.
本発明において、前記方法により製造された立方状の炭酸カルシウムは方解石であり、より詳しくは、前記方解石はＸ線回折分析における主回折角（２θ）が３．０３Å（１０４）、２．２８５Å（１１３）、および２．０９Å（２０２）であることが確認できる。図２を参照する。 In the present invention, the cubic calcium carbonate produced by the above method is calcite, and more specifically, the calcite has a main diffraction angle (2θ) in X-ray diffraction analysis of 3.03Å (104), 2.285Å ( 113) and 2.09 cm (202). Please refer to FIG.
本発明は、同一の反応器内で単一工程により繊維状の透角閃石を立方状の結晶性に優れた炭酸カルシウムとして効率的に製造でき、それだけでなく、二酸化炭素を安定して固定化または貯蔵できる、２つの有害環境問題を同時に解決できる長所がある。 The present invention can efficiently produce fibrous amphibole as calcium carbonate with excellent cubic crystallinity in a single process in the same reactor, and also stably fix carbon dioxide. It can also be stored, and has the advantage of solving two harmful environmental problems simultaneously.
本発明に係る石綿を用いた立方状の炭酸カルシウムの製造方法は、環境有害物質である石綿を用いて単一工程により経済的で、かつ結晶性に優れた炭酸カルシウムを製造できる長所がある。 The method for producing cubic calcium carbonate using asbestos according to the present invention has the advantage that it can be produced economically and with excellent crystallinity by a single process using asbestos which is an environmentally hazardous substance.
また、本発明に係る石綿を用いた立方状の炭酸カルシウムの製造方法は、石綿の繊維状結晶を完全に除去して根本的に石綿の有害性を除去でき、それだけでなく、二酸化炭素も安定して固定化または貯蔵できるため、２つの有害環境問題を同時に解決できる長所がある。 In addition, the method for producing cubic calcium carbonate using asbestos according to the present invention can completely remove the asbestos fiber crystals and completely remove the harmfulness of asbestos, and also stabilize carbon dioxide. Thus, the two harmful environmental problems can be solved simultaneously.
本発明は、下記実施例により具体的に説明する。しかし、下記実施例は、本発明を容易に理解するためのものであり、本発明の範囲がこれら実施例により限定されることはない。 The present invention will be specifically described by the following examples. However, the following examples are for easy understanding of the present invention, and the scope of the present invention is not limited by these examples.
ここで使用される技術用語および科学用語は、特に定義しなければ、この発明が属する技術分野で通常の知識を有する者であれば通常的に理解できる意味であり、以下の説明および添付図面において、本発明の要旨をかえって不明にすると判断される場合、公知機能および構成に対する説明は省略する。 Unless otherwise defined, technical and scientific terms used herein have a meaning that can be generally understood by those who have ordinary knowledge in the technical field to which the present invention belongs. In the following description and the accompanying drawings, When it is determined that the gist of the present invention is not clear, descriptions of known functions and configurations are omitted.
攪拌ミル（Ａｔｔｒｉｔｉｏｎ Ｍｉｌｌ、ＫＭＣ−１Ｂ、ＫＭＣ．）を用いて１Ｌポートに大きさ２ｍｍのジルコンボールを、装入量を６０％に調節し、回転速度１５００ｒｐｍで１時間攪拌することにより、透角閃石を１０μｍ程度の大きさに粉砕して透角閃石粉末を製造した。 By using a stirring mill (Attrition Mill, KMC-1B, KMC.), The zircon ball having a size of 2 mm was adjusted to the 1 L port, the charging amount was adjusted to 60%, and stirring was performed at a rotational speed of 1500 rpm for 1 hour. Splenite was pulverized to a size of about 10 μm to produce a hornblende powder.
また、蒸溜水２００ｃｃにアンモニア水（ＮＨ４ＯＨ、ＯＣＩ ｃｏｍｐａｎｙ Ｌｔｄ．）１ｃｃを添加してｐＨを１１に調節した後、１Ｌ反応容器に前記粉砕した透角閃石粉末１０ｇと共に投入した。 Further, 1 cc of aqueous ammonia (NH 4 OH, OCI company Ltd.) was added to 200 cc of distilled water to adjust the pH to 11, and then charged into a 1 L reaction vessel with 10 g of the pulverized amphibole powder.
前記反応容器に二酸化炭素（ＣＯ２）ガスを５ｂａｒ注入した後、２９０℃で攪拌しながら約５０分間反応させて安定した炭酸カルシウムスラリーを製造した。前記炭酸化反応後のｐＨは６．４１であった。 After injecting 5 bar of carbon dioxide (CO 2 ) gas into the reaction vessel, the mixture was reacted at 290 ° C. for about 50 minutes to produce a stable calcium carbonate slurry. The pH after the carbonation reaction was 6.41.
前記製造された炭酸カルシウムスラリーを、遠心分離機あるいはプレスフィルタなどを用いて固体と液体を分離し、脱水した後９０℃の温度で乾燥して粉砕することにより、白色の炭酸カルシウム粉末９．２４ｇを得た。 The manufactured calcium carbonate slurry is separated into solid and liquid using a centrifuge or a press filter, dehydrated, dried at a temperature of 90 ° C., and pulverized to obtain 9.24 g of white calcium carbonate powder. Got.
前記実施例で製造された炭酸カルシウムの成分をＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ）機器を用いて分析した。前記ＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ）分析は、Ｈｉｇｈ Ｒｅｓｏｌｕｔｉｏｎ Ｘ−Ｒａｙ Ｄｉｆｆｒａｃｔｏｍｅｔｅｒ（Ｘ’Ｐｅｒｔ ＰＲＯ Ｍｕｌｔｉ Ｐｕｒｐｏｓｅ Ｘ−Ｒａｙ Ｄｉｆｆｒａｃｔｏｍｅｔｅｒ；Ｃｕ ２ＫＷ（Ｍａｘ．６０ｋＶ ５５ｍＡ））、２θ範囲、１〜７０で分析した。 The components of the calcium carbonate prepared in the above example were analyzed using an XRD (X-ray diffusion) instrument. The XRD (X-ray diffraction) analysis was performed using High Resolution X-Ray Diffractometer (X'Pert Multi Purpose X-Ray Diffractometer; Cu 2KW (Max. 60 kV, 55 mA), 70 range).
図２のＸ線回折分析でも確認できるように、ｄ＝３．０３Å（１０４）、２．２８５Å（１１３）、２．０９Å（２０２）を示し、前記結果から反応容器内で直接炭酸化過程を介して単一工程により短時間内に結晶性の良好な方解石が製造されたことを確認できた。
［比較例１］
As can be confirmed by the X-ray diffraction analysis of FIG. 2, d = 3.03 Å (104), 2.285 Å (113), and 2.09 Å (202) are shown. Thus, it was confirmed that calcite having good crystallinity was produced in a short time by a single step.
[Comparative Example 1]
前記実施例のように、攪拌ミル（Ａｔｔｒｉｔｉｏｎ Ｍｉｌｌ、ＫＭＣ−１Ｂ、ＫＭＣ．）を用いて透角閃石粉末を製造した。また、蒸溜水２００ｃｃにアンモニア水（ＮＨ４ＯＨ、ＯＣＩ ｃｏｍｐａｎｙ Ｌｔｄ．）０．５ｃｃを添加してｐＨ９に調節した後、１Ｌ反応容器に前記粉砕した透角閃石粉末１０ｇと共に投入した。 The amphibole powder was manufactured using the stirring mill (Attrition Mill, KMC-1B, KMC.) Like the said Example. Further, 0.5 cc of ammonia water (NH 4 OH, OCI company Ltd.) was added to 200 cc of distilled water to adjust the pH to 9, and then charged into a 1 L reaction vessel with 10 g of the pulverized amphibole powder.
前記反応容器に二酸化炭素（ＣＯ２）ガスを５ｂａｒ注入した後、２９０℃で攪拌しながら約５０分間反応させて安定した炭酸カルシウムスラリーを製造した。前記炭酸化反応後のｐＨは６．２であった。 After injecting 5 bar of carbon dioxide (CO 2 ) gas into the reaction vessel, the mixture was reacted at 290 ° C. for about 50 minutes to produce a stable calcium carbonate slurry. The pH after the carbonation reaction was 6.2.
前記製造された炭酸カルシウムスラリーを遠心分離機あるいはプレスフィルタなどを用いて固体と液体を分離し、脱水した後９０℃の温度で乾燥して粉砕することにより、白色の粉末８．７ｇを得た。 The produced calcium carbonate slurry was separated into solid and liquid using a centrifuge or a press filter, dehydrated, dried at a temperature of 90 ° C. and pulverized to obtain 8.7 g of a white powder. .
前記比較例１で製造された炭酸カルシウムの成分をＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ）機器を用いて分析したが、図４でも確認できるように、方解石は全く製造されなかったことを確認できた。
［比較例２］
Although the component of the calcium carbonate manufactured by the said comparative example 1 was analyzed using the XRD (X-ray diffraction) apparatus, it has confirmed that calcite was not manufactured at all so that it could confirm also in FIG.
[Comparative Example 2]
前記実施例のように攪拌ミル（Ａｔｔｒｉｔｉｏｎ Ｍｉｌｌ、ＫＭＣ−１Ｂ、ＫＭＣ．）を用いて透角閃石粉末を製造した。また、蒸溜水２００ｃｃにアンモニア水（ＮＨ４ＯＨ、ＯＣＩ ｃｏｍｐａｎｙ Ｌｔｄ．）１ｃｃを添加してｐＨを１１に調節した後、１Ｌ反応容器に前記粉砕した透角閃石粉末１０ｇと共に投入した。 The amphibole powder was produced using a stirring mill (Attrition Mill, KMC-1B, KMC.) As in the above example. Further, 1 cc of aqueous ammonia (NH 4 OH, OCI company Ltd.) was added to 200 cc of distilled water to adjust the pH to 11, and then charged into a 1 L reaction vessel with 10 g of the pulverized amphibole powder.
前記反応容器に二酸化炭素（ＣＯ２）ガスを５ｂａｒ注入した後、２４０℃で攪拌しながら約５０分間反応させて安定した炭酸カルシウムスラリーを製造した。 After 5 bar of carbon dioxide (CO 2 ) gas was injected into the reaction vessel, the mixture was reacted at 240 ° C. for about 50 minutes to produce a stable calcium carbonate slurry.
前記製造された炭酸カルシウムスラリーを遠心分離機あるいはプレスフィルタなどを用いて固体と液体を分離し、脱水した後９０℃の温度で乾燥して粉砕することにより、白色の粉末８．９ｇを得た。 The manufactured calcium carbonate slurry was separated into solid and liquid using a centrifuge or a press filter, dehydrated, dried at 90 ° C. and pulverized to obtain 8.9 g of white powder. .
前記比較例２で製造された炭酸カルシウムの成分をＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ）機器を用いて分析したが、前記比較例１のように、方解石は全く製造されなかったことを確認できた。 Although the component of the calcium carbonate manufactured by the said comparative example 2 was analyzed using the XRD (X-ray diffraction) apparatus, it was confirmed that the calcite was not manufactured at all like the said comparative example 1.
Claims (4)
ａ）粉砕された透角閃石粉末にｐＨが１０〜１４であるアルカリ溶液を添加して混合物を製造した後、二酸化炭素を注入するステップと、
ｂ）二酸化炭素の存在下で、前記混合物を３〜２０ｂａｒの二酸化炭素のガス分圧下で、２５０〜３５０℃の反応温度および３０〜２００ｂａｒの反応圧力で、炭酸化反応させてスラリーを製造するステップと、
ｃ）前記製造されたスラリーから結晶化された炭酸カルシウムを得るステップと、
を含むことを特徴とする石綿を用いた立方状の炭酸カルシウムの製造方法。 In the presence of carbon dioxide, in the cubic of the manufacturing method of the calcium carbonate with asbestos you prepared mixture directly by carbonation reaction of tremolite powder and alkaline solution,
a) adding an alkaline solution having a pH of 10 to 14 to the pulverized amphibole powder to produce a mixture, and then injecting carbon dioxide;
b) producing a slurry by carbonation reaction of the mixture in the presence of carbon dioxide under a gas partial pressure of 3-20 bar carbon dioxide at a reaction temperature of 250-350 ° C. and a reaction pressure of 30-200 bar. When,
c) obtaining crystallized calcium carbonate from the prepared slurry;
A method for producing cubic calcium carbonate using asbestos, comprising
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