JPS60103025A - Manufacture of calcium carbonate - Google Patents
Manufacture of calcium carbonateInfo
- Publication number
- JPS60103025A JPS60103025A JP20795083A JP20795083A JPS60103025A JP S60103025 A JPS60103025 A JP S60103025A JP 20795083 A JP20795083 A JP 20795083A JP 20795083 A JP20795083 A JP 20795083A JP S60103025 A JPS60103025 A JP S60103025A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- chain
- added
- carbonation
- specific surface
- 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
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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- 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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はＢ １４ ’Ｐ比表面積（以下比表面積と記す
）６Ｏｆ７１″／ｇ以上の極微細な炭酸カルシウムの製
造方法に関するものである。詳しくは連鎖状の非常に発
達１７だ極微細な炭酸カルシウムの製造方法に係るもの
である。Detailed Description of the Invention The present invention relates to a method for producing extremely fine calcium carbonate having a B 14 'P specific surface area (hereinafter referred to as specific surface area) of 6Of71''/g or more. No. 17 relates to a method for producing extremely fine calcium carbonate.
便来、ゴノ・、プラスチック用充填剤あるいは塗料、イ
ンＡ用顔料として拡〈使用されている炭酸カルシウムに
は石灰石を機械的に粉砕する重質炭酸カルシウムと化学
反応から得られる沈降炭酸カルシウムとがあり、沈降炭
酸力ルシウＪ・には比表面積１０ゴ／ｇ未満の軽質炭酸
カルシウムと１０ ’ｎ” ／ ９以上の極微細炭酸カ
ルシウムとに別けられる。Calcium carbonate used as a filler for plastics, paints, and pigments for in-A includes heavy calcium carbonate obtained by mechanically crushing limestone, and precipitated calcium carbonate obtained from a chemical reaction. Precipitated carbonate is divided into light calcium carbonate with a specific surface area of less than 10g/g and ultrafine calcium carbonate with a specific surface area of 10'n''/9 or more.
沈降炭酸カルシウムは、一般に水酸化カルシウム水懸濁
液に炭酸ガスを吹込み炭酸化反応を行う方法の中で、濃
度、温度、炭酸ガス吹込み量などの条件を適宜調節して
、比表面積１（Ｉｎ”７ｇ未満の結晶粒子の大きい軽質
炭酸カルシウムと比表面積１０ ｍ” ／ ｊｉ以上の
結晶粒子の小さい極微細炭酸カルシウムとが製造、市販
されている。このうち比表面積１０ｍ”／、９以上の極
微細炭酸カルシウムは炭酸化工程において、炭酸ガス吹
込み量の比較的多い条件で生成するが。Precipitated calcium carbonate is generally produced by a method in which a carbonation reaction is carried out by blowing carbon dioxide gas into an aqueous suspension of calcium hydroxide, by appropriately adjusting conditions such as concentration, temperature, and amount of carbon dioxide gas blown into a calcium hydroxide aqueous suspension. (In"Light calcium carbonate with large crystal particles of less than 7 g and ultrafine calcium carbonate with small crystal particles with a specific surface area of 10 m"/ji or more are manufactured and commercially available. Among these, calcium carbonate with a specific surface area of 10 m"/, 9 or more Ultrafine calcium carbonate is produced in the carbonation process under conditions where a relatively large amount of carbon dioxide gas is blown.
その細かさはこれまでの所比表面積で約５０〜でいない
。また、試験的に得られたとしても結晶粒子がブドウ房
状に固く凝集した所謂アグリゲート（Ａｇｇｒｅｇａｔ
ｅ ）な粒子の炭酸カルシウムしか得られず。これら粉
末をそのままゴム、プラスチック、塗料、インキなど有
機高分子、溶剤に混合応用しても分散性が非常に劣るた
め、これまでに製品化されたことがない。The fineness has so far been about 50 or more in terms of specific surface area. In addition, even if obtained experimentally, so-called aggregates in which crystal particles are tightly aggregated in the shape of a bunch of grapes may be produced.
e) Only calcium carbonate particles can be obtained. Even when these powders are mixed and applied directly to organic polymers and solvents such as rubber, plastics, paints, and inks, their dispersibility is extremely poor, so they have never been commercialized to date.
そこで、極微細炭酸カルシウムでは分散性を改良するた
め、結晶粒子がミタラシ団子風の連鎖状炭酸カルシウム
が研死、検討された。それらの方法としては水酸化カル
シウム水懸濁液の炭酸化反応において、炭酸化途中の粘
稠な膠状乳濁液に変性した時点で、加水分解にょシ水酸
化亜鉛となるＩＪＩｌ、ｊイ）塩を加える方法（特公昭
５７−５１９号）、水ｆｊｊ性アグネシウム塩を加える
方法（特公昭４７−２２９４ｆ号）および硫酸または水
溶性硫酸塩（但し、亜鉛およびマグネシウムは除く）全
加える方法（特公昭５ｏ−３６９９５号）、水酸化カル
シウム水懇濁液に硫酸を加えて炭酸化反応を行う方法（
特公昭５６Ｖｔ化カルシウノ・水）１■；濁液を炭酸化
する際の反応条件、即ち濃１０−１温度、炭酸ガス吹込
み量をただ単に調節しで」１“ｌる方法に較べて２粒子
が多少微細化され、ｆ′のために連鎖状に成長した粒子
が極く一部認められたりするが、大刀はブドウ房状に二
次凝結した大きな塊状状態の炭酸カルシウム凝集体をな
し、これらを有機高″分子、溶剤中に混合しても分散に
関してはとても充分満足した状態のものが得られない。Therefore, in order to improve the dispersibility of ultrafine calcium carbonate, a chain-shaped calcium carbonate with crystal particles similar to Mitarashi dango was polished and investigated. These methods include carbonation reaction of an aqueous suspension of calcium hydroxide, which is hydrolyzed into zinc hydroxide at the point where it denatures into a viscous colloid emulsion during carbonation. The method of adding salt (Japanese Patent Publication No. 57-519), the method of adding aqueous agnesium salt (Japanese Patent Publication No. 47-2294F), and the method of adding all sulfuric acid or water-soluble sulfates (excluding zinc and magnesium) (Special Publication No. 57-519), Publication No. 5o-36995), a method of carrying out a carbonation reaction by adding sulfuric acid to a calcium hydroxide water suspension (
Comparing to the method of simply adjusting the reaction conditions when carbonating a turbid liquid, namely the concentrated 10-1 temperature and the amount of carbon dioxide gas blown in. The particles have become somewhat finer, and some particles that have grown in a chain due to f′ can be seen in a small part, but the large sword is a large block of calcium carbonate aggregates that has been secondary condensed in the shape of a grape cluster. Even if these are mixed into organic polymers and solvents, very satisfactory dispersion cannot be obtained.
さらにまた。Yet again.
先ずキレート剤を含む水酸化カルシウム懸濁液に炭酸ガ
スを吹込んで炭酸化反応をスタートし。First, carbon dioxide gas is blown into a calcium hydroxide suspension containing a chelating agent to start the carbonation reaction.
炭酸化途中に水溶性金属塩を加える方法（特公昭５６−
２６６１３号）が提案されているが。Method of adding water-soluble metal salts during carbonation (Special Publication 1986-
No. 26613) has been proposed.
この方法でも結晶粒子は微細化され、連鎖状粒子も認め
られるが、どちらかというとその連鎖状粒子が数本から
数十水束になった連鎖束状の二次凝集体を形成し、有機
高分子、溶剤に対する分散性はやはり充分とはいえない
う
ゴム、プラスチック用充填剤あるいは塗料。Even with this method, the crystal particles are made finer and chain particles are also observed, but rather the chain particles form secondary aggregates in the form of chain bundles with several to tens of water bundles. Rubber, plastic fillers, and paints have insufficient dispersibility in polymers and solvents.
インキ用顔料としての炭酸カルシウムは、その配合物の
物性向上が強く望まれており、それにこのような理由か
ら、ゴム、プラスチック。Calcium carbonate is used as a pigment for ink, and it is strongly desired to improve the physical properties of its compounds, and for this reason, it is used in rubber and plastics.
塗料、インキなどの充填剤あるいは顔料としての炭酸カ
ルシウムは粒子をより微細化し、それらの粒子が炭酸化
工程あるいは脱水、乾燥工程において固く凝結せず、普
通の機械粉砕で一次粒子まで解砕できれば、ゴム、／ラ
スチｙりなどに配合して１分散性の改善はもとより、補
強性などの物性を一層回上せしめることができる。Calcium carbonate, which is used as a filler or pigment in paints, inks, etc., makes the particles finer, and if these particles do not solidify during the carbonation process, dehydration, or drying process, and can be broken down to primary particles by ordinary mechanical grinding, It can be added to rubber, rubber/lasty, etc. to not only improve dispersibility but also to further improve physical properties such as reinforcing properties.
本発明者らは比表面積６０ｙｄ／、９以上の極微細な連
鎖状粒子で、その連鎖状粒子が塊状あるいは束状に凝結
しなくて、普通の粉砕機で解砕して分散性の良好な炭酸
カルシウムについて種々研死を１ねた結果、水酸化カル
シウム水懸濁液を炭酸化する際、添加薬品と反応条件を
適当に選択することにより、比表面積６ｏ＃／ｇ以上の
極微細な連鎖状の非常に発達した炭酸カルシウムが容易
にイＧられること金兄い出し２本発明を完成するにいた
った。The present inventors have discovered that ultrafine chain particles with a specific surface area of 60 yd/. As a result of conducting various experiments on calcium carbonate, we found that when carbonating an aqueous suspension of calcium hydroxide, by appropriately selecting the additive chemicals and reaction conditions, extremely fine chains with a specific surface area of 6o#/g or more can be created. The fact that highly developed calcium carbonate can be easily produced led to the completion of the present invention.
ここで云う炭酸化率とは反応液中の炭酸カルシウムの重
３１（−ｗ 、水酸化カルシウムの重量Ｗｌとしたとき
次式ＶＣよって定義されるものである。The carbonation rate referred to herein is defined by the following formula VC, where the weight of calcium carbonate in the reaction solution is 31 (-w) and the weight of calcium hydroxide is Wl.
炭酸化率＝ｗ＋７□ ×１００
ＢＥＴ比表面積とは低温窒素吸着法である。粒子形状は
電子顕微鏡観察による。Carbonation rate=w+7□×100 BET specific surface area is a low temperature nitrogen adsorption method. The particle shape is determined by electron microscopy observation.
本発明は比表面に−Ｒ６０ｄ／１１以上の炭酸カルシウ
ムを製造するにあたり、水酸化カルシウム水懸濁液に結
晶核形成剤を加えてから、濃度１５Ｖ％以上の炭酸ガス
を流速” １１ ／ ｍｉｎ／しｃａ（ｏＨ）２以上で
吹込み、炭酸化率が４０９６に達するまでに連鎖粒子形
成促進剤を加えて炭酸化反応を行うことを特徴とする連
鎖状の非常に発達しだ極微細な炭酸カルシウムの製造方
法を提供するものである。In the present invention, when producing calcium carbonate with a specific surface of -R60d/11 or more, a crystal nucleating agent is added to a calcium hydroxide aqueous suspension, and then carbon dioxide gas with a concentration of 15V% or more is flowed at a flow rate of 11/min/ Very fine carbonic acid with a highly developed chain structure, characterized by the fact that the carbonation reaction is carried out by adding a chain particle formation accelerator until the carbonation rate reaches 4096. A method for producing calcium is provided.
本発明に使用する添加薬品の添加時期は、結晶核形成剤
は炭酸化反応前の水酸化カルシウム水懸濁液に加えてお
くことによって比表面積の大きい極微細粒子が得られる
。この結晶核形成剤を炭酸化反応途中に加えても炭酸化
反応前に加えたものよυ比表面積の大きいものが得られ
ない。連鎖粒子形成促進剤は炭酸化率４０％までに加え
ると連鎖状を形成する効果が大きく。When adding the additive chemicals used in the present invention, ultrafine particles with a large specific surface area can be obtained by adding the crystal nucleating agent to the aqueous suspension of calcium hydroxide before the carbonation reaction. Even if this crystal nucleating agent is added during the carbonation reaction, a product with a larger υ specific surface area cannot be obtained than when added before the carbonation reaction. When the chain particle formation promoter is added up to a carbonation rate of 40%, the effect of forming chains becomes large.
また、形成された連鎖状粒子の凝結が少ない。Furthermore, there is little aggregation of the formed chain particles.
連鎖粒子形成促進剤を結晶核形成剤より先に加効果が少
なく、炭酸化反応終了後の脱水、乾燥物が固くなる。Addition of the chain particle formation promoter before the crystal nucleation agent has little effect, and the dehydrated and dried product becomes hard after the carbonation reaction is completed.
本発明に使用する結晶核形成剤は塩酸、硫酸。The crystal nucleating agents used in the present invention are hydrochloric acid and sulfuric acid.
硝酸などの鉱酸、蟻酸、酢酸、プロピオン酸などの低級
カルボン酸および／またはそれらのアンモニウム塩、ア
ルカリ金属塩１．アルミニウム。Mineral acids such as nitric acid, lower carboxylic acids such as formic acid, acetic acid, propionic acid, and/or ammonium salts and alkali metal salts thereof1. aluminum.
亜鉛、マダイ、シウムなどの水可溶金属塩；ツルピント
、ペンタエリスリットなどの多価アルコール類およびシ
ョ糖などが挙られるう
本発明に使用する連鎖粒子形成促進剤はクエン酸、リン
ゴ酸などのヒドロキシカルボン酸。Examples include water-soluble metal salts such as zinc, red sea bream, and sium; polyhydric alcohols such as turpinto and pentaerythritol; and sucrose. Chain particle formation promoters used in the present invention include citric acid, malic acid, etc. Hydroxycarboxylic acid.
グルコン酸、〜１１石酸などのポリぼドロキシカルボン
酸、エナレンジアミン四酢酸、二Ｆリロトリ酢酸などの
アミノカルボン酸、トリポリリン酸ナトリウノ１．ヘギ
サメタりん酸ナトリウムなどのボリリんｒＲＪノ、Ａ
Ｉどのキレート剤およびイソブチレン−マレイン酸共重
合物、スチレノ〜マレイン酸共Ｚｎ ｒｒ物、アクリル
酸−マレイン酸共重合物、ポリアクリル酸などの高分子
ポリカルホン酸のアルカリ金属塩、アンモニウム塩テあ
るアニオン性高分子化合物が挙られる。Gluconic acid, polyhydroxycarboxylic acids such as ~11 tartaric acid, aminocarboxylic acids such as enalediaminetetraacetic acid, 2F lilotriacetic acid, and sodium tripolyphosphate. Boririn rRJ, such as sodium hegisametaphosphate, A
I Any chelating agent and alkali metal salts and ammonium salts of polymeric polycarphonic acids such as isobutylene-maleic acid copolymer, styrene-maleic acid copolymer, acrylic acid-maleic acid copolymer, polyacrylic acid, etc. Examples include polymeric compounds.
本発明に使用する結晶核形成剤の添加量は水酸化カルシ
ウム１００重量部に対して０．５〜１５重量部、好まし
くは１〜１２重１に部である。The amount of the crystal nucleating agent used in the present invention is 0.5 to 15 parts by weight, preferably 1 to 12 parts by weight per 100 parts by weight of calcium hydroxide.
添加量が０．５重量部未満の場合は生成粒子の比表面積
が小さくなる。添加量が１５重ｈｌ：部を上回ると異形
粒子が生成してくる。When the amount added is less than 0.5 parts by weight, the specific surface area of the particles produced becomes small. If the amount added exceeds 15 parts by weight, irregularly shaped particles will be produced.
本発明に使用する連鎖粒子形成促進剤の添加量は水酸化
カルシウム１００重量部に対して［１０５〜８重量部、
好ましくは０．１〜７重量部である。添加量がα０５重
量部未満の場合は連鎖状形成する粒子が少ない。添加量
が８重量部を上回ると連鎖状粒子の凝結物が生成し、比
表面積が低下する。The amount of the chain particle formation promoter used in the present invention is [105 to 8 parts by weight,
Preferably it is 0.1 to 7 parts by weight. If the amount added is less than α05 parts by weight, fewer particles will form a chain. If the amount added exceeds 8 parts by weight, aggregates of chain particles will be formed and the specific surface area will decrease.
本発明で使用する炭酸ガス濃度は１５Ｖ％以上必要であ
る。炭酸ガス濃度が１５Ｖ％未満の場合は粗大粒子が生
成する。The carbon dioxide concentration used in the present invention needs to be 15V% or more. When the carbon dioxide concentration is less than 15V%, coarse particles are generated.
本発明使用する炭酸ガス吹込み量は４０１／ｍｉｎ／
Ｈｐ Ｏａ （ＯＨ）２以上、好ましくは５０〜１５゜
１ ／ ｍｉｎ／ ＫＰＯａ （ＯＨ）２である。炭酸
ガス流速が４０ ＩＩ ／ ｍｉｎ／ ｂ Ｃａ （Ｏ
Ｈ）２未満の場合は連鎖状粒子の凝結物が生成する、
本発明で使用する水酸化カルシウム水懸濁液と生成粒子
の形状が不均一となり、比表面積も小さくなる。The carbon dioxide gas injection rate used in the present invention is 401/min/
Hp Oa (OH)2 or more, preferably 50-15°1/min/KPOa (OH)2. When the carbon dioxide gas flow rate is 40 II / min / b Ca (O
H) If it is less than 2, aggregates of chain particles will be produced, and the shape of the aqueous calcium hydroxide suspension used in the present invention and the particles produced will be non-uniform, and the specific surface area will also be small.
本発明で使用する水酸化カルシウム水懸濁液の温度は０
〜２５°Ｃ９好ましくは３〜２０°Ｃである。温度が２
５゛Ｃを上回ると粗大粒子が生成してくる。The temperature of the calcium hydroxide aqueous suspension used in the present invention is 0.
-25°C9, preferably 3-20°C. temperature is 2
When the temperature exceeds 5°C, coarse particles are generated.
本発明の炭酸カルシウムは炭酸化反応終了後。The calcium carbonate of the present invention is obtained after the carbonation reaction is completed.
プレス脱水し、これを乾燥、粉砕して粉末状製品を得た
。Press dehydration was carried out, and this was dried and ground to obtain a powdered product.
このように本発明の炭酸カルシウムは水酸化カルシウム
水懸濁液に加える選択された添加薬品の添加順序、添加
時期と炭酸化の際の厳しい条件によって、比表面精６０
が／ｙ以上の極微細な連鎖状粒子で、その極微細連鎖状
粒子が凝結せず単一に分散された品がはじめて得られた
つまた１本発明の炭酸カルシウムはカサの高い。As described above, the calcium carbonate of the present invention has a specific surface roughness of 60 depending on the order and timing of addition of the selected additive chemicals added to the calcium hydroxide aqueous suspension and the severe conditions during carbonation.
The calcium carbonate of the present invention has a high bulk, and is the first to obtain a product with ultrafine chain particles having a diameter of /y or more, in which the ultrafine chain particles are not aggregated but are dispersed in a single manner.
指頭による触感のなめらかな粉末であった。It was a powder that felt smooth to the touch with the tip of a finger.
本発明の炭酸カルシウムはゴム、プラスチックの充填剤
として配合すると容易に分散され°。The calcium carbonate of the present invention is easily dispersed when blended as a filler in rubber and plastics.
その配合物は高引張シ強さ、高剛性を与える。The formulation provides high tensile strength and high stiffness.
塗料の体質顔料として混練すると早期分散が良更に公知
の表面処理を施すことによって、充填剤あるいは顔料と
して１分散性、補強性などの物性を一層改善し得ること
は云うまでもない。It goes without saying that when kneaded as an extender pigment in a paint, early dispersion is excellent, and physical properties such as monodispersibility and reinforcing properties can be further improved as a filler or pigment by applying known surface treatments.
次に本発明の製造方法を実施例により具体的に説明する
。Next, the manufacturing method of the present invention will be specifically explained using examples.
実施例 １
濃度６Ｗｔ、％、温度１５°Ｃに調製した水酸化カルシ
ウム水懸濁液１０００１ｊを反応容器に入れ。Example 1 A calcium hydroxide aqueous suspension 10001j prepared at a concentration of 6 Wt% and a temperature of 15°C was placed in a reaction vessel.
これに濃度１０Ｗｉ、％に調製した硫酸アルミニウム水
浴液６０辱加えて混合してから、Ｉａ＋１５５Ｖ％の炭
酸ガスを流速８０ Ｉ！／ ｍｉｎ／ Ｉ（７０ａ（Ｏ
ｉ（）Ｑで吹込み、炭酸化率１５９６まで炭酸化する。To this, 60 drops of aluminum sulfate water bath solution adjusted to a concentration of 10 Wi, % was added and mixed, and then carbon dioxide gas of Ia + 155 V% was added at a flow rate of 80 I! /min/I(70a(O
Blow in with i()Q and carbonate to a carbonation rate of 1596.
ついで濃度１０ Ｗｔ、％に調製したクエン酸すｌ−Ｉ
Ｊウム水溶液５．６１を加えて、炭酸化反応を行い。Then, citric acid l-I adjusted to a concentration of 10 Wt%
A carbonation reaction was carried out by adding 5.6 liters of Jum aqueous solution.
連鎖状の非常忙発達した極微細な炭酸カルシラ五を得た
。この炭酸カルシウム１ｕｌｌはプレス脱水機によシ母
液を分離９ついで乾燥、粉砕して約５ｏＫＰ仕上げた。A chain-like extremely developed ultrafine carbonate Calcilla 5 was obtained. The mother liquor of 1 µl of this calcium carbonate was separated using a press dehydrator, and then dried and pulverized to give a final product of approximately 5oKP.
得られた本発明の先成物を試験した結果を第１表および
連鎖状炭酸カルシウムの電子顕微鏡写真を第１図に示す
。なお。The results of testing the obtained preform of the present invention are shown in Table 1, and an electron micrograph of chain calcium carbonate is shown in FIG. In addition.
第１表には実施例２〜４で得られた生成物についての結
果も併せて示す。Table 1 also shows the results for the products obtained in Examples 2-4.
実施例 ２
濃度ａＷｔ、％、温度２ｏ″Ｃに調製した水酸化カルシ
ウム水懸濁液１０００１１１を反応容器に入れ。Example 2 A calcium hydroxide aqueous suspension 1000111 prepared at a concentration aWt, % and a temperature of 2o''C was placed in a reaction vessel.
これに濃度１０Ｗｔ、％に調製した酢酸水容器２８しを
加えて混合してから、濃度３５Ｖ％の炭酸ガスを流速５
０ ｄ／ｍｉｎ／ Ｋｙ （Ｅ！１（ＯＨ）２ テ吹込
ミ、炭酸化率２５％寸で炭酸化する。ついで濃度１−Ｏ
Ｗｔ。After adding and mixing 28 glasses of acetic acid water adjusted to a concentration of 10Wt%, carbon dioxide gas with a concentration of 35V% was added at a flow rate of 5%.
0 d/min/Ky (E!1(OH)2) Carbonate at a carbonation rate of 25%. Then, the concentration is 1-O.
Wt.
％に調製したアニオン性高分子化合物（商品名；インパ
ン、四〇クラレ製イソブチレｙ” −無水マレイン酸共
重合物のナトリウム塩）水溶液２゜ｔを加えて炭酸化反
応を行い、連鎖状の非常に発達した極微細な炭酸カルシ
ウムを得た。この炭酸カルシウム懸濁物はプレス脱水機
に、より母液を分離、ついで乾燥、粉砕して約５３１ｊ
仕上げた。% of an anionic polymer compound (trade name: Inpan, sodium salt of isobutylene-maleic anhydride copolymer manufactured by Shio Kuraray) was added to carry out a carbonation reaction to form a chain-like polymer. This calcium carbonate suspension was separated from the mother liquor using a press dehydrator, then dried and pulverized to give a powder of about 531J.
Finished.
実施例 ３
濃度７Ｗｔ、％、温度１８°Ｃに調製した水酸化カルシ
ウム水懸濁液１０００ＫＰを反応容器に入れ。Example 3 A 1000 KP calcium hydroxide aqueous suspension prepared at a concentration of 7 Wt% and a temperature of 18°C was placed in a reaction vessel.
これに濃度１０ Ｗｔ、％に調製したソルビット水溶液
１０．５ ＫＰを加えて混合してから、濃度３５Ｖ％の
炭酸ガスを流速Ｉ Ｄ ０７１ ／ ｍｉｎ／４０ａ（
ＯＨ）２で吹込み炭酸化率７％まで炭酸化する。ついで
蒙度ＳＷｔ、％に調製したエチレンジアミンデトラ四酢
酸二ナトリウム７シを加えて炭酸化゛反応を行い、連鎖
状の非常に発達した極微細な炭酸カルシウムを得た。こ
の炭酸カルシウム懸濁物はプレス脱水機により母液を分
離、ついで乾燥。To this was added and mixed sorbitol aqueous solution 10.5 KP prepared to a concentration of 10 Wt, %, and then carbon dioxide gas with a concentration of 35 V% was added at a flow rate of ID 071/min/40a (
Carbonate by blowing with OH)2 to a carbonation rate of 7%. Next, 7 ml of disodium ethylenediaminedetratetraacetate adjusted to a concentration of SWt% was added to carry out a carbonation reaction to obtain extremely fine calcium carbonate with a highly developed chain structure. The mother liquor of this calcium carbonate suspension is separated using a press dehydrator and then dried.
粉砕して約９４１仕上げた。I crushed it and finished about 941 pieces.
実施例 ４ 濃度ＳＷｔ、％、温度１２°温度１梨 ルシウム水懸濁液１０００ＫＰを反応容゛器に入れ。Example 4 Concentration SWt, %, temperature 12°temperature 1 pear Put 1000 KP of lucium water suspension into the reaction vessel.
これに濃度１０Ｗｔ，％に調製したショ糖水溶液２５Ｋ
Ｐを加えて混合してから，濃度ＸＳＶ％の炭酸ガスを流
速１２０１ ／ｍｉｎ／Ｋｐ ０ａ（ＯＨ）２で吹込み
，炭酸化車重３９６まで炭酸化する。ついで濃度１０Ｗ
ｔ．％に調製したトリポリりん酸ナトリウノ・水溶液２
５ １（７ ％７加えて炭酸化反応を行い，連鎖状の
非常に発達した極微細な炭酸カルシウムを得た。この炭
酸カルシウム懸濁物はプレス脱水機によ＃）１υ液全分
離，ついで乾燥，粉砕して約６７Ｆｙに仕トげた。Add to this a 25K sucrose aqueous solution prepared to a concentration of 10Wt and %.
After adding and mixing P, carbon dioxide gas having a concentration of XSV% is blown in at a flow rate of 1201/min/Kp 0a(OH)2 to carbonate the mixture to a carbonation vehicle weight of 396. Then the concentration is 10W
t. Sodium tripolyphosphate aqueous solution prepared in %
5 1 (7%7) was added and a carbonation reaction was performed to obtain extremely fine calcium carbonate with a very developed chain. This calcium carbonate suspension was passed through a press dehydrator to completely separate the 1υ liquid, and then It was dried and ground to about 67 Fy.
粉砕前の乾燥塊状物の硬さは硬い方から．「硬」「やや
硬」「軟Ｊ とした。The hardness of the dried lumps before pulverization starts from the hardest. It was rated as ``hard'', ``slightly hard'', and ``soft J''.
第１表および第１図の結果から１本発明品は特に連鎖状
の非常に発達した極微細な炭酸カルシウムであるがとが
明らかである。From the results shown in Table 1 and FIG. 1, it is clear that the product of the present invention is extremely fine calcium carbonate with a highly developed chain structure.
比較例１〜５
水酸化カルシウム水懸濁液に硫酸アルミニウムとクエン
酸ナトリウムを同時に加えたか（比較例１）、硫酸アル
ミニウムを加えなかったか（比較例２）、クエン酸ナト
リウムを加えなかったか（比較例３）、硫酸アルミニウ
ム・の代りにクエン酸ナトリウムを加え、クエン酸すト
リウムの代りに硫酸アルミニウムを加えたか（比較例４
）、または硫酸アルミニウム、クエン酸ナトリウムを全
く加えない（比較例５）以外は実施例１と同様にして、
炭酸化反応を行い、得られた比較例の生成物を試験した
結果を第２表および比較例４の連鎖束状炭酸カルシウム
の電果を併せて示す。Comparative Examples 1 to 5 Aluminum sulfate and sodium citrate were added to the calcium hydroxide aqueous suspension at the same time (Comparative Example 1), aluminum sulfate was not added (Comparative Example 2), and sodium citrate was not added (Comparative Example 1). Example 3), sodium citrate was added instead of aluminum sulfate, and aluminum sulfate was added instead of thorium citrate (Comparative Example 4).
), or in the same manner as in Example 1 except that aluminum sulfate and sodium citrate were not added at all (Comparative Example 5),
The carbonation reaction was carried out, and the results of testing the obtained product of Comparative Example are shown in Table 2, together with the electrical results of the chain bundled calcium carbonate of Comparative Example 4.
比較例６〜８
濃度１０Ｗｔ、％の硫酸アルミニウム水溶液を６を加え
るか（比較例６）、濃度１０Ｗｔ、％のクエン酸ナトリ
ウム水ｒＲ液を０．２し加えるか（比較例７）またはク
エン酸ナトリウム溶液を災炭酸化率５０％の時点で加え
る（比較例日）以外は実施例１と全く同様にして、炭酸
化反応を行った。Comparative Examples 6 to 8 Adding 6% of an aluminum sulfate aqueous solution with a concentration of 10Wt and % (Comparative Example 6), adding 0.2% of a sodium citrate aqueous rR solution with a concentration of 10Wt and % (Comparative Example 7), or adding citric acid A carbonation reaction was carried out in the same manner as in Example 1, except that the sodium solution was added at the point when the carbonation rate reached 50% (comparative example day).
比較例９〜１２
水酸化カルシウム水懸濁液の濃度を１０Ｗｔ、％とイる
か（比較例９）、水酸化カルシウム水懸濁液の温度を３
０°Ｃとするか（比較例１０）。Comparative Examples 9 to 12 The concentration of the calcium hydroxide aqueous suspension was set to 10 Wt, % (Comparative Example 9), and the temperature of the calcium hydroxide aqueous suspension was set to 3.
0°C (Comparative Example 10).
炭酸ガス濃度を１０Ｖ％とするか（比較例１１）、また
は炭酸ガス吹込み速度を３０ ｌ／ｍｉｎ／に’ｙ Ｏ
ａ（ＯＨ） ２とする（比較例１２）以外は実施例３と
全く同様にして、炭酸化反応を行った。The carbon dioxide concentration was set to 10V% (Comparative Example 11), or the carbon dioxide gas blowing rate was set to 30 l/min/'y O
A carbonation reaction was carried out in the same manner as in Example 3 except that a(OH) 2 was used (Comparative Example 12).
参考例１
実施例１の発明品１００重量部、５ＢＲ１５０２１００
重量部、亜鉛華５重量部、ステアリン酸１重晋部、促進
剤ＤＭ１．２重量部、ＴＴｏ、２重量部および硫黄２電
縫部を混練し、加硫ゴム物性を測定した結果を＠６表に
示す。第４表には比較例３および比較例４の炭酸カルシ
ウム、市販炭酸カルシウムを比較市販品Ａ（表面処理炭
酸カルシウム、＼Ｘ方状、比表面積ｓ ｏ ｄ／Ｐ ）
、比較市阪品Ｂ（軽質炭酸カルシウム、紡錘状、比表
面積５ ｎ？／Ｖ−）として２本発明に代えて使用した
結果をもイＪｌ ＋！：（示すう
第３表
分散性評価；加硫コ゛ム断面につい−ｒ、ｌＮ１１Ｉｌ
ｖＣ，，ｌ：とした。Reference Example 1 100 parts by weight of the invention of Example 1, 5BR1502100
Parts by weight, 5 parts by weight of zinc white, 1 part by weight of stearic acid, 1.2 parts by weight of accelerator DM, 2 parts by weight of TTo, and 2 parts by weight of sulfur, and the results of measuring the physical properties of the vulcanized rubber are shown in Table 6. Shown below. Table 4 shows the comparison of the calcium carbonate of Comparative Examples 3 and 4, commercially available calcium carbonate, and commercial product A (surface-treated calcium carbonate, \X square, specific surface area s o d/P)
, the results of using the comparative Ichisaka product B (light calcium carbonate, spindle shape, specific surface area 5 n?/V-) in place of the present invention are also shown. : (Table 3 dispersibility evaluation; -r, lN11Il for cross section of vulcanized comb)
vC,,l:.
本発明品は第３表の結果７５＼らＢ、ｌｌら力＼な如（
。The product of the present invention is as shown in Table 3 as shown in Table 3.
.
比較例の炭酸カルシウムお上ｒメ比較゛ヴ） ｉｔｊ
ＩＩ藺１シＪ酸カルシウムに比べて１分散４生−ｂ：
ｌ！Ａ ’７会しこよ（、高いモジュラスを付与し、高
い弓１り長りｒａｔさ、 高（ｉｅ度を与え、補強効果
が大きい。Comparative example of calcium carbonate (comparison)
1 Dispersion 4 Raw-b compared to II 1 J Calcium Acid:
l! A '7-kai Shikoyo(, gives high modulus, high bow length, high (ie degree), and has a great reinforcing effect.
第１図は本発明方法により得た実／ｌ０１（付１１のｊ
東鎖状の非常に発達した極微細な１欠酸カット、２／
＋＞ム。
第２図は比較例４の連鎖束状炭酸−７７Ａ・シ・ジノ、
の電子顕微鏡写真を示す。
（以 ト）
特許出願人 株式会社白石中央荀［究ｐｌｉ第１図
手続補正書（方式）
昭和５９乍２月スＩ日
１ 事件の表示 昭和５８年特許願第２０７９５０号２
、Ｑ明ノ名称 炭酸カルシウムの！ｌＩ９造方法６ 補
正する者
事件との１ノＪ係 特許出願人
任 所 尼崎市元浜町４丁目ｙ ８１片Ｊ［ＩＩ５ 補
正話合の日付 昭和５９年１月３１日６、補正の対象
［図面の簡単な説明］の１１３６、・Ａ１− ′
補 正 の 内 容
明細書第ｔ？、＋（ｉ目ＩＭ、ｌ ＋＋＋ｉの簡単な説
明」の欄の全文を下記訂正し１す、
記
第１図は本発明）Ｊθミによる実施例１で得られた炭酸
カルシウムの連鎖状に、１ぐ発、・トシた極微細な粒子
べ（訃告、第２図は比較）４す４でイＨられた炭酸カル
シウムの連鎖束状の粒子（１１￥ｆ５１ｒをそＩｔぞれ
示す電子ｈｉｒｒ倣境グ真であろう（以 ト）Figure 1 shows the fruit/l01 (J in Attachment 11) obtained by the method of the present invention.
Very finely developed eastern chain-like 1-deficient cut, 2/
＋＞Mu. Figure 2 shows the chain bundled carbonic acid-77A Si-Jino of Comparative Example 4;
An electron micrograph is shown. (Hereinafter) Patent Applicant: Shiraishi Chuosun Co., Ltd. [Kyupli Diagram 1 Procedural Amendment (Method) Date: February 1, 1982 Case Indication: 1982 Patent Application No. 207950 2
, Q Akeno name of calcium carbonate! lI9 Construction method 6 Part 1 No. J with the person making the amendment Patent applicant location 4-y Motohama-cho, Amagasaki-shi 81 Piece J [II5 Date of amendment discussion January 31, 1980 6, Subject of amendment
[Brief Description of Drawings] 1136, ・A1-' Amendment Contents Part t? ,+(i-th IM, l +++ i) The full text of the column "Brief explanation of i-th IM, l +++i" has been corrected as below. 1st shot, ultra-fine particles (obituary, Figure 2 is for comparison) Chain bundle-like particles of calcium carbonate (11 yen f51r each shown as an electron hirr imitation) It's probably true (below)
Claims (1)
製造するにあたり、水酸化カルシウム水懸濁液に結晶核
形成剤を加えてから。 濃度１５Ｖ％以上の炭酸ガスを流速４０／／ ｍｉｎ／
Ｋｙ Ｏａ （ＯＨ）２以上で吹込み、炭酸化率が４
０９６に達するまでに連鎖粒子形成促進剤を加えて炭酸
化反応を行うことを特徴とする連鎖状の非常に発達した
極微細な炭酸カルシウムの製造方法。 ■ 結晶核形成剤が鉱酸、低級カルボン酸および／また
は＼それら酸のアンモニウム塩。 アルカリ金属塩、水可溶金属塩、多価アルコール類およ
びショ糖である特許請求の範囲第１項記載の炭酸カルシ
ウムの製造方法。 ■ 連鎖粒子形成促進剤がキレート剤、アニオン性高分
子化合物である特許請求の範囲第１ 項記載ノ炭、酸カ
ルシウムの製造方法。[Claims] ■ In producing calcium carbonate having a BET specific surface area of 60♂/g or more, a crystal nucleating agent is added to an aqueous suspension of calcium hydroxide. Carbon dioxide gas with a concentration of 15V% or more at a flow rate of 40//min/
Ky Oa (OH) blown at 2 or more, carbonation rate 4
1. A method for producing ultrafine calcium carbonate with a highly developed chain, characterized by adding a chain particle formation promoter and carrying out a carbonation reaction until reaching 096. ■ The crystal nucleating agent is a mineral acid, a lower carboxylic acid and/or an ammonium salt of these acids. The method for producing calcium carbonate according to claim 1, which comprises an alkali metal salt, a water-soluble metal salt, a polyhydric alcohol, and sucrose. (2) The method for producing carbonate and calcium oxide as described in claim 1, wherein the chain particle formation promoter is a chelating agent or an anionic polymer compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20795083A JPS60103025A (en) | 1983-11-04 | 1983-11-04 | Manufacture of calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20795083A JPS60103025A (en) | 1983-11-04 | 1983-11-04 | Manufacture of calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60103025A true JPS60103025A (en) | 1985-06-07 |
| JPH0346404B2 JPH0346404B2 (en) | 1991-07-16 |
Family
ID=16548218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20795083A Granted JPS60103025A (en) | 1983-11-04 | 1983-11-04 | Manufacture of calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60103025A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01252525A (en) * | 1987-11-19 | 1989-10-09 | Pfizer Inc | Production of calcium carbonate having large surface area |
| US4888160A (en) * | 1985-12-20 | 1989-12-19 | J.M. Huber Corporation | Process for producing calcium carbonate and products thereof |
| JPH0455464A (en) * | 1990-06-25 | 1992-02-24 | Toray Ind Inc | Thermoplastic polyester composition |
| WO1997020771A1 (en) * | 1995-12-05 | 1997-06-12 | Minerals Technologies Inc. | Process for the preparation of discrete particles of calcium carbonate |
| FR2826950A1 (en) * | 2001-07-04 | 2003-01-10 | Solvay | PROCESS FOR OBTAINING PRECIPITED CALCIUM CARBONATE PARTICLES STRUCTURED ON THE NANOMETRIC SCALE |
| JP2013506613A (en) * | 2009-10-02 | 2013-02-28 | カルシテック・サンテティク・ミネラルズ・リミテッド | Formation of calcium carbonate |
| JP2018012638A (en) * | 2011-10-05 | 2018-01-25 | ソルヴェイ（ソシエテ アノニム） | Precipitated calcium carbonate particle and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5626613A (en) * | 1979-08-13 | 1981-03-14 | Nippon Steel Corp | Roller table for adjusting pass line |
| JPS5731530A (en) * | 1980-08-03 | 1982-02-20 | Kyowa Sogyo:Kk | Integral molding of hinge of box with frp resin cover |
-
1983
- 1983-11-04 JP JP20795083A patent/JPS60103025A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5626613A (en) * | 1979-08-13 | 1981-03-14 | Nippon Steel Corp | Roller table for adjusting pass line |
| JPS5731530A (en) * | 1980-08-03 | 1982-02-20 | Kyowa Sogyo:Kk | Integral molding of hinge of box with frp resin cover |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4888160A (en) * | 1985-12-20 | 1989-12-19 | J.M. Huber Corporation | Process for producing calcium carbonate and products thereof |
| JPH01252525A (en) * | 1987-11-19 | 1989-10-09 | Pfizer Inc | Production of calcium carbonate having large surface area |
| JPH0555449B2 (en) * | 1987-11-19 | 1993-08-17 | Pfizer | |
| JPH0455464A (en) * | 1990-06-25 | 1992-02-24 | Toray Ind Inc | Thermoplastic polyester composition |
| WO1997020771A1 (en) * | 1995-12-05 | 1997-06-12 | Minerals Technologies Inc. | Process for the preparation of discrete particles of calcium carbonate |
| FR2826950A1 (en) * | 2001-07-04 | 2003-01-10 | Solvay | PROCESS FOR OBTAINING PRECIPITED CALCIUM CARBONATE PARTICLES STRUCTURED ON THE NANOMETRIC SCALE |
| WO2003004414A1 (en) * | 2001-07-04 | 2003-01-16 | Solvay (Société Anonyme) | Method for obtaining precipitated calcium carbonate particles of nanometric scale structure |
| JP2004533396A (en) * | 2001-07-04 | 2004-11-04 | ソルヴェイ | Method for producing precipitated calcium carbonate particles having nanoscale structure |
| US7501107B2 (en) | 2001-07-04 | 2009-03-10 | Solvay (Societe Anonyme) | Method for obtaining precipitated calcium carbonate particles of nanometric scale structure |
| US7708973B2 (en) | 2001-07-04 | 2010-05-04 | Solvay (Societe Anonyme) | Method for obtaining precipitated calcium carbonate particles of nanometric scale structure |
| JP2013506613A (en) * | 2009-10-02 | 2013-02-28 | カルシテック・サンテティク・ミネラルズ・リミテッド | Formation of calcium carbonate |
| JP2018012638A (en) * | 2011-10-05 | 2018-01-25 | ソルヴェイ（ソシエテ アノニム） | Precipitated calcium carbonate particle and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0346404B2 (en) | 1991-07-16 |
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