JP5015457B2 - Method for producing tubular calcium carbonate - Google Patents
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- JP5015457B2 JP5015457B2 JP2005380061A JP2005380061A JP5015457B2 JP 5015457 B2 JP5015457 B2 JP 5015457B2 JP 2005380061 A JP2005380061 A JP 2005380061A JP 2005380061 A JP2005380061 A JP 2005380061A JP 5015457 B2 JP5015457 B2 JP 5015457B2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims description 111
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 235000010216 calcium carbonate Nutrition 0.000 claims description 58
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 27
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000013535 sea water Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000011162 core material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、中空柱状アラゴナイトからなるチューブ状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 tubular calcium carbonate made of hollow columnar aragonite.
従来、炭酸カルシウムの工業的製法は、水酸化カルシウム懸濁液に炭酸ガスを吹き込む石灰乳炭酸化法に代表される。
また、中空柱状炭酸カルシウムの製法については、柱状硫酸カルシウムを芯とし、その外側に炭酸カルシウム結晶を付着させ、その後、芯となっている硫酸カルシウムを溶解させる方法が提案されている(特許文献1参照)。しかし、この方法は、炭酸カルシウム以外に別途無機カルシウム芯材を要し、工程が多段で煩雑な上に、得られる炭酸カルシウムは、カルサイト形微結晶の集合体に限られるという問題がある。
Conventionally, an industrial production method of calcium carbonate is represented by a lime milk carbonation method in which carbon dioxide gas is blown into a calcium hydroxide suspension.
As for a method for producing hollow columnar calcium carbonate, a method is proposed in which columnar calcium sulfate is used as a core, calcium carbonate crystals are adhered to the outside thereof, and then the calcium sulfate serving as the core is dissolved (Patent Document 1). reference). However, this method requires a separate inorganic calcium core material in addition to calcium carbonate, and the process is complicated and complicated, and the resulting calcium carbonate is limited to an aggregate of calcite-type microcrystals.
本発明の課題は、新規なチューブ状炭酸カルシウム、及びそれを簡易に製造する方法を提供することにある。 An object of the present invention is to provide a novel tubular calcium carbonate and a method for easily producing the same.
本発明者らは、前記チューブ状炭酸カルシウム、及びその簡易な製造法について鋭意研究を重ねた結果、工業的炭酸カルシウム製法である石灰乳炭酸化法において、その反応過程中の素反応に相当する炭酸水素カルシウム水溶液からの炭酸カルシウムの析出過程に着目し、その炭酸カルシウムの製造への応用を図り、飽和炭酸水素カルシウム水溶液やそれに類する液を熱水に滴下することにより、前記チューブ状炭酸カルシウムが容易に析出することを見出し、この知見に基づいて本発明をなすに至った。 As a result of intensive research on the tubular calcium carbonate and its simple production method, the present inventors corresponded to the elementary reaction during the reaction process in the lime milk carbonation method, which is an industrial calcium carbonate production method. Paying attention to the precipitation process of calcium carbonate from aqueous calcium hydrogen carbonate solution, aiming at its application to the production of calcium carbonate, dripping a saturated calcium hydrogen carbonate aqueous solution or similar liquid into hot water, the tube-like calcium carbonate becomes Based on this finding, the present inventors have found that it easily precipitates and have made the present invention.
すなわち、本発明によれば、以下の発明が提供される。
(1)柱状アラゴナイトであって、その長軸方向に中空で、かつ両端が開口してなるチューブ状炭酸カルシウムを製造する方法であって、他の無機電解質が共存していてもよい炭酸水素カルシウム水溶液又は海水を、炭酸水素カルシウムの飽和あるいは過飽和状態下、熱水に滴下することを特徴とするチューブ状炭酸カルシウムの製造方法。
(2)滴下液滴径を変化させてチューブ径を変化させる前記(1)記載の製造方法。
(3)熱水の温度が90℃以上である前記(1)又は(2)記載の製造方法。
(4)前記炭酸水素カルシウム水溶液又は海水が、前記飽和あるいは過飽和状態下、100℃以下の温度に調整される前記(1)ないし(3)のいずれかに記載の製造方法。
(5)前記炭酸水素カルシウム水溶液又は海水が、前記飽和あるいは過飽和状態下、50℃以下の温度に調整される前記(1)ないし(3)のいずれかに記載の製造方法。
That is, according to the present invention, the following inventions are provided.
(1) A method for producing a tubular calcium carbonate which is a columnar aragonite and is hollow in the major axis direction and is open at both ends, in which other inorganic electrolytes may coexist. A method for producing tubular calcium carbonate, comprising dropping an aqueous solution or seawater into hot water under a saturated or supersaturated state of calcium bicarbonate.
(2) The manufacturing method according to (1), wherein the diameter of the dropped droplet is changed to change the tube diameter.
(3) The manufacturing method according to (1) or (2), wherein the temperature of hot water is 90 ° C. or higher.
(4) The production method according to any one of (1) to (3), wherein the aqueous calcium hydrogen carbonate solution or seawater is adjusted to a temperature of 100 ° C. or lower under the saturated or supersaturated state.
(5) The production method according to any one of (1) to (3), wherein the aqueous calcium hydrogen carbonate solution or seawater is adjusted to a temperature of 50 ° C. or lower under the saturated or supersaturated state.
本発明炭酸カルシウムは、柱状アラゴナイトであって、その長軸方向に中空で、かつ両端が開口してなるチューブ状のものである。
本発明炭酸カルシウムは、両端が開口しているので、中空内部は外部と連通し、中空内部に炭酸カルシウムと異なる充填物質を懸濁液状態で包含させる場合、中空内部の液と母液との圧力差がなく、操作が容易である。
このような充填物質としては、例えばイオン、分子、又は微粒子状のものが挙げられる。
本発明には、このように本発明炭酸カルシウムの中空に炭酸カルシウムと異なる充填物質を包含させてなる包接炭酸カルシウムも包含される。
The calcium carbonate of the present invention is a columnar aragonite that is hollow in the major axis direction and has a tube shape that is open at both ends.
Since both ends of the calcium carbonate of the present invention are open, the hollow interior communicates with the exterior, and when the hollow interior contains a filler substance different from calcium carbonate in a suspension state, the pressure between the liquid inside the hollow and the mother liquor There is no difference and operation is easy.
Examples of such a filling material include ions, molecules, and fine particles.
The present invention also includes an inclusion calcium carbonate in which a filler different from calcium carbonate is included in the hollow of the calcium carbonate of the present invention.
本発明炭酸カルシウムは、本発明方法、すなわち、他の無機電解質が共存していてもよい炭酸水素カルシウム水溶液又は海水を、炭酸水素カルシウムの飽和あるいは過飽和状態下、熱水に滴下する方法により製造することができる。
本発明方法において、炭酸水素カルシウムの飽和あるいは過飽和状態については、炭酸水素カルシウム水溶液では、その調製に当たり予めそのような状態にするようにしてもよいし、また、炭酸水素カルシウム水溶液の調製後に液温調整等の調整手段により上記飽和あるいは過飽和状態にするようにしてもよく、海水では、その温度によっては上記飽和あるいは過飽和状態下にしうるし、さもなければ液温調整等の調整手段により上記飽和あるいは過飽和状態にすればよい。
The calcium carbonate of the present invention is produced by the method of the present invention, that is, a method in which an aqueous solution of calcium hydrogen carbonate or seawater in which other inorganic electrolytes may coexist is dropped into hot water in a saturated or supersaturated state of calcium bicarbonate. be able to.
In the method of the present invention, regarding the saturated or supersaturated state of calcium hydrogen carbonate, the aqueous solution of calcium hydrogen carbonate may be brought into such a state in advance for its preparation. The saturated or supersaturated state may be achieved by adjusting means such as adjusting. In seawater, depending on the temperature, the saturated or supersaturated state may be obtained. Otherwise, the saturated or supersaturated state may be achieved by adjusting means such as liquid temperature adjusting. It should be in a state.
本発明方法において、炭酸水素カルシウムは、例えばその水溶液として供され、この溶液中には他の無機電解質を共存させることもできる。この無機電荷質としては、例えば、NaClやKClやMgCl2を挙げることができる。
また、炭酸水素カルシウムは、それを相当量溶解していることがよく知られている海水として供されてもよい。
海水は、いわば、無機電解質を溶解させた水溶液と見ることができるので、人工的に、作製した無機電荷質水溶液、例えば、NaClやKClやMgCl2を単独又は混合溶解させて作製した水溶液中に、CaCO3またはCa(OH)2の粒子を懸濁させ、そこに炭酸ガスを吹き込むことにより作製した、炭酸水素カルシウム水溶液なども海水に類するものとして用いることができる。
これらの炭酸水素カルシウム水溶液又は海水は、炭酸水素カルシウムが飽和あるいは過飽和状態にあるように調整され、通常100℃以下、好ましくは50℃以下の温度に調整して用いられる。この温度調整については、Ca濃度は温度依存性であり、温度の低い方が高くなるため、収量を多くするには、より低温とするのがよい。
In the method of the present invention, calcium bicarbonate is provided, for example, as an aqueous solution thereof, and other inorganic electrolytes can coexist in this solution. Examples of the inorganic charge material include NaCl, KCl, and MgCl 2 .
In addition, calcium bicarbonate may be provided as seawater, which is well known to dissolve a considerable amount thereof.
Seawater can be considered as an aqueous solution in which an inorganic electrolyte is dissolved, so it is artificially prepared in an aqueous solution of an inorganic charge produced, for example, an aqueous solution prepared by dissolving NaCl, KCl, or MgCl 2 alone or in combination. An aqueous solution of calcium bicarbonate prepared by suspending CaCO 3 or Ca (OH) 2 particles and blowing carbon dioxide into the particles can also be used as similar to seawater.
These aqueous calcium bicarbonate solutions or seawater are adjusted so that calcium bicarbonate is in a saturated or supersaturated state, and are usually adjusted to a temperature of 100 ° C. or lower, preferably 50 ° C. or lower. For this temperature adjustment, the Ca concentration is temperature-dependent, and the lower the temperature, the higher the temperature. Therefore, the lower the temperature, the better.
本発明方法において、滴下させる液滴の径を変化させることにより、所定炭酸カルシウム結晶の長径を変化させることができ、滴下液滴径を小さくすれば、該長径を小さくすることができる。例えば、炭酸カルシウム結晶が中空柱状アラゴナイト単結晶の場合、その長径を2μm〜50μmの範囲で変動させることができる。 In the method of the present invention, the major axis of the predetermined calcium carbonate crystal can be changed by changing the diameter of the droplet to be dropped, and the major axis can be reduced by reducing the droplet diameter. For example, when the calcium carbonate crystal is a hollow columnar aragonite single crystal, the major axis can be varied in the range of 2 μm to 50 μm.
海水は、いわば、無機電解質を溶解させた水溶液と見ることができるので、人工的に、作製した無機電荷質水溶液、例えば、NaClやKClやMgCl2を単独又は混合溶解させて作製した水溶液中に、CaCO3またはCa(OH)2の粒子を懸濁させ、そこに炭酸ガスを吹き込むことにより作製した、炭酸水素カルシウム水溶液を用いても、中空柱状アラゴナイト単結晶を製造できる。無機電解質を含有した水溶液中の炭酸水素カルシウムの濃度は、蒸留水を母液とした炭酸水素カルシウムの濃度よりも高くなり、その分、生産性が向上するので有利である。 Seawater can be considered as an aqueous solution in which an inorganic electrolyte is dissolved, so it is artificially prepared in an aqueous solution of an inorganic charge produced, for example, an aqueous solution prepared by dissolving NaCl, KCl, or MgCl 2 alone or in combination. A hollow columnar aragonite single crystal can also be produced by using an aqueous calcium hydrogen carbonate solution prepared by suspending CaCO 3 or Ca (OH) 2 particles and blowing carbon dioxide therethrough. The concentration of calcium hydrogen carbonate in the aqueous solution containing the inorganic electrolyte is higher than the concentration of calcium hydrogen carbonate in which distilled water is used as a mother liquor, which is advantageous because productivity is improved correspondingly.
本発明方法に用いられる熱水は、その温度が90℃以上、好ましくは95℃以上であることが肝要である。この温度が低すぎると中空で、かつ両端が開口したチューブ状のものが得られにくくなる。 It is important that the hot water used in the method of the present invention has a temperature of 90 ° C or higher, preferably 95 ° C or higher. When this temperature is too low, it becomes difficult to obtain a hollow tube-like thing having both ends opened.
本発明炭酸カルシウムは、充填剤または添加剤、特に開放された中空部はその中に空気を包含するので、断熱材用充填剤や、各種資材、例えば建材、包装材等の軽量化用の充填剤として効果的である。 The calcium carbonate of the present invention is a filler or additive, particularly the open hollow portion contains air therein, so that fillers for heat insulating materials and filling for weight reduction of various materials such as building materials and packaging materials, etc. It is effective as an agent.
本発明炭酸カルシウムは、両端が開口しているので、中空内部は外部と連通し、中空内部に炭酸カルシウムと異なる充填物質を懸濁液状態で包含させる場合、中空内部の液と母液との圧力差がなく、操作が容易であるという利点を有する。このような利点は、例えば一方の端部が閉じられ、他方の端部が開放されている空間部を有する柱状炭酸カルシウムと比較すると、この比較用炭酸カルシウムでは、片方端が閉じているので、中空内部の液の圧力の方が母液の圧力よりも高くなり、充填物質を包含させるのが困難になることと対照的である。
また、本発明方法によれば、炭酸水素カルシウム溶液と水を用いるだけで、簡易に本発明炭酸カルシウムを製造することができ、また、炭酸水素カルシウム溶液として海水も用いることができる。
そして、海水は無尽蔵に存在し、その中にはカルシウムが炭酸水素カルシウムとしても相当量溶解しているので、原料源として量的にも適しているなど種々の利点がある。
Since both ends of the calcium carbonate of the present invention are open, the hollow interior communicates with the exterior, and when the hollow interior contains a filler substance different from calcium carbonate in a suspension state, the pressure between the liquid inside the hollow and the mother liquor There is an advantage that there is no difference and operation is easy. Such an advantage is that, for example, compared with columnar calcium carbonate having a space portion in which one end portion is closed and the other end portion is open, in this comparative calcium carbonate, one end is closed, This is in contrast to the pressure of the liquid inside the hollow being higher than the pressure of the mother liquor, making it difficult to incorporate the packing material.
Moreover, according to the method of the present invention, the calcium carbonate of the present invention can be produced simply by using the calcium hydrogen carbonate solution and water, and seawater can also be used as the calcium hydrogen carbonate solution.
And seawater exists inexhaustably, and since calcium is dissolved in a considerable amount even as calcium hydrogen carbonate, it has various advantages such as being suitable as a raw material source.
次に、実施例により本発明を実施するための最良の形態を説明するが、本発明はこれらの例により何ら限定されるものではない。
なお、各例中のLは、リットルを意味する。
Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples.
In addition, L in each example means a liter.
2Lビーカーに試薬炭酸カルシウムを10g採り、20℃の蒸留水1000mlを添加して懸濁液とし、この懸濁液を撹拌しながら、それに炭酸ガスを20dm3/分の速度で1時間吹き込み、懸濁液をろ過して残渣を取り除き、Ca濃度0.02モル/Lの炭酸水素カルシウム水溶液を調製した。他方、2Lビーカーに蒸留水100mlを採り、オイルバスで温度100℃に調整した。この蒸留水に、先に準備した炭酸水素カルシウム水溶液を10ml/分の速度で3mmφチューブより液滴径3mmφで滴下し、炭酸カルシウムを析出させ、ろ過、乾燥した。得られた炭酸カルシウムは0.9gであった。
これを走査型電子顕微鏡により観察すると、長軸方向の両端が開口している長さ40μmの中空柱状アラゴナイト結晶であることが分かった。
この炭酸カルシウムのSEM写真を図1に示す。
Take 10 g of reagent calcium carbonate in a 2 L beaker and add 1000 ml of 20 ° C. distilled water to make a suspension. While stirring this suspension, carbon dioxide is blown into it at a rate of 20 dm 3 / min for 1 hour. The suspension was filtered to remove the residue, and an aqueous calcium bicarbonate solution having a Ca concentration of 0.02 mol / L was prepared. On the other hand, 100 ml of distilled water was taken in a 2 L beaker and adjusted to a temperature of 100 ° C. with an oil bath. To this distilled water, the previously prepared calcium hydrogen carbonate aqueous solution was dropped at a rate of 10 ml / min from a 3 mmφ tube with a droplet diameter of 3 mmφ to precipitate calcium carbonate, which was filtered and dried. The obtained calcium carbonate was 0.9 g.
When this was observed with a scanning electron microscope, it was found to be a hollow columnar aragonite crystal having a length of 40 μm with both ends in the major axis direction being open.
An SEM photograph of this calcium carbonate is shown in FIG.
3mmφチューブに代えて0.05mmφのチューブを用い、液滴径を0.5mmφに変えた以外は実施例1と同様にして炭酸カルシウム0.85gを得た。
これを走査型電子顕微鏡により観察すると、長軸方向の両端が開口している長さ20μmの中空柱状アラゴナイト結晶であることが分かった。
0.85 g of calcium carbonate was obtained in the same manner as in Example 1 except that a 0.05 mmφ tube was used instead of the 3 mmφ tube and the droplet diameter was changed to 0.5 mmφ.
When this was observed with a scanning electron microscope, it was found to be a hollow columnar aragonite crystal having a length of 20 μm with both ends in the major axis direction being open.
滴下を、超音波式噴霧装置を用い5ml/分の速度で液滴径0.01mmφで行った以外は実施例1と同様にして炭酸カルシウム0.2gを得た。
これを走査型電子顕微鏡により観察すると、長軸方向の両端が開口している長さ5μmの中空柱状アラゴナイト結晶であることが分かった。
0.2 g of calcium carbonate was obtained in the same manner as in Example 1 except that dropping was performed at a rate of 5 ml / min with a droplet diameter of 0.01 mmφ using an ultrasonic spray device.
When this was observed with a scanning electron microscope, it was found to be a hollow columnar aragonite crystal having a length of 5 μm and open at both ends in the major axis direction.
蒸留水に代えて海水を用い、Ca濃度0.04モル/Lの炭酸水素カルシウム溶液を調製した以外は実施例1と同様にして炭酸カルシウム1.5gを得た。
これを走査型電子顕微鏡により観察すると、長軸方向の両端が開口している長さ40μmの中空柱状アラゴナイト結晶であることが分かった。
1.5 g of calcium carbonate was obtained in the same manner as in Example 1 except that seawater was used instead of distilled water and a calcium hydrogen carbonate solution having a Ca concentration of 0.04 mol / L was prepared.
When this was observed with a scanning electron microscope, it was found to be a hollow columnar aragonite crystal having a length of 40 μm with both ends in the major axis direction being open.
比較例1
使用される蒸留水の温度を80℃に調整した以外は実施例1と同様にして柱状炭酸カルシウムが得られたが、それは中空ではないものであった。
Comparative Example 1
Columnar calcium carbonate was obtained in the same manner as in Example 1 except that the temperature of distilled water used was adjusted to 80 ° C., but it was not hollow.
本発明炭酸カルシウムは、充填剤または添加剤、特に断熱材用充填剤や、各種資材、例えば建材、包装材等の軽量化用の充填剤として利用可能である。 The calcium carbonate of the present invention can be used as a filler or an additive, particularly a filler for a heat insulating material, and a filler for reducing the weight of various materials such as building materials and packaging materials.
Claims (5)
他の無機電解質が共存していてもよい炭酸水素カルシウム水溶液又は海水を、炭酸水素カルシウムの飽和あるいは過飽和状態下、熱水に滴下することを特徴とするチューブ状炭酸カルシウムの製造方法。 Columnar aragonite, a method for producing tubular calcium carbonate that is hollow in the major axis direction and is open at both ends ,
A method for producing tubular calcium carbonate, characterized in that an aqueous calcium hydrogen carbonate solution or seawater in which other inorganic electrolytes may coexist is dropped into hot water in a saturated or supersaturated state of calcium bicarbonate .
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