JPH01261225A - Production of calcium carbonate of aragonite crystal form - Google Patents
Production of calcium carbonate of aragonite crystal formInfo
- Publication number
- JPH01261225A JPH01261225A JP63089705A JP8970588A JPH01261225A JP H01261225 A JPH01261225 A JP H01261225A JP 63089705 A JP63089705 A JP 63089705A JP 8970588 A JP8970588 A JP 8970588A JP H01261225 A JPH01261225 A JP H01261225A
- Authority
- JP
- Japan
- Prior art keywords
- aragonite
- cao
- water
- calcium carbonate
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 title abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 235000019738 Limestone Nutrition 0.000 claims abstract description 11
- 239000006028 limestone Substances 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 14
- 229910021532 Calcite Inorganic materials 0.000 abstract description 12
- 239000000049 pigment Substances 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 3
- 239000000920 calcium hydroxide Substances 0.000 abstract 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 3
- 235000011116 calcium hydroxide Nutrition 0.000 abstract 3
- 239000002245 particle Substances 0.000 description 13
- 230000029087 digestion Effects 0.000 description 12
- 235000010216 calcium carbonate Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アラゴナイト結晶形炭酸カルシウム（以下、
アラゴナイトと略す）の製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to aragonite crystal form calcium carbonate (hereinafter referred to as
The present invention relates to a method for producing aragonite.
炭酸カルシウムは古くからゴム、プラスチック、塗料、
シーリング材、製紙等の分野で工業用原材料として広く
使用され、それぞれ優れた機能を発揮している。例えば
ゴム分野では補強性、■料分野ではダレ止め効果、プラ
スチックでは加工作業性の向上環の目的で使用されてい
る。これらの炭酸カルシウムは、結晶形から分類すれば
殆ど全てカルサイト結晶形炭酸カルシウム（以下、カル
サイトと略す）である。アラゴナイトは製紙の分野で一
部使用されており、例えばコーティングカラーの顔料、
薄紙のてん料等である。アラゴナイトはカルサイトに比
べて各分野で優れた物性を発揮し、又、今後−層その用
途開発が期待されている。Calcium carbonate has long been used in rubber, plastics, paints,
It is widely used as an industrial raw material in fields such as sealants and paper manufacturing, and each exhibits excellent functionality. For example, it is used for reinforcement in the rubber field, to prevent sag in the materials field, and to improve processing workability in plastics. Almost all of these calcium carbonates are calcite crystal calcium carbonate (hereinafter abbreviated as calcite) when classified based on their crystal forms. Aragonite is used in some areas of paper manufacturing, for example as a pigment for coating colors,
Filling for thin paper, etc. Aragonite exhibits superior physical properties in various fields compared to calcite, and further applications are expected to be developed in the future.
従って、アラゴナイトの効率的な工業的生産方法の確立
が待望されているのが現状である。Therefore, it is currently desired to establish an efficient industrial production method for aragonite.
（従来技術と問題点）
アラゴナイトはカルサイトに比べて粒子の分散性が優れ
ている。又、カルサイトにはない柱状というＣｒｙｓｔ
ａｌ ｈａｂｂｉｔは、カルサイトでは期待できない色
ルの特性を発揮する。従って、従来から工業的にアラゴ
ナイトをより効率的に生産することが試みられて来た。(Prior art and problems) Aragonite has better particle dispersibility than calcite. Also, Cryst has a columnar shape that is not found in Calcite.
al habitat exhibits color properties that cannot be expected from calcite. Therefore, attempts have been made to industrially produce aragonite more efficiently.
例えば、Ｃａ （ＯＨ） ｚスラリーとＣＯ，ガスとの
気）色反応に関する技術としては、炭酸化工程でＣＯ□
ガス量を各段階で調整して行う方法（特公昭５５ ５１
８５２） 、Ｃａ（ＯＨ）ｚスラリーにあらかじめ結晶
核形成剤を加える方法（特開昭５９−２２３２２５）
、炭酸化の各段階で加温する方法（特開昭６３−３０３
１６）等がある。For example, as a technology related to the color reaction between Ca (OH) z slurry and CO gas, CO□
Method of adjusting the amount of gas at each stage
852), a method of adding a crystal nucleating agent to Ca(OH)z slurry in advance (JP-A-59-223225)
, method of heating at each stage of carbonation (Japanese Patent Application Laid-Open No. 63-303
16) etc.
しかし乍ら、これらの方法は品質及び製造設備の点で多
（の問題点を含んでいる。まず品質面では、これらの方
法は各生成条件を非常に微Ｉｆｌに規定しないと、高純
度なアラゴナイトは得られない。However, these methods have many problems in terms of quality and manufacturing equipment.Firstly, in terms of quality, these methods cannot produce high purity unless each production condition is specified to a very small Ifl. Aragonite is not available.
従って製造設備も大変ｙ５雑となり、高価なものとなる
。その結果として、製造コストの高騰が免れない。Therefore, the manufacturing equipment becomes very complicated and expensive. As a result, manufacturing costs inevitably rise.
本発明者らは上記実情に鑑み鋭意研究の結果、前述のよ
うな従来技術が直面する問題点を一挙に解決することに
成功し、本発明を完成した。In view of the above-mentioned circumstances, the inventors of the present invention have conducted extensive research, and as a result have succeeded in solving all of the problems faced by the prior art as described above, and have completed the present invention.
即ち、本発明は、石灰石を焼成して生成させたＣａＯを
、水温が７０℃以下の場合は、ＣａＯにえ、Ｉするモル
比で１５倍以下の１１□０で消化し、水温が７０℃を越
える場合は、任意の量のＨ２Ｏで消化して生成させたＣ
ａ （ＯＲ） ｚの水スラリーを濃度５〜４０−ｔχ、
温度を５〜６５℃に調整し、攪拌しながらＣＯ，ガス（
１００％ＣＯ，とじて）を４１ ／ｗｉｎ ／ｋｇ−Ｃ
ａ （Ｏｉり ２以下の量で炭酸化させることにより、
アラゴナイト結晶形炭酸カルシウムを生成させることを
特徴とするアラゴナイト結晶形炭酸カルシウムの製造方
法を内容とするものである。That is, in the present invention, when the water temperature is 70°C or less, CaO produced by calcining limestone is digested at a molar ratio of 11□0, which is 15 times or less, to CaO and I when the water temperature is 70°C. If the amount exceeds the
a (OR) z water slurry at a concentration of 5 to 40-tχ,
Adjust the temperature to 5-65℃, and add CO, gas (
100% CO, 41/win/kg-C
a (Oi Ri) By carbonating in an amount of 2 or less,
The content is a method for producing aragonite crystalline calcium carbonate, which is characterized by producing aragonite crystalline calcium carbonate.
本発明で使用するＣａ （ＯＨ） ｚは、゛水温が７０
℃以下の場合は、ＣａＯに対するモル比で１５倍以下の
Ｈ，Ｏで、好ましくは９倍以下のＨｉＯで消化して生成
させたものである。水温が７０℃以上の場合はこのよう
な制限はなく、任意の量でよい、 Ｃａ（ＯＲ）２の水
スラリー濃度は５〜４０ｗｔχ、好ましくは８〜２０ｗ
ｔ％程度が良い、温度は５〜６５℃、好ましくは１５〜
４５℃程度が良い。Ｃ１ｈのガス量（ＣＯ，ガスｌＯＯ
％純度として）は、４１ ／ｓｉｎ／ ｋｇ−Ｃａ （
ＯＨ） ｚ以下とする必要があり１、より好ましくは２
Ｉｌ／ｍ’ｔｎ ／ ｋｇ −Ｃａ（ＯＨ）を以下で
ある。The Ca (OH) z used in the present invention is
If the temperature is below 0.degree. C., it is produced by digestion with H, O at a molar ratio of 15 times or less to CaO, preferably 9 times or less HiO. When the water temperature is 70°C or higher, there is no such restriction and any amount may be used. The concentration of Ca(OR)2 water slurry is 5 to 40wtχ, preferably 8 to 20w.
About t% is good, the temperature is 5-65℃, preferably 15-65℃
A temperature of about 45°C is good. Gas amount of C1h (CO, gas lOO
% purity) is 41/sin/kg-Ca (
OH) must be less than or equal to 1, more preferably 2
Il/m'tn/kg -Ca(OH) is as follows.
ＣＯ□のガス濃度は、好ましくは１０〜４０％、より好
ましくは２０〜３５％程度が良い。The gas concentration of CO□ is preferably about 10 to 40%, more preferably about 20 to 35%.
Ｃａ （ＯＨ） ｔはその製造方法によってＣｏｔとの
反応性が異なる０例えば、石灰石を高温で短時間のうち
に焼成してＣａＯとＣＯ２に分解し、このＣａＯに過剰
の水を加えて生成させたＣａ（Ｏｌ１）ｚはＣＯｌとの
反応性が乏しい。一方、出来るだけ低温で、長時間かけ
て石灰石を分解したＣａＯに少量の水で消化して生成さ
せたＣａ （ＯＨ） ＊はＣｏｔとの反応性が良い。Ca (OH) t has different reactivity with Cot depending on its production method. For example, limestone is calcined at high temperature for a short time to decompose it into CaO and CO2, and excess water is added to this CaO to generate it. Ca(Ol1)z has poor reactivity with COl. On the other hand, Ca (OH) *, which is produced by digesting CaO by decomposing limestone with a small amount of water at the lowest possible temperature over a long period of time, has good reactivity with Cot.
アラゴナイトの生成に関しては、前者より後者を使用し
た方がはるかに生成しやすい。Regarding the generation of aragonite, it is much easier to generate using the latter than the former.
本発明者らはかかる観点からアラゴナイトを生成するＣ
ａ （Ｏｌ１） ｚについて研究を進めた。石灰石の焼
成温度の違いによって生成するＣａＯの結晶粒子の大き
さは異なる。これらを同一条件で消化した場合、生成す
るＣａ （ＯＨ） ｚの結晶粒子の大きさは、ＣａＯの
結晶粒子が小さい程小さい結晶粒子が生成する。即ち、
Ｃａ （ＯＨ） ｚの結晶粒子が小さい程、アラゴナイ
トが生成しやすい。このような結晶粒子の小さいＣａ
（ＯＨ） Ｚを生成させるためには、出来るだけ高温状
態で消化させるのがよい。ＣａＯ＋ｌＩ□Ｏ−＝ Ｃａ
（ＯＨ） ｚは強い発熱反応であるため、消化時の水
の量が少ない方が反応系内の温度は高くなる。From this point of view, the present inventors have discovered that C
We conducted research on a (Ol1) z. The size of CaO crystal particles produced differs depending on the firing temperature of limestone. When these are digested under the same conditions, the smaller the Ca (OH) z crystal particles produced, the smaller the CaO crystal particles. That is,
The smaller the crystal particles of Ca (OH) z, the easier it is to generate aragonite. Ca with such small crystal particles
In order to generate (OH) Z, it is best to perform digestion at as high a temperature as possible. CaO+lI□O−= Ca
(OH) Since z is a strongly exothermic reaction, the smaller the amount of water during digestion, the higher the temperature in the reaction system.
従って出来るだけ少量の水で消化する方が結晶粒子が小
さい、即ち、アラゴナイトが生成しゃすいＣａ （ＯＨ
） ｚが得られる。具体的には、水温が７０℃以下の場
合は、モル比でＣａＯ／ ＩＩ２Ｏ＝１ ／ １５、好
ましくはｌ／９よりも１１．０の量を減らせば良い。Therefore, it is better to digest with as little water as possible because the crystal particles are smaller, that is, aragonite is formed.
) z is obtained. Specifically, when the water temperature is 70° C. or lower, the molar ratio of CaO/II2O is 1/15, preferably 11.0 less than 1/9.
水温が７０℃以上の場合は、１１．０の量は任意の滑で
結晶粒子が小さいＣａ （Ｏｌ１） ｚを生成するが、
上述の説明より、この場合でもＨ２Ｏの量が出来るだけ
少ない方が好ましいことは言うまでもない。石灰石を出
来るだけ低温で長時間かけて分解させたＣａＯは、消化
時のＣａＯに対する水の比率が比較的多くても、アラゴ
ナイトを生成するＣａ（ＯＨ）ｚを与える。逆に高温で
短時間で分解させたＣａＯは、消化時のＣａＯに対する
水の比率を少なくしないとアラゴナイトを生成するＣａ
（０）１） ｔを与えない、勿論これらの比率は上述
の範囲内での加減である。このことはアラゴナイトが出
来るＣａ（ＯＲ）ｚを作るためには、石灰石の焼成条件
とＣａＯの消化条件の２点が大きく関係し、その中でも
ＣａＯの消化条件の方がはるかに大きく影響するが、石
灰石の焼成条件も十分考慮しなければならないと言うこ
とである。When the water temperature is above 70°C, an amount of 11.0 will produce Ca (Ol1) z with arbitrary smoothness and small crystal particles, but
From the above explanation, it goes without saying that even in this case, it is preferable that the amount of H2O is as small as possible. CaO obtained by decomposing limestone at the lowest possible temperature over a long period of time gives Ca(OH)z, which produces aragonite, even if the ratio of water to CaO during digestion is relatively high. On the other hand, CaO decomposed in a short time at high temperature will produce aragonite unless the ratio of water to CaO during digestion is reduced.
(0)1) t is not given.Of course, these ratios are adjusted within the above range. This means that in order to produce Ca(OR)z, which is the product of aragonite, there are two major factors: the calcination conditions for limestone and the conditions for digestion of CaO. Of these, the conditions for digestion of CaO have a far greater influence. This means that the firing conditions for limestone must also be carefully considered.
一方、これらのＣａ （ＯＨ） ｚの結晶状態をＸ線回
折で観察すると、Ｃａ （ＯＨ） ｚはミラー指数で表
される結晶面が６点検出される。 ！ＩＩち、（０２Ｏ
，１）、（１２Ｏ２Ｏ）、（１２Ｏ，１）、（１２Ｏ゜
２） （１，１，Ｏ）、（１，１，１）である、これ
らの結晶面の中でＸ線回折強度比１／Ｔｏが消化状態の
相異（結果として活性度の相異）によって異なるのは（
０，Ｏ，ｌ１面である。具体的には７ラゴナイトを生成
するＣａ （Ｏｆｆ） ｔはアラゴナイトを生成しない
Ｃａ （ＯＨ） ｚに比べて（０，Ｏ，Ｉ）面の強度比
が小さ（、その値（１／１．）は７５以下である。下限
は特に限定されないが、５０程度が好ましい。しかし乍
ら、このようなＸ線回折強度比を有するＣａ （Ｏｆｆ
） ｔを使用すれば必ず７ラゴナイトを高純度で生成す
る訳ではなく、上述のような反応条件下で炭酸化を行う
必要がある。特にＣｏｔのガス量は厳守しなければアラ
ゴナイトを高純度で生成させることはできない。On the other hand, when the crystal state of Ca (OH) z is observed by X-ray diffraction, six crystal planes expressed by Miller indices are detected in Ca (OH) z. ! II, (02O
,1), (12O2O), (12O,1), (12O゜2) (1,1,O), (1,1,1), and the X-ray diffraction intensity ratio 1 among these crystal planes. The reason why /To differs depending on the state of digestion (as a result, the degree of activity) is (
0, O, l1 plane. Specifically, Ca (Off) t, which produces 7lagonite, has a smaller intensity ratio of the (0, O, I) plane than Ca (OH) z, which does not produce aragonite (and its value (1/1)). is 75 or less.The lower limit is not particularly limited, but is preferably about 50.However, it is important to note that Ca (Off
) The use of t does not necessarily produce highly pure 7lagonite, and carbonation must be carried out under the reaction conditions described above. In particular, aragonite cannot be produced with high purity unless the amount of Cot gas is strictly observed.
こうしてできたアラゴナイトは長径０．５〜１０゜０μ
ｍ、短径０．０２〜１．０μｍ、アスペクト比５以上の
柱状もしくは針状形状をしている。粒子の大小の調整に
ついては、Ｃａ （Ｏｉ１） ｚ水スラリーの温度が低
い程粒子は小さ（なり、Ｃａ（Ｏｉ１）を水スラリーの
温度が高い程粒子が大きくなる。The aragonite made in this way has a major axis of 0.5~10゜0μ.
m, has a columnar or needle-like shape with a minor axis of 0.02 to 1.0 μm and an aspect ratio of 5 or more. Regarding adjustment of the size of the particles, the lower the temperature of the Ca(Oi1) water slurry, the smaller the particles (become), and the higher the temperature of the Ca(Oi1) water slurry, the larger the particles.
上記の如くして得られるアラゴナイトは各使用用途に応
じてスラリーでも、ペーストでも製品となる。スラリー
の場合は３〜３５％、ペーストの場合は分散を入れて４
５〜６５％程度の濃度が好 。The aragonite obtained as described above can be made into a slurry or paste depending on the intended use. 3-35% for slurry, 4% including dispersion for paste
A concentration of about 5 to 65% is preferable.
ましい、また、アラゴナイトスラリーを脱水、乾燥して
粉体として製品化しても良い。Alternatively, the aragonite slurry may be dehydrated and dried to produce a product as a powder.
本発明のアラゴナイトは、従来カルサイトが使用されて
いた分野の中でも特に製紙、プラスチックの分野でその
特性を顕著に発揮する。製紙分野では、カルサイトに比
ベアラゴナイトは分散性が優れているため、紙の填料と
して又コーティングカラーの顔料として使用した場合、
優れた隠ペイ性を発揮する。従って、従来隠ペイ性付与
のために使用されていたＴｉ０１が大幅に節減できる。The aragonite of the present invention exhibits its properties particularly in the fields of paper manufacturing and plastics, among the fields where calcite has conventionally been used. In the paper manufacturing field, bare aragonite has superior dispersibility compared to calcite, so when used as a paper filler or as a coating color pigment,
Demonstrates excellent concealment performance. Therefore, Ti01, which was conventionally used to provide concealment properties, can be significantly reduced.
また、コーティングカラーの顔料としてカオリン等と併
用使用した場合、従来からこの分野に使用されている立
方体形状のカルサイトに比べて、優れた印刷適性を示す
、特に印刷光沢、ピンキングが良い。In addition, when used in combination with kaolin etc. as a coating color pigment, it shows superior printability compared to the cubic calcite conventionally used in this field, especially in printing gloss and pinking.
更に、白紙光沢もカルサイトより優れている。コーティ
ングカラーに使用した場合のこれらの優れた物性は、ア
ラゴナイトのＣｒｙｓｔａｌ ｈａｂｂｉｔである柱状
又は針状という方向性をもった粒子形状に起因する。Furthermore, white paper gloss is also superior to calcite. These excellent physical properties when used in a coating color are due to the crystal habit of aragonite, which is a columnar or needle-like directional particle shape.
以下、本発明を実施例及び比較例を挙げて更に詳細に説
明するが、本発明はこれらにより何ら制限されるもので
はない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way.
実施例１
石灰石を９００℃で２４時間焼成してＣａＯとＣ０２に
分解させた。このＣａＯに水温２０℃のＨｔＯをＣａＯ
に対するモル比で６倍量加え（ｗｔＸでＣａＯ／ｌｈＯ
＝ １ ／ ２ ） Ｃａ（Ｏｎ）ｚを生成させ、１時
間以上放置させた後、更にＨ２Ｏを加えて濃度が１３０
ｇ／ｌとなるようなＣａ （Ｏｆｆ） ｚ水スラリーに
調整した。Example 1 Limestone was calcined at 900°C for 24 hours to decompose it into CaO and CO2. Add HtO at a water temperature of 20°C to this CaO.
(CaO/lhO in wtX)
= 1/2) After generating Ca(On)z and leaving it for more than 1 hour, H2O was further added until the concentration was 130.
The Ca (Off) z water slurry was adjusted to have a concentration of g/l.
その後、温度を３５℃に調整したＣａ （Ｏ）１） ！
水スラリー３０１にＣｏｚｔｌ度３０％である空気とＣ
Ｏ□混合ガスを６１ ／ ｓｉｎ ／ ｋｇ−Ｃａ（Ｏ
Ｈ） ｚの割合で吹き込んでＣａ （ＯＲ） ｘを炭酸
化した。こうして出来た炭酸カルシウムをＸ線でアラゴ
ナイト含有量を、また、電子顕微鏡で粒子形状を観察し
た。結果を第１表に示す、尚、用いたＣａ （ＯＨ）
ｔのＸ線回折強度比（ｊ／１゜）は６５．６であった。After that, the temperature was adjusted to 35 °C and Ca(O)1)!
Water slurry 301 with air and C having a Coztl degree of 30%
O□ Mixed gas at 61/sin/kg-Ca(O
H) Ca (OR) x was carbonated by blowing at a rate of z. The aragonite content of the calcium carbonate thus produced was observed using X-rays, and the particle shape was observed using an electron microscope. The results are shown in Table 1, and the Ca(OH) used
The X-ray diffraction intensity ratio (j/1°) at t was 65.6.
実施例２
実施例１において、石灰石の焼成温度を１４００℃で５
時間とした以外は全て実施例１と同様に操作した。尚、
用いたＣａ（Ｏｔ１）ｚのＸ″＋Ｑ回折強度比（■／！
。）は６７、ｌであった。Example 2 In Example 1, the firing temperature of limestone was set at 1400°C for 5
All operations were performed in the same manner as in Example 1 except for changing the time. still,
X″+Q diffraction intensity ratio of the Ca(Ot1)z used (■/!
. ) was 67.l.
実施例３
実施例１において、消化時の水温を１００℃、消化時の
ＨｘＯの量をＣａＯに対するモル比で２２倍ｌ（ｗｔχ
でＣａＯ／Ｈ２０″＝１／７）とした以外は全て実施例
１と同様に操作した。用いたＣａ（ＯＨ）ｚのＸ線回折
強度比（Ｉ／１゜）は６６．７であった。Example 3 In Example 1, the water temperature during digestion was 100°C, and the amount of HxO during digestion was 22 times the molar ratio to CaO (wtχ
All operations were performed in the same manner as in Example 1, except that CaO/H20'' = 1/7).The X-ray diffraction intensity ratio (I/1°) of the Ca(OH)z used was 66.7. .
比較例１
実施例１において、消化時の水の量をＣａＯに対するモ
ル比で１７倍ｉ１（ｗｔχでＣａＯ／ｌ１ｇｏ ＝ １
１５．５）とした以外は全て実施例１と同様に操作した
。尚、用いたＣａ（ＯＨ）ｚのＸｉ、？！回折強度比（
１／！。）は７９．９であった。Comparative Example 1 In Example 1, the amount of water during digestion was increased by 17 times the molar ratio to CaO i1 (wtχ, CaO/l1go = 1
15.5) All operations were carried out in the same manner as in Example 1, except that the procedure was as follows. In addition, Xi of Ca(OH)z used, ? ! Diffraction intensity ratio (
1/! . ) was 79.9.
比較例２
実施例１において、炭酸化時の混合ガス量を２０１ ／
＋＊ｉｎ ／ ｋｇ−Ｃａ（ＯＨ）ｚとした以外は全て
実施例１と同様に操作した。尚、用いたＣａ （Ｏｌ１
） ２のＸ線回折強度比Ｎ／Ｉｏ ）は７８．６であっ
た。Comparative Example 2 In Example 1, the amount of mixed gas during carbonation was changed to 201 /
All operations were performed in the same manner as in Example 1 except that +*in/kg-Ca(OH)z. In addition, the Ca (Ol1
) The X-ray diffraction intensity ratio N/Io ) of 2 was 78.6.
比較例３
実施例１において、消化時の水温を６０℃、消化時の１
１□０の量をＣａＯに対するモル比で２５倍１（ｗｔχ
でＣａＯ／ｕ、ｏ Ｉ−＋１ ／ ８ ）とした以外は
全て実施例１と同様に段作した。尚、用いたＣａ （Ｏ
ｌ１） ｚのＸ線回折強度比（■／１゜）は８０．５で
あった。Comparative Example 3 In Example 1, the water temperature during digestion was 60°C, and
The molar ratio of 1□0 to CaO is 25 times 1 (wtχ
Step production was performed in the same manner as in Example 1, except that CaO/u, o I-+1/8) was used. In addition, the Ca (O
l1) The X-ray diffraction intensity ratio (■/1°) of z was 80.5.
第 １ 表
上記の結果かられかるように、本発明の実施例１〜３は
高純度にアラゴナイトを生成するが、比較例１〜３は全
くアラゴナイトを生成しないか、生成しても含有率が極
めて低い。Table 1 As can be seen from the above results, Examples 1 to 3 of the present invention produce aragonite with high purity, but Comparative Examples 1 to 3 either do not produce aragonite at all or even if they do produce it, the content is low. Extremely low.
応用例１
実施例１及び２で生成させたアラゴナイトを紙の填料と
して使用し、第２表に示した配合で抄紙試験を実施した
。尚、比較のために、従来の紡錘形カルサイトを用い同
様の試験を実施した。その結果を第３表に示す。Application Example 1 A paper making test was conducted using the aragonite produced in Examples 1 and 2 as a paper filler and the formulations shown in Table 2. For comparison, a similar test was conducted using conventional spindle-shaped calcite. The results are shown in Table 3.
第 ２ 表
配合
（ａ）パルプ（Ｌ／Ｎ ＝ １／３） 、 １
００部（重Ｖ部）（ｂ） ＣａＣＯ３６０部
（ｃ）水 バルブ濃度２．５％（ｄ
）カナオンデンプン １部（ｅ）硫酸バ
ンド ０．５部（ｆ）サイズ剤（
バーサイズ八に−１８８） ０．２部（ｇ）定着剤
（カイメン５５７Ｈ） ０．０５部（ｈ）
歩留向上剤０１Ｒ４１Ｌ）Ｉ） （１２Ｏ
２部※１
１−ｎ、／ ＄１■ １／１１閃−Ｒ■Ｒｏ＝黒板反
射率
Ｒ■：完全に不透明な紙束の反射率
Ｗ：坪量
※２
Ｓｆ：未充填紙の比散乱係数
Ｓａ：充填紙の比散乱係数
ｙ：充填量
第 ３ 表
以上の結果より、本発明品を紙の填料として使用すれば
、（Ｉれた白色度、不透明度、紙Ｓ値、顔ネ４Ｓ（直が
得られることがわかる。Table 2 Mixture (a) Pulp (L/N = 1/3), 1
00 parts (heavy V part) (b) 360 parts of CaCO (c) Water Bulb concentration 2.5% (d
) Canaon starch 1 part (e) Bandon sulfate 0.5 part (f) Sizing agent (
Bar size Hachi-188) 0.2 parts (g) Fixing agent (Kaimen 557H) 0.05 parts (h)
Retention aid 01R41L)I) (12O
2 parts *1 1-n, / $1 ■ 1/11 flash - R ■ Ro = blackboard reflectance R ■: Reflectance of completely opaque paper stack W: Basis weight *2 Sf: Specific scattering of unfilled paper Coefficient Sa: Specific scattering coefficient of filled paper y: Filling amount From the results shown in Table 3, if the product of the present invention is used as a paper filler, (You can see that you can get direct results.
応用例２
次に、実施例！で得られたアラゴナイトを塗工用顔料と
してのテストを実施した。同時に、比較のために従来か
ら塗工用顔料として広く使用されている一辺約０．５μ
ｍの立方体炭酸カルシウムを用いて同時にテストした。Application example 2 Next, an example! The aragonite obtained in the above was tested as a coating pigment. At the same time, for comparison, a pigment of approximately 0.5μ per side, which has been widely used as a coating pigment, is used.
Simultaneously tested with m cubic calcium carbonate.
塗工試験結果（片面塗工物性）を第４表に示した。The coating test results (physical properties of single-sided coating) are shown in Table 4.
向、カラー処方、■１方法及び塗工物性測定条件は下記
の通りとした。The direction, color prescription, method (1), and coating property measurement conditions were as follows.
（イ）カラー処方
試料スラリー ： １００重量部
Ｌａｔｅｘ ＪＳＲＯ’６９２ ： １３重量部５Ｌ
ａｒｃｈ ＭＳ ４６００ ； ７重量部固形分濃
度 ： ５５重量％
ステンレス容器に試料スラリー、ラテックス、スターチ
と水を投入しラボデイスパーで、分散を行いカラーを調
整した。(a) Color prescription sample slurry: 100 parts by weight Latex JSRO'692: 13 parts by weight 5L
Arch MS 4600; 7 parts by weight Solid content concentration: 55% by weight Sample slurry, latex, starch and water were put into a stainless steel container and dispersed using a lab disper to adjust the color.
（ロ） 塗工方ン去
原紙（坪１６８／ｎ（のコート原紙）を使用し、コーテ
ィングロートで１５ｇ／ｍの片面塗工を行った。これを
直ちに熱風乾燥機に入れ、１２０℃で２分間キユアリン
グを行った後に２０℃、６５％ＲＨの高温恒湿槽中で１
２時間コンデショニングを行い、スーパーカレンダーを
かけて塗工紙を得た。(b) Coating method Using base paper (coated base paper of 168 tsubo 168/n), one side was coated with a coating funnel at a rate of 15 g/m. This was immediately placed in a hot air dryer and heated at 120°C for 2 hours. After curing for 1 minute, it was placed in a high temperature and humidity chamber at 20℃ and 65% RH.
Conditioning was performed for 2 hours and supercalendering was performed to obtain coated paper.
スーパーカレンダー処理条件
線 圧：１０ｋｇ／ｃｄ
温 度−６０℃
通紙回数＝３回
カレンダー速度： ８１１／５ｉｎ
（ハ）塗工物性測定条件
塗工量：ｌ０ＸＩＯ（ｄ＋＞の塗工紙の重量を化学天秤
で秤量し、原紙の秤量を差
し引いて測定、１０枚の試験片の平
均値。Super calender processing conditions Line pressure: 10 kg/cd Temperature -60°C Number of paper passes = 3 times Calendar speed: 811/5 in (c) Coating physical properties measurement conditions Coating amount: 10XIO (weight of coated paper with d+> Measured by weighing on a chemical balance and subtracting the weight of the base paper, average value of 10 test pieces.
白紙白色度： ＪＩＳ−Ｐ−８１２３１０枚の試験片の
測定値の平均値。White paper whiteness: Average value of the measured values of 10 test pieces of JIS-P-8123.
白紙光沢度： ＪＩＳ−Ｐ−８１４２１０枚の試験片の
測定値の平均値。White paper glossiness: Average value of measurements of 10 JIS-P-8142 test pieces.
印刷光沢度： ＪＩＳ−Ｐ−８１４２１０枚の試験片の
測定値の平均値。Print glossiness: Average value of measurements of 10 JIS-P-8142 test pieces.
周速１陽／ｓｅｃ、１回転層色、イ ンキ供給量０．４ｍｌ。Peripheral speed 1y/sec, 1 rotation layer color, i Ink supply amount 0.4ml.
（使用インキ：東洋インキ製
ＴＫブライトＧ墨−口）
Ｒ１−Ｄｒｙ −Ｉ’ｉｃｋ ： ５点法で評価、１０
枚の試験片の測定値の平均値。(Ink used: Toyo Ink TK Bright G ink-mouth) R1-Dry-I'ick: Evaluation on a 5-point scale, 10
Average value of the measured values of two test pieces.
周速３＋１１／ｓｅｃ、１５回回転層、インキ供給１０
．３５ｍｊ！。Peripheral speed 3+11/sec, 15 rotation layers, ink supply 10
．． 35mj! .
（使用インキ二人日本インキ
製タックグレードＴＶ＝１４墨）
■・Ｉｎｋ −Ｓｅｔ ：目視評価しＳｅｔ完了の時
間（編ｉｎ ）で表示。(The ink used was Nippon Ink's tack grade TV = 14 ink.) - Ink-Set: Visually evaluated and displayed as the set completion time (edited in).
周速１ｍ／５ｅｅＳ１回転展色、イ
ンキ（共給量０．３ｍ１
（使用インキ：東洋インキ製
ＴＫブライトＧ紅−口）
Ｒ１−ＷｅＬ着肉；印刷白色度を測定、白色度低下率で
表示。Circumferential speed: 1 m/5ee S1 rotating color spread, ink (co-supplied amount: 0.3 m1 (ink used: Toyo Ink TK Bright G Red) R1-WeL inking; printing whiteness was measured and expressed as whiteness reduction rate.
周速３ｍ１ｓｅｃ、 １回転層色、湿 し水２．５ｓｆ繰り込み、イン 主供給１０．６ｍｌ。Circumferential speed 3m1sec, 1 rotation layer color, humidity Shimizu 2.5sf renormalization, in Main supply 10.6ml.
（使用インキ：東洋インキ製 ＴＫブライトＧ紅−口） ｋ＆に濃度：印刷白色度を測定、白色度低下率で表示。(Ink used: Toyo Ink TK Bright G Red-Mouth) Density: Measures printing whiteness and displays the whiteness reduction rate.
に龜Ｋｉｎｋ ２ｍ１ｎ値 墨淵度：印別白色度を測定、白色度低下率で表示。Niku Kink 2m1n value Sumibuchi degree: Measures the whiteness of each stamp and displays it as a whiteness reduction rate.
亜麻仁油黒色ＩＮＫ ４０ｓｅｃ値
測定機器
恒温恒湿槽：ＦＲ４ｎタバイ製作所
スーパーカレンダー：熊谷理工■
Ｒ１・■型テスター；■明製作所
グロスメーター：村上色彩技研 ＧＭ−３Ｍハンター式
比色度計： Ｉ’ｋ１４４１ ＴＳＳ型■東洋精機Ｂ型
粘度計：東京計器
第 ４ 表
第４表の結果から、本発明品は塗工用顔料としても優れ
た効果があることが理解される。Flaxseed oil black INK 40sec value measuring equipment Temperature and humidity chamber: FR4n Tabai Seisakusho Super Calendar: Kumagai Riko ■ R1/■ type tester; ■ Mei Seisakusho gloss meter: Murakami Color Giken GM-3M Hunter type colorimeter: I'k1441 TSS type ■ Toyo Seiki B type viscometer: Tokyo Keiki Table 4 From the results shown in Table 4, it is understood that the product of the present invention has excellent effects as a coating pigment.
Claims (1)
℃以下の場合は、ＣａＯに対するモル比で１５倍以下の
Ｈ＿２Ｏで消化し、水温が７０℃を越える場合は任意の
量のＨ＿２Ｏで消化して生成させたＣａ（ＯＨ）＿２の
水スラリーを濃度５〜４０ｗｔ％、温度を５〜６５℃に
調整し、攪拌しながらＣＯ＿２ガス（１００％ＣＯ＿２
として）を４ｌ／ｍｉｎ／ｋｇ・Ｃａ（ＯＨ）＿２以下
の量で炭酸化させることにより、アラゴナイト結晶形炭
酸カルシウムを生成させることを特徴とするアラゴナイ
ト結晶形炭酸カルシウムの製造方法。 ２、生成させたＣａ（ＯＨ）＿２のミラー指数で示され
る結晶面（０、０、１）に対するＸ線回折強度化（Ｉ／
Ｉ＿０）が７５以下である請求項１記載の製造方法。 ３、ＣＯ＿２ガス（１００％ＣＯ＿２として）が２ｌ／
ｍｉｎ／ｋｇ・Ｃａ（ＯＨ）＿２以下の量である請求項
１又は２記載の製造方法。[Claims] 1. CaO produced by calcining limestone is heated to a water temperature of 70°C.
℃ or less, digest with H_2O at a molar ratio of 15 times or less to CaO, and if the water temperature exceeds 70℃, digest with any amount of H_2O to produce a water slurry of Ca(OH)_2. 5 to 40 wt%, the temperature was adjusted to 5 to 65°C, and CO_2 gas (100% CO_2
1. A method for producing aragonite crystalline calcium carbonate, the method comprising producing aragonite crystalline calcium carbonate by carbonating (as) aragonite crystalline calcium carbonate in an amount of 4 l/min/kg・Ca(OH)_2 or less. 2. X-ray diffraction intensity enhancement (I/
The manufacturing method according to claim 1, wherein I_0) is 75 or less. 3. CO_2 gas (as 100% CO_2) is 2l/
The manufacturing method according to claim 1 or 2, wherein the amount is less than min/kg.Ca(OH)_2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63089705A JP2652032B2 (en) | 1988-04-12 | 1988-04-12 | Method for producing aragonite crystalline calcium carbonate |
| KR1019890003606A KR970001526B1 (en) | 1988-04-12 | 1989-03-22 | Process for the preparation of aragonite type calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63089705A JP2652032B2 (en) | 1988-04-12 | 1988-04-12 | Method for producing aragonite crystalline calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01261225A true JPH01261225A (en) | 1989-10-18 |
| JP2652032B2 JP2652032B2 (en) | 1997-09-10 |
Family
ID=13978195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63089705A Expired - Fee Related JP2652032B2 (en) | 1988-04-12 | 1988-04-12 | Method for producing aragonite crystalline calcium carbonate |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2652032B2 (en) |
| KR (1) | KR970001526B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04295010A (en) * | 1991-03-22 | 1992-10-20 | Okutama Kogyo Kk | Production of aragonite columner calcium carbonate |
| WO2000056661A1 (en) * | 1999-03-19 | 2000-09-28 | Yabashi Industries Co., Ltd. | Process for producing calcium carbonate |
| JP2008273761A (en) * | 2007-04-26 | 2008-11-13 | New Raimu Kenkyusha:Kk | Method for manufacturing aragonitic acicular or columnar calcium carbonate agglomerate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100720859B1 (en) * | 2005-12-30 | 2007-05-23 | 한국지질자원연구원 | Control of particle size of aragonite precipitated calcium carbonate |
-
1988
- 1988-04-12 JP JP63089705A patent/JP2652032B2/en not_active Expired - Fee Related
-
1989
- 1989-03-22 KR KR1019890003606A patent/KR970001526B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04295010A (en) * | 1991-03-22 | 1992-10-20 | Okutama Kogyo Kk | Production of aragonite columner calcium carbonate |
| WO2000056661A1 (en) * | 1999-03-19 | 2000-09-28 | Yabashi Industries Co., Ltd. | Process for producing calcium carbonate |
| AU768281B2 (en) * | 1999-03-19 | 2003-12-04 | Yabashi Industries Co., Ltd. | Process for producing calcium carbonate |
| JP2008273761A (en) * | 2007-04-26 | 2008-11-13 | New Raimu Kenkyusha:Kk | Method for manufacturing aragonitic acicular or columnar calcium carbonate agglomerate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2652032B2 (en) | 1997-09-10 |
| KR890015960A (en) | 1989-11-27 |
| KR970001526B1 (en) | 1997-02-11 |
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