JP2000264628A - Production of calcium carbonate - Google Patents
Production of calcium carbonateInfo
- Publication number
- JP2000264628A JP2000264628A JP11071777A JP7177799A JP2000264628A JP 2000264628 A JP2000264628 A JP 2000264628A JP 11071777 A JP11071777 A JP 11071777A JP 7177799 A JP7177799 A JP 7177799A JP 2000264628 A JP2000264628 A JP 2000264628A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- slaked lime
- aragonite
- weight
- producing
- 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は硫酸塩法またはソー
ダ法によるパルプ製造工程の苛性化工程において製紙用
填料及び、製紙用塗工顔料として有用な性能を与えるア
ラゴナイト系イガグリ状炭酸カルシウムを製造する方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to produce an aragonite-based calcium carbonate that gives useful properties as a filler for papermaking and a coating pigment for papermaking in a causticizing step of a pulp manufacturing process by a sulfate method or a soda method. It is about the method.
【0002】[0002]
【従来の技術】印刷あるいは筆記用に使用される紙に
は、通常、白色度、不透明度、平滑性、筆記性、手触
り、印刷適性等の改良を目的として填料が内添される。
この抄紙方法として、填料にタルク、クレー、酸化チタ
ン等を使用し、pH4.5付近で紙を抄く、いわゆる酸
性抄紙と、pH7〜8.5の中性〜弱アルカリ性域で紙
を抄く、いわゆる中性抄紙がある。中性抄紙では、輸入
品で高価なタルク、クレーに変わって、国産の炭酸カル
シウムを填料として使用することが可能となる。近年、
紙の保存性等の問題から中性抄紙によって得られる中性
紙が着目されるようになり、またこのほかにも紙質、コ
スト、環境対策等の面でもメリットが多いことから、中
性抄紙への移行が進んできており、今後ともその普及が
拡大する情勢にある。2. Description of the Related Art Generally, a filler is internally added to paper used for printing or writing for the purpose of improving whiteness, opacity, smoothness, writability, touch, printability and the like.
As this papermaking method, talc, clay, titanium oxide, or the like is used as a filler, and paper is made at around pH 4.5, so-called acidic papermaking, and paper is made at a pH of 7 to 8.5 in a neutral to weakly alkaline range. And so-called neutral papermaking. In neutral papermaking, it becomes possible to use domestically produced calcium carbonate as a filler instead of imported talc and clay which are expensive. recent years,
Neutral paper obtained by neutral papermaking has attracted attention due to problems such as paper storability.Besides, there are many advantages in terms of paper quality, cost, environmental measures, etc. The transition is progressing, and it is in a situation where its spread will continue to expand in the future.
【0003】安価で軽量な中性紙への要求が高まってく
るなかで、填料としての炭酸カルシウムの位置づけは非
常に重要である。この中性抄紙で填料として用いられる
炭酸カルシウムには、天然石灰石を乾式あるいは湿式で
機械粉砕して得られる重質炭酸カルシウムと、化学的方
法によって得られる沈降性炭酸カルシウム(合成炭酸カ
ルシウム)がある。[0003] With the increasing demand for cheap and lightweight neutral paper, the position of calcium carbonate as a filler is very important. Calcium carbonate used as a filler in this neutral papermaking includes heavy calcium carbonate obtained by mechanically pulverizing natural limestone in a dry or wet manner, and precipitated calcium carbonate (synthetic calcium carbonate) obtained by a chemical method. .
【0004】ところが、天然石灰石をボールミル等の粉
砕機を使用して得られた重質炭酸カルシウムは、内添填
料として使用した場合、抄紙の際に激しくプラスチック
ワイヤを磨耗させてしまう。さらに、この填料を使用し
て、通常の上質紙、塗工紙を抄造製造した場合、嵩、白
色度、不透明度等において不十分である。[0004] However, heavy calcium carbonate obtained by using natural limestone using a pulverizer such as a ball mill, when used as an internal filler, causes severe wear of the plastic wire during papermaking. Further, when ordinary high quality paper and coated paper are manufactured by papermaking using this filler, the bulk, whiteness, opacity and the like are insufficient.
【0005】一方、化学的方法によって得られる沈降性
炭酸カルシウム(合成炭酸カルシウム)は、反応系が比
較的簡単(水、消石灰、炭酸ガス)なこともあり、製紙
工場のオンサイトにて実際に製造される例もいくつか見
られる。On the other hand, precipitated calcium carbonate (synthetic calcium carbonate) obtained by a chemical method has a relatively simple reaction system (water, slaked lime, carbon dioxide gas), and is actually used on-site at a paper mill. Some examples are produced.
【0006】しかしながら、この方法は、炭酸カルシウ
ムが唯一の産物であることから、非常に製造コストが高
く、ユーザーの要望する低コスト化にはそぐわず、安価
な紙には使用できないか、あるいはその使用量も大きく
制限される。However, this method has a very high production cost since calcium carbonate is the only product, does not meet the cost reduction demanded by the user, and cannot be used for inexpensive paper, or is not used. Usage is also greatly limited.
【0007】そこで考えられるのが、クラフトパルプ製
造工程の蒸解薬品の回収・再生を行う苛性化工程で副生
する炭酸カルシウムを製紙用原料として使用する方法で
ある。[0007] A possible method is to use calcium carbonate by-produced in the causticizing step of recovering and regenerating the cooking chemicals in the kraft pulp manufacturing process as a raw material for papermaking.
【0008】しかし、従来ここで得られる炭酸カルシウ
ムは形状コントロールが難しいため、サイコロ状や六角
面体などの種々雑多な形状を有し、粒子径も大きく、何
れも不定形あるいは塊状で、従来の重質炭酸カルシウム
に近いものであるため、この填料を使用して通常の上質
紙、塗工紙を製造した場合、嵩、白色度、不透明度等に
おいては不十分であった。また、近年、抄紙機が大型化
し、抄紙速度もより高速化する中にあって、プラスチッ
クワイヤの磨耗性とウェットエンドでの歩留まり性にも
大きな問題を抱えていた。However, the calcium carbonate obtained heretofore is difficult to control in shape, so it has various shapes such as a dice and a hexagon, and has a large particle diameter. When the filler is used to produce ordinary high-quality paper or coated paper, the bulk, whiteness, opacity, etc. are insufficient. Further, in recent years, as the paper machine has been increased in size and the papermaking speed has been further increased, there has been a great problem in the abrasion property of the plastic wire and the yield at the wet end.
【0009】これに対し最近、特開平10−22697
4号公報では、生石灰の消和反応と苛性化反応の条件を
特定することで上記問題を解決した製紙用に有用な炭酸
カルシウムの製造方法が開示されている。しかし、この
製造方法により得られる炭酸カルシウムでは、抄紙時の
ワイヤ歩留まり、ワイヤ摩耗性、さらに得られる紙の不
透明度が十分に良好でなかった。On the other hand, recently, Japanese Patent Application Laid-Open No. 10-22697
No. 4 discloses a method for producing calcium carbonate useful for papermaking, which solves the above-mentioned problem by specifying conditions for slaking reaction and causticizing reaction of quicklime. However, with the calcium carbonate obtained by this production method, the wire yield during papermaking, wire abrasion, and the opacity of the obtained paper were not sufficiently satisfactory.
【0010】[0010]
【発明が解決しようとする課題】以上のような状況に鑑
み、抄紙時には、ウェットエンドでのワイヤ歩留まりが
良く、ワイヤ磨耗性に優れ、またこれを紙の製造に用い
た場合には、さらに不透明度が高く、印刷品質等の優れ
た上質紙や塗工紙を提供するために、苛性化工程を利用
して、製紙用に有用な安価なアラゴナイト系イガグリ状
炭酸カルシウムを製造する改良方法の提供を本発明の課
題とした。In view of the above situation, in papermaking, the wire yield at the wet end is good, the wire is excellent in abrasion, and when it is used in the production of paper, it is even more difficult. Provision of an improved method for producing inexpensive aragonite-based igashigari-like calcium carbonate useful for paper making using a causticizing process in order to provide high quality paper and coated paper with high transparency and excellent print quality. Was made the subject of the present invention.
【0011】[0011]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意研究を重ねた結果、硫酸塩法又は
ソーダ法によるパルプ製造工程の苛性化工程を利用し
て、生成時の生石灰と水のモル比が特定範囲で、かつ特
定量の炭酸カルシウムを含有する消石灰をpH5.5〜
13.5の液でスラリー化させることによって得られる
消石灰乳に、硫酸塩法又はソーダ法によるパルプ製造工
程の苛性化工程から出る緑液を連続的に添加し、その添
加速度及び反応温度を制御することによって解決できる
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。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, the production of pulp using the causticizing step of the pulp manufacturing process by the sulfate method or the soda method has been carried out. Slaked lime having a molar ratio of quicklime and water in a specific range and containing a specific amount of calcium carbonate at pH 5.5 to 5.5
Green liquor from the causticizing step of the pulp manufacturing process by the sulfate method or the soda method is continuously added to slaked lime milk obtained by slurrying with the liquid of 13.5, and the addition rate and the reaction temperature are controlled. Thus, the present invention has been made based on this finding.
【0012】[0012]
【発明の実施の形態】本発明の第1段工程であるスラリ
ー化において使用する消石灰は、消石灰生成時の生石灰
と水のモル比が、生石灰:水=1:1〜1:5の消石灰
を使用する。水の量が生石灰:水=1:1より少ない場
合には、生石灰が全量消石灰とならず、第2段工程の反
応が不均一となり、生成する炭酸カルシウムのアラゴナ
イト結晶含有率が低下し、不定形あるいは塊状粒子が増
加し、ワイヤ磨耗性に劣ると共に、良好な紙質が得られ
ない。水の量が生石灰:水=1:5を超えても生成する
炭酸カルシウムのアラゴナイト結晶含有率が低下し、不
定形あるいは塊状粒子が増加し、ワイヤ磨耗性に劣ると
共に、良好な紙質が得られない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Slaked lime used in the slurrying of the first step of the present invention is slaked lime having a molar ratio of quicklime: water = 1: 1 to 1: 5 when slaked lime is produced. use. If the amount of water is less than quicklime: water = 1: 1, the entire amount of quicklime does not become slaked lime, the reaction in the second step becomes uneven, and the content of aragonite crystals in the generated calcium carbonate decreases. Regular or massive particles increase, resulting in inferior wire abrasion and good paper quality. Even when the amount of water exceeds quicklime: water = 1: 5, the content of aragonite crystals in the calcium carbonate formed decreases, irregular or massive particles increase, wire abrasion is poor, and good paper quality is obtained. Absent.
【0013】消石灰中の炭酸カルシウム含量について
は、消石灰の重量を基準として0.05〜8重量%の炭
酸カルシウムを含有するものを使用する。8重量%を超
えれば、生成する炭酸カルシウムのアラゴナイト結晶含
有率が低下し、不定形あるいは塊状粒子が増加し、ワイ
ヤ磨耗性に劣ると共に、良好な紙質が得られない。また
一方、0.05重量%未満のものを得るためには、原料
生石灰の焼成に要するエネルギーが極度に増加したり、
あるいは焼成装置に特別な工夫を必要とするなどがあ
り、不経済となる。As for the calcium carbonate content in slaked lime, one containing 0.05 to 8% by weight of calcium carbonate based on the weight of slaked lime is used. If it exceeds 8% by weight, the content of aragonite crystals in the generated calcium carbonate decreases, irregular or massive particles increase, wire abrasion is poor, and good paper quality cannot be obtained. On the other hand, in order to obtain less than 0.05% by weight, the energy required for firing the raw quicklime is extremely increased,
Alternatively, a special device is required for the firing apparatus, which is uneconomical.
【0014】ここで、消石灰の生成において使用する生
石灰については、由来は特に限定されないが、炭酸カル
シウムを主成分とする石灰石、及び硫酸塩法またはソー
ダ法によるパルプ製造の苛性化工程において炭酸ナトリ
ウムを水酸化ナトリウムに転化する際に生成する炭酸カ
ルシウムを焼成したものが好ましい。Here, the origin of the quicklime used in the production of slaked lime is not particularly limited, but limestone containing calcium carbonate as a main component, and sodium carbonate in the causticizing step of pulp production by the sulfate method or the soda method. It is preferable that calcium carbonate produced upon conversion to sodium hydroxide is calcined.
【0015】消石灰のスラリー化に用いる液としては、
pH5.5〜13.5を有するものを使用する。この液
には、苛性化工程で補充される水、あるいは緑液や白液
中の沈殿物(ドレッグス、炭酸カルシウムスラッジ)を
洗浄した上澄液である弱液が使用できる。特に弱液を使
用する場合、pH13.5を超えると、NaOHやNa
2CO3濃度が高くなるため生成する炭酸カルシウムのア
ラゴナイト結晶含有率が低下し、不定形あるいは塊状粒
子が増加し、ワイヤー摩耗性に劣ると共に、良好な紙質
が得られない。一方、苛性化工程で補充される水を使用
する場合は、一般的な工業用水の水質レベルのpH5.
5以上であれば特に問題ない。また、消石灰のスラリー
化に水あるいは弱液を使用した場合、ここでの使用に相
当する、苛性化工程で補充される水量あるいはスメルト
溶解用弱液の量を減少させることで、苛性化工程内の水
バランスを調整できる。このことより、苛性化工程の操
業上重要な問題となる白液濃度の低下を伴うこともなく
苛性化反応を行うことができる。The liquid used for making slaked lime into a slurry is as follows:
One having a pH of 5.5 to 13.5 is used. As this liquid, water replenished in the causticizing step, or a weak liquid which is a supernatant liquid obtained by washing a precipitate (dregs, calcium carbonate sludge) in green liquor or white liquor can be used. Particularly when a weak solution is used, if the pH exceeds 13.5, NaOH or Na
Since the concentration of 2 CO 3 is increased, the content of aragonite crystals in the generated calcium carbonate is reduced, irregular or aggregated particles are increased, and wire abrasion is poor, and good paper quality cannot be obtained. On the other hand, when water replenished in the causticizing step is used, the pH of general industrial water is set at pH5.
If it is 5 or more, there is no particular problem. When water or a weak liquid is used for making slaked lime slurry, the amount of water replenished in the causticizing step or the amount of the weak liquid for dissolving the smelt, which corresponds to the use here, is reduced. Water balance can be adjusted. Accordingly, the causticization reaction can be performed without lowering the concentration of white liquor, which is an important problem in the operation of the causticizing process.
【0016】スラリー化時の消石灰濃度は、10〜60
重量%、好ましくは15〜55重量%で行う。60重量
%を超えると液粘度が高すぎて現実的に攪拌が困難とな
り、一方10重量%未満では、生成する炭酸カルシウム
のアラゴナイト結晶含有率が低下し、不定形あるいは塊
状粒子が増加し、ワイヤ磨耗性に劣ると共に、良好な紙
質が得られない。The slaked lime concentration during slurrying is 10 to 60.
%, Preferably 15 to 55% by weight. If it exceeds 60% by weight, the liquid viscosity is too high and stirring becomes difficult in practice, while if it is less than 10% by weight, the content of aragonite crystals in the calcium carbonate formed decreases, the amorphous or massive particles increase, and In addition to poor abrasion, good paper quality cannot be obtained.
【0017】スラリー化時における消石灰と液との混合
には、通常の攪拌力を有する一般的な攪拌羽根式、ポン
プ式、押し出し機類、捏和機類、混練機類の中から、混
合時の液あるいはスラリーの粘度にあわせて適宜選定し
て使用すれば良い(昭和63年3月18日丸善株式会社
発行、化学工学便覧参照)。The mixing of slaked lime and the liquid at the time of slurrying may be performed by using a general stirring blade type, a pump type, an extruder, a kneader, or a kneader having a normal stirring force. It may be appropriately selected and used in accordance with the viscosity of the liquid or slurry (see Maruzen Co., Ltd., March 18, 1988, Chemical Engineering Handbook).
【0018】スラリー化時の温度は、後で添加する緑液
の温度により適宜設定する。スラリー化時の時間は、均
一混合できる時間が取れれば良く、濃度、温度、攪拌力
等により適宜設定する。The temperature during slurrying is appropriately set according to the temperature of the green liquor to be added later. The time at which the slurry is formed may be any time that allows uniform mixing, and is appropriately set according to the concentration, temperature, stirring power, and the like.
【0019】本発明の第2段工程である苛性化反応に用
いる緑液は、一般的な硫酸塩法又はソーダ法の苛性化工
程から発生するものを使用し、その濃度はトータルアル
カリで80〜160g/L{その内、Na2CO3が65〜
130g/L(Na2O換算、以下同じ)}、好ましくは
トータルアルカリ100〜150g/L(その内、Na 2
CO3が85〜130g/L)である。For use in the second step of the present invention, the causticizing reaction.
Green liquor is a common sulfate or soda process caustic
From the process, and the concentration is
80-160g / L in potash, including NaTwoCOThreeIs 65-
130 g / L (NaTwoO conversion, the same applies hereinafter)}, preferably
Total alkali 100-150 g / L (of which Na Two
COThreeIs 85 to 130 g / L).
【0020】第1段工程で調製された消石灰乳と緑液の
混合方法は、消石灰乳に対する緑液の添加速度を0.0
2〜0.4cc(緑液)/min/g(生石灰換算値)、好
ましくは0.05〜0.35cc(緑液)/min/g
(生石灰換算値)で行う。0.02cc(緑液)/min/
g(生石灰換算値)より小さい添加速度では、生産性が劣
り現実的でなく、また一方0.4cc(緑液)/min/
g(生石灰換算値)より大きい添加速度では、生成する炭
酸カルシウムのアラゴナイト結晶含有率が低下し、不定
形あるいは塊状粒子が増加し、ワイヤ磨耗性に劣ると共
に、良好な紙質が得られない。The mixing method of the slaked lime milk and the green liquor prepared in the first step is performed by adjusting the addition rate of the green liquor to the slaked lime milk to 0.0
2 to 0.4 cc (green liquor) / min / g (quick lime conversion value), preferably 0.05 to 0.35 cc (green liquor) / min / g
(Quick lime conversion value). 0.02cc (green liquid) / min /
If the addition rate is less than g (quick lime equivalent), the productivity is poor and not realistic, and on the other hand, 0.4 cc (green liquor) / min /
If the addition rate is greater than g (calculated lime value), the content of aragonite crystals in the generated calcium carbonate will decrease, irregular or massive particles will increase, wire abrasion will be poor, and good paper quality will not be obtained.
【0021】苛性化反応温度については、反応温度が2
5〜75℃、好ましくは30〜70℃で行う。75℃よ
り高い場合には、生成する炭酸カルシウムのアラゴナイ
ト結晶含有率が低下し、不定形あるいは塊状粒子が増加
し、ワイヤ磨耗性に劣ると共に、良好な紙質が得られな
い。また、一方25℃より低い場合にも、生成する炭酸
カルシウムのアラゴナイト結晶含有率が低下し、不定形
あるいは塊状粒子が増加し、ワイヤ磨耗性に劣ると共
に、良好な紙質が得られない。さらに、冷却のための装
置の工夫およびそれに伴う経費がかさみ不経済である。As for the causticization reaction temperature, the reaction temperature is 2
The reaction is carried out at 5 to 75 ° C, preferably 30 to 70 ° C. If the temperature is higher than 75 ° C., the content of aragonite crystals in the generated calcium carbonate decreases, irregular or aggregated particles increase, wire abrasion is poor, and good paper quality cannot be obtained. On the other hand, when the temperature is lower than 25 ° C., the content of aragonite crystals in the generated calcium carbonate decreases, amorphous or massive particles increase, wire abrasion is poor, and good paper quality cannot be obtained. Furthermore, the device for cooling and the accompanying cost are expensive and uneconomical.
【0022】苛性化反応時の攪拌には、一般的な攪拌羽
根式、ポンプ式、押し出し機類、捏和機類、混練機類の
中から、第1段工程で調製された消石灰乳と緑液が均一
に混合できるものを適宜選定して使用すれば良い(昭和
63年3月18日丸善株式会社発行、化学工学便覧参
照)。The stirring at the time of the causticizing reaction may be performed by using a general stirring blade type, a pump type, an extruder, a kneader, or a kneader from the slaked lime milk prepared in the first step and the green. What can be uniformly mixed with the liquid may be suitably selected and used (see Chemical Engineering Handbook, published by Maruzen Co., Ltd. on March 18, 1988).
【0023】以上のような条件下において、短径が0.
1〜1.5μmで、長径が0.3〜6.0μmの棒状あ
るいは針状粒子がランダムに凝集した、平均粒子径が
2.5〜10.0μmで、アラゴナイト結晶を50〜8
5%含有したアラゴナイト系のイガグリ状炭酸カルシウ
ムが調製可能となる。Under the conditions as described above, the minor axis is equal to 0.
Bar-shaped or needle-shaped particles having a length of 1 to 1.5 μm and a long diameter of 0.3 to 6.0 μm are randomly aggregated. The average particle diameter is 2.5 to 10.0 μm.
An aragonite-based igashi-like calcium carbonate containing 5% can be prepared.
【0024】本発明によって得られるアラゴナイト系イ
ガグリ状炭酸カルシウムは、従来のクラフトパルプ製造
工程の蒸解薬品回収を行う苛性化工程で得られたアラゴ
ナイト系針状苛性化軽カルに比べて、歩留まり性に優
れ、これを内添することで上質紙、塗工紙の不透明度等
に優れた特徴を与える。The aragonite-based calcium carbonate of the aragonite type obtained according to the present invention has a higher yield compared to the aragonite-based acicular caustic light calcium obtained by the causticizing step of recovering the cooking chemicals in the conventional kraft pulp manufacturing process. Excellent, opacity of high quality paper and coated paper is given by adding this internally.
【0025】本発明では、原料として消石灰の固体を使
用することにより、ワイヤー歩留まり、ワイヤー磨耗及
び不透明度などの点で、従来よりも優れたアラゴナイト
系イガグリ状炭酸カルシウムが得られたと考えられる。According to the present invention, it is considered that the use of slaked lime solid as a raw material provided an aragonite-based limestone-like calcium carbonate which was superior to the conventional one in terms of wire yield, wire abrasion and opacity.
【0026】[0026]
【実施例】以下に本発明を実施例および比較例をあげて
より詳細に説明するが、当然ながら、本発明は実施例の
みに限定されるものではない。 [試験法]アルカリの測定:TAPPI624hm−85
あるいはこれに準じて測定した。EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to only Examples. [Test method] Measurement of alkali: TAPPI 624 hm-85
Or it measured according to this.
【0027】消石灰中の炭酸カルシウム含量:SSC
5100 TG/DTA22システム(セイコー電子工
業株式会社)使用 生成炭酸カルシウムの平均粒子径:生成物を水洗濾過
し、水で希釈後、レーザー回折式粒度分布計(シーラス
社製モテ゛ル715)で平均粒子径を測定した。短径、長径は、
電子顕微鏡写真(日本電子(株)製JSM-5300)から
実測した。Calcium carbonate content in slaked lime: SSC
5100 TG / DTA22 system (Seiko Denshi Kogyo Co., Ltd.) used Average particle diameter of generated calcium carbonate: The product is washed with water, filtered, diluted with water, and then averaged with a laser diffraction particle size distribution analyzer (Model 715, manufactured by Cirrus Co.). Was measured. The minor axis and major axis are
It was actually measured from an electron micrograph (JSM-5300 manufactured by JEOL Ltd.).
【0028】形態観察:生成物を水洗濾過し、乾燥後
走査型電子顕微鏡(日本電子(株)製JSM-5300)で形
態観察した。 結晶系:Rigaku製 X線回折RAD−2Cによ
り測定した。Morphological observation: The product was washed with water, filtered, dried, and observed with a scanning electron microscope (JSM-5300, manufactured by JEOL Ltd.). Crystal system: manufactured by Rigaku X-ray diffraction was measured by RAD-2C.
【0029】アラゴナイト結晶含有率(%):硝酸カ
ルシウムと尿素よりアラゴナイト結晶を製造{Gyps
um&Lime No.245(P 234参照、Ri
gaku製 X線回折RAD−2Cの測定ではカルサイ
トピークなし}し、試薬のカルサイト結晶含有率99.
9%との混合比率を変えて、X線回折RAD−2Cで測
定する。この時のX線回折ピークの2θ=26.2°
(アラゴナイト結晶)と2θ=29.4°(カルサイト
結晶)の強度から次の計算式{26.2°の強度÷(2
6.2°の強度+29.4°の強度)}より強度比を求
めて、混合割合と強度比の検量線を作成した。この検量
線を使用し、アラゴナイト含有率を求めた。 [実施例1]1Lの4ツ口フラスコ容器(以下の実施例・
比較例についても同じ容器使用)に、生成時の生石灰と
水のモル比が、生石灰:水=1:1.4であり、かつ消
石灰の重量を基準として1.6重量%の炭酸カルシウム
を含有する消石灰74gと、pH6.8の苛性化工程で
補充される水を用い、消石灰濃度が30重量%になる割
合で混合、スラリー化させて消石灰乳をつくり、緑液
(組成:Na2CO3=110g/L、Na2S=34g
/L、NaOH=6g/L。いずれもNa2O換算値
で、以下の実施例・比較例について同じ)添加速度0.
22cc/min/g(生石灰換算値)、添加時間60
分、温度50℃、攪拌速度250rpm(KYOEI社
POWER STIRRER TYPE PS-2N使用、以下の実施例・比較例
について同じ攪拌機使用)の条件で苛性化反応を行わせ
た。生成反応物の平均粒子径測定および形態観察を行っ
た結果、平均長径3.5μm、平均短径0.2μmの一
次粒子から構成される、平均粒子径が6.0μmのアラ
ゴナイト系イガグリ状炭酸カルシウムが認められた。実
験条件および結果を表1に示す。 [実施例2]生成時の生石灰と水のモル比が、生石灰:
水=1:1.8でありかつ消石灰の重量を基準として
3.0%の炭酸カルシウムを含有する消石灰74gと、
実施例1と同じ補充水、緑液および装置を用い、消石灰
濃度が20重量%になる割合で混合、スラリー化させて
消石灰乳をつくり、緑液添加速度0.044cc/min
/g(生石灰換算値)、添加時間300分、温度45
℃、攪拌速度250rpmの条件で苛性化反応を行わせ
た。生成反応物の平均粒子径測定および形態観察を行っ
た結果、平均長径4.5μm、平均短径0.2μmの一
次粒子から構成される、平均粒子径が6.5μmのアラ
ゴナイト系イガグリ状炭酸カルシウムが認められた。実
験条件および結果を表1に示す。 [実施例3]生成時の生石灰と水のモル比が、生石灰:
水=1:3.0でありかつ消石灰の重量を基準として
5.0重量%の炭酸カルシウムを含有する消石灰74g
と、pH13.1の弱液を用い、消石灰濃度が40重量
%になる割合で混合、スラリー化させて消石灰乳をつく
り、実施例1と同じ緑液を添加速度0.11cc/min
/g(生石灰換算値)、添加時間120分、温度40
℃、実施例1と同じ装置の攪拌速度300rpmの条件
で苛性化反応を行わせた。生成反応物の平均粒子径測定
および形態観察を行った結果、平均長径3.5μm、平
均短径0.25μmの一次粒子から構成される、平均粒
子径が6.0μmのアラゴナイト系イガグリ状炭酸カル
シウムが認められた。実験条件および結果を表1に示
す。 [比較例1]炭酸カルシウム含有率3.0重量%の生石
灰50gと、pH13.1の弱液を用い、生石灰濃度が
30重量%になる割合で混合、消和させて石灰乳をつく
り、実施例1と同じ緑液を添加速度0.11cc/mi
n/g(生石灰)、添加時間120分、温度85℃、攪
拌速度1000rpmの条件で苛性化反応を行わせた。
反応生成物は、平均長径3.8μm、平均短径0.3μ
mであるアラゴナイト系針状炭酸カルシウムであること
が認められた。実験条件および結果を表2に示す。 [比較例2]炭酸カルシウム含有率7.0重量%のキル
ン焼成生石灰を使用した以外は、比較例1と同様に実験
を行った。反応生成物は、平均長径8.0μm、平均短
径0.4μmであるアラゴナイト系針状炭酸カルシウム
であることが認められた。実験条件および結果を表2に
示す。 [比較例3]消石灰のスラリー化に用いる液のpHを1
3.9にした以外は、実施例1と同様に実験を行った。
この時の反応生成物は、平均粒子径が8.2μmであ
り、その構成一次粒子が不定形あるいは塊状の炭酸カル
シウムであることが認められた。実験条件および結果を
表2に示す。 [比較例4]消石灰スラリー化時の消石灰濃度を5重量
%にした以外は、実施例1と同様に実験を行った。この
時の反応生成物は、平均粒子径が9.5μmであり、そ
の構成一次粒子が不定形の炭酸カルシウムであることが
認められた。実験条件および結果を表2に示す。 [比較例5]苛性化反応時の緑液添加速度を、0.88
cc/min/g(生石灰換算値)、添加時間15分にした
以外は、実施例1と同様に実験を行った。この時の反応
生成物は、平均粒子径が8.5μmであり、その構成一
次粒子が不定形あるいは塊状の炭酸カルシウムであるこ
とが認められた。実験条件および結果を表2に示す。 [比較例6]消石灰中の炭酸カルシウム含有率を10重
量%にした以外は、実施例1と同様に実験を行った。こ
の時の反応生成物は、平均粒子径が10.4μmであ
り、その構成一次粒子が不定形あるいは塊状の炭酸カル
シウムであることが認められた。実験条件および結果を
表2に示す。 [比較例7]生成時の生石灰と水のモル比を、生石灰:
水=1:8.0にした以外は、実施例1と同様に実験を
行った。この時の反応生成物は、平均粒子径が8.4μ
mであり、その構成一次粒子が不定形あるいは塊状の炭
酸カルシウムであることが認められた。実験条件および
結果を表2に示す。 [比較例8]苛性化反応時の温度を15℃にした以外
は、実施例1と同様に実験を行った。この時の反応生成
物は、平均粒子径が8.7μmであり、その構成一次粒
子が不定形あるいは塊状の炭酸カルシウムであることが
認められた。実験条件および結果を表2に示す。 [比較例9]苛性化反応時の温度を90℃にした以外
は、実施例1と同様に実験を行った。この時の反応生成
物は、平均粒子径が8.7μmであり、その構成一次粒
子が不定形あるいは塊状の炭酸カルシウムであることが
認められた。実験条件および結果を表2に示す。 [応用例1]カナダ標準濾水度(以下C.S.F.と略
記する)が300mlの晒し化学パルプの単独スラリー
に、対パルプ当たり内添サイズ剤(アルキルケテンダイ
マー)0.02%、硫酸バンド0.5%、カチオン変性
デンプン0.3%、実施例1〜3と比較例1〜9で得た
それぞれの炭酸カルシウムを15%(各種苛性化軽カル
は、サンドグラインダーで3μmに粉砕したものを用い
た)、並びに200ppmの歩留まり向上剤(ポリアク
リルアミド、アニオン性分子量400万〜5OO万)を
内添し調製したスラリーをテストマシンで抄紙した。こ
の様にして得られた紙の坪量、密度、不透明度の測定は
20℃、65%RHで1昼夜調湿した後、JISに準じ
て行った。また填料の歩留りおよびワイヤ摩耗試験を実
施した。試験方法を以下に、また得られた結果を表1及
び表2に示す。Aragonite crystal content (%): Aragonite crystals are produced from calcium nitrate and urea.
um & Lime No. 245 (see page 234, Ri
There was no calcite peak in the measurement of X-ray diffraction RAD-2C manufactured by Gaku, and the calcite crystal content of the reagent was 99.
X-ray diffraction is measured by RAD-2C while changing the mixing ratio with 9%. At this time, 2θ of the X-ray diffraction peak = 26.2 °
(Aragonite crystal) and the intensity of 2θ = 29.4 ° (calcite crystal), the following formula {intensity of 26.2 °} (2
(Intensity at 6.2 ° + Intensity at 29.4 °) The intensity ratio was determined from}, and a calibration curve of the mixing ratio and the intensity ratio was prepared. Using this calibration curve, the aragonite content was determined. Example 1 1 L 4-neck flask container (Example
(The same container was used for the comparative example), the molar ratio of quicklime and water at the time of formation was quicklime: water = 1: 1.4, and 1.6% by weight calcium carbonate was contained based on the weight of slaked lime. Using 74 g of slaked lime and water replenished in a causticizing step of pH 6.8, the slaked lime is mixed and slurried at a ratio of 30% by weight to form slaked lime milk, and a green liquor (composition: Na 2 CO 3) = 110g / L, Na 2 S = 34g
/ L, NaOH = 6 g / L. All of them are in terms of Na 2 O and are the same for the following Examples and Comparative Examples.
22 cc / min / g (quick lime equivalent), addition time 60
Min, temperature 50 ° C, stirring speed 250rpm (KYOEI
(The use of POWER STIRRER TYPE PS-2N, the same stirrer was used for the following Examples and Comparative Examples). As a result of measuring the average particle diameter and observing the morphology of the produced reaction product, an aragonite-based calcium carbonate having an average particle diameter of 6.0 μm, composed of primary particles having an average major axis of 3.5 μm and an average minor axis of 0.2 μm, was obtained. Was observed. Table 1 shows the experimental conditions and results. [Example 2] The molar ratio of quicklime and water at the time of formation was
74 g of slaked lime, with water = 1: 1.8 and containing 3.0% calcium carbonate based on the weight of slaked lime;
Using the same replenishing water, green liquor and apparatus as in Example 1, mixed and slurried at a ratio of slaked lime concentration of 20% by weight to make slaked lime milk, green liquor addition rate 0.044 cc / min
/ G (quick lime equivalent), addition time 300 minutes, temperature 45
Causticization reaction was carried out at a temperature of 250 ° C. and a stirring speed of 250 rpm. As a result of measuring the average particle diameter and observing the morphology of the produced reaction product, an aragonite-based calcium carbonate having an average particle diameter of 6.5 μm, composed of primary particles having an average major diameter of 4.5 μm and an average minor diameter of 0.2 μm, was found. Was observed. Table 1 shows the experimental conditions and results. [Example 3] The molar ratio of quicklime and water at the time of formation was quicklime:
74 g of slaked lime with water = 1: 3.0 and containing 5.0% by weight of calcium carbonate, based on the weight of slaked lime
And a weak liquor having a pH of 13.1 were mixed and slurried at a ratio of slaked lime concentration of 40% by weight to form slaked lime milk. The same green liquor as in Example 1 was added at a rate of 0.11 cc / min.
/ G (quick lime equivalent), addition time 120 minutes, temperature 40
The causticization reaction was carried out at a temperature of 300 ° C. and a stirring speed of 300 rpm in the same apparatus as in Example 1. As a result of measuring the average particle diameter and observing the morphology of the produced reaction product, an aragonite-based calcium carbonate having an average particle diameter of 6.0 μm, composed of primary particles having an average major axis of 3.5 μm and an average minor axis of 0.25 μm, was obtained. Was observed. Table 1 shows the experimental conditions and results. [Comparative Example 1] Using 50 g of quicklime having a calcium carbonate content of 3.0% by weight and a weak liquid having a pH of 13.1, mixing and slaking at a ratio at which the quicklime concentration becomes 30% by weight to produce lime milk, and implemented. The same green liquor as in Example 1 was added at a rate of 0.11 cc / mi.
The causticization reaction was performed under the conditions of n / g (quick lime), addition time 120 minutes, temperature 85 ° C., and stirring speed 1000 rpm.
The reaction product had an average major axis of 3.8 μm and an average minor axis of 0.3 μm.
m was found to be aragonite-based acicular calcium carbonate. Table 2 shows the experimental conditions and results. Comparative Example 2 An experiment was performed in the same manner as in Comparative Example 1, except that calcined calcined lime having a calcium carbonate content of 7.0% by weight was used. The reaction product was found to be aragonite-based acicular calcium carbonate having an average major axis of 8.0 μm and an average minor axis of 0.4 μm. Table 2 shows the experimental conditions and results. [Comparative Example 3] The pH of a solution used for making slaked lime slurry was 1
An experiment was performed in the same manner as in Example 1 except that the value was changed to 3.9.
The reaction product at this time had an average particle diameter of 8.2 μm, and it was confirmed that the constituent primary particles were amorphous or massive calcium carbonate. Table 2 shows the experimental conditions and results. Comparative Example 4 An experiment was carried out in the same manner as in Example 1 except that the slaked lime concentration at the time of forming slaked lime slurry was 5% by weight. The reaction product at this time had an average particle size of 9.5 μm, and it was confirmed that the constituent primary particles were amorphous calcium carbonate. Table 2 shows the experimental conditions and results. [Comparative Example 5] The green liquor addition rate during the causticization reaction was 0.88
The experiment was carried out in the same manner as in Example 1 except that the addition time was 15 minutes in cc / min / g (calculated value of lime). The reaction product at this time had an average particle size of 8.5 μm, and it was recognized that the constituent primary particles were amorphous or massive calcium carbonate. Table 2 shows the experimental conditions and results. Comparative Example 6 An experiment was performed in the same manner as in Example 1 except that the content of calcium carbonate in slaked lime was changed to 10% by weight. The reaction product at this time had an average particle diameter of 10.4 μm, and it was recognized that the constituent primary particles were amorphous or massive calcium carbonate. Table 2 shows the experimental conditions and results. [Comparative Example 7] The molar ratio of quicklime and water at the time of formation was calculated as follows:
The experiment was performed in the same manner as in Example 1 except that the water was set to 1: 8.0. The reaction product at this time had an average particle size of 8.4 μm.
m, and it was recognized that the constituent primary particles were amorphous or massive calcium carbonate. Table 2 shows the experimental conditions and results. Comparative Example 8 An experiment was performed in the same manner as in Example 1 except that the temperature during the causticization reaction was set to 15 ° C. The reaction product at this time had an average particle size of 8.7 μm, and it was recognized that the constituent primary particles were amorphous or massive calcium carbonate. Table 2 shows the experimental conditions and results. Comparative Example 9 An experiment was performed in the same manner as in Example 1 except that the temperature during the causticization reaction was set to 90 ° C. The reaction product at this time had an average particle size of 8.7 μm, and it was recognized that the constituent primary particles were amorphous or massive calcium carbonate. Table 2 shows the experimental conditions and results. [Application Example 1] To a slurry of bleached chemical pulp having a Canadian standard freeness (hereinafter abbreviated as CSF) of 300 ml, 0.02% of an internal sizing agent (alkyl ketene dimer) per pulp, Sulfuric acid band 0.5%, cation-modified starch 0.3%, each calcium carbonate obtained in Examples 1 to 3 and Comparative Examples 1 to 9 15% (various causticized light calcium is pulverized to 3 μm by a sand grinder) And a slurry prepared by internally adding 200 ppm of a retention improver (polyacrylamide, anionic molecular weight of 4,000,000 to 500,000) was prepared by a test machine. The basis weight, density and opacity of the paper thus obtained were measured at 20 ° C. and 65% RH for one day and night, and then measured according to JIS. Filler yield and wire abrasion tests were also performed. The test method is shown below, and the obtained results are shown in Tables 1 and 2.
【0030】[0030]
【表1】 [Table 1]
【0031】[0031]
【表2】 [Table 2]
【0032】[試験法] (1)ワイヤー摩耗測定法 ・試験器:日本フィルコン式磨耗試験装置 ・ワイヤ:日本フィルコンCOS−60ポリエステルワ
イヤ ・スラリー濃度:2重量% ・荷重:1250g ・磨耗時間:90分 ・磨耗量:磨耗試験前後のワイヤ重量減量(mg) (2)歩留まり測定法 ・使用パルプ:C.S.F.300mlに叩解したパル
プ 紙料濃度:0.5重量%(パルプ/填料=60/40) 薬品添加順序:パルプ→硫酸バンド(1%)→カチオン
化デンプン(0.2%)→填料→コロイダルシリカ
(0.02%) ( )内は対パルプ添加量で重量% ・測定装置:ブリットジャーテスター使用 ・測定条件:薬品添加時シェア 700rpm 測定時シェア 1500rpm 使用ワイヤ 200メッシュ 紙料のファーストパスリテンションを測定 [応用例2]応用例1で作製したそれぞれの紙に、サイ
ズプレスで酸化デンプンを乾燥後の重量が2g/m2になる
ように表面サイズプレスし乾燥した。その後ソフトカレ
ンダー処理(南千住製作所製、60℃、50kg/cm一定で処
理)した。塗工液組成として、平均粒子径が0.6μm
の重質炭酸カルシウム(商品名:ハイドロカーボ90、
白石カルシウム(株)製)60重量%、平均粒子径0.
5μmのカオリン(商品名:ウルトラホワイト90、エ
ンゲルハード(株)製)40重量%に対し、接着剤とし
てリン酸エステル化デンプン4重量%、スチレン・ブタ
ジエン系ラテックス10重量%および分散剤0.3重量
%とを含有した濃度64%の塗工液を、テストブレード
コータで、片面当り10g/m2を両面に塗工、乾燥さ
せた。得られたものについての品質評価方法を以下に、
また得られた結果を表3及び表4に示す。[Test Method] (1) Wire abrasion measurement method-Tester: Japan Filcon type abrasion test device-Wire: Nippon Filcon COS-60 polyester wire-Slurry concentration: 2% by weight-Load: 1250 g-Wear time: 90 Min.-Amount of wear: Weight loss of wire before and after the wear test (mg) (2) Yield measurement method-Pulp used: C.I. S. F. Pulp beaten to 300 ml Paper stock concentration: 0.5% by weight (pulp / filler = 60/40) Chemical addition order: Pulp → sulfuric acid band (1%) → cationized starch (0.2%) → filler → colloidal silica (0.02%) The value in parentheses is the amount added to the pulp in% by weight.-Measuring device: Use a brit jar tester.-Measurement conditions: Share at the time of adding chemicals 700 rpm. Share at the time of measurement 1500 rpm. Wire used 200 mesh. Measure the first pass retention of paper stock. [Application Example 2] Each paper produced in Application Example 1 was subjected to surface size pressing so that the weight after drying of the oxidized starch was 2 g / m 2 by a size press and dried. Thereafter, a soft calender treatment (manufactured by Minami-Senju Seisakusho, 60 ° C., constant treatment at 50 kg / cm) was performed. The coating liquid composition has an average particle size of 0.6 μm
Heavy calcium carbonate (trade name: Hydrocarbo 90,
60% by weight, average particle size: 0.
For 40% by weight of kaolin (trade name: Ultra White 90, manufactured by Engelhard Co., Ltd.) of 5 μm, 4% by weight of a phosphate esterified starch, 10% by weight of a styrene / butadiene-based latex and 0.3 of a dispersant are used as adhesives. A coating solution containing 64% by weight and a concentration of 64% was applied on both sides at 10 g / m 2 per one side by a test blade coater and dried. The quality evaluation method for the obtained product is shown below.
Tables 3 and 4 show the obtained results.
【0033】[0033]
【表3】 [Table 3]
【0034】[0034]
【表4】 [Table 4]
【0035】[品質評価方法] (1)白紙光沢度:JIS P−8142に従い測定 (2)不透明度:JIS P−8138に従い測定 (3)印刷後光沢:RI印刷機(明製作所製)を用い、
サカタインクス製ダイヤトーンGSL紅を使用し、イン
キ量0.35cc一定で印刷し、JIS P−8142
に従い角度75度で測定[Quality evaluation method] (1) Blank gloss: Measured according to JIS P-8142 (2) Opacity: Measured according to JIS P-8138 (3) Gloss after printing: Using a RI printer (manufactured by Meiji Seisakusho) ,
Using Sakata Inx Diatone GSL Red, printing at a constant ink amount of 0.35 cc, JIS P-8142
Measured at an angle of 75 degrees according to
【0036】[0036]
【発明の効果】実施例1〜3に示す如く、本発明による
炭酸カルシウムはアラゴナイト系イガグリ状炭酸カルシ
ウムであった。As shown in Examples 1 to 3, the calcium carbonate according to the present invention was an aragonite-based igakiri-like calcium carbonate.
【0037】また応用例1の紙質試験の結果、本発明に
よるアラゴナイト系イガグリ状炭酸カルシウムは不透明
度が高く、填料の歩留り性およびプラスチックワイヤ摩
耗性も優れていた。Further, as a result of the paper quality test of the application example 1, the aragonite-based calcium carbonate with aragonite type according to the present invention had high opacity, and was excellent in the retention property of the filler and the abrasion property of the plastic wire.
【0038】応用例2の本発明のイガグリ状炭酸カルシ
ウム内添紙から作られた塗工紙は、従来の炭酸カルシウ
ム内添紙に比べ不透明度、印刷品質等の点で優れた結果
が得られた。The coated paper made from the internally-coated calcium carbonate-based paper of Application Example 2 of the present invention has excellent results in terms of opacity, print quality, and the like, as compared with conventional calcium-carbonated internal paper. Was.
【図面の簡単な説明】[Brief description of the drawings]
【図1】実施例1で得られたアラゴナイト系イガグリ状
炭酸カルシウムの結晶粒子構造を示す走査型電子顕微鏡
写真である。FIG. 1 is a scanning electron micrograph showing a crystal particle structure of an aragonite-based igaguri calcium carbonate obtained in Example 1.
【図2】実施例1で得られた生成物についてのX線回折
の結果を示す図である。FIG. 2 is a view showing a result of X-ray diffraction of a product obtained in Example 1.
【図3】実施例2で得られたアラゴナイト系イガグリ状
炭酸カルシウムの結晶粒子構造を示す走査型電子顕微鏡
写真である。FIG. 3 is a scanning electron micrograph showing the crystal particle structure of an aragonite-based igaguri calcium carbonate obtained in Example 2.
【図4】実施例3で得られたアラゴナイト系イガグリ状
炭酸カルシウムの結晶粒子構造を示す走査型電子顕微鏡
写真である。FIG. 4 is a scanning electron micrograph showing the crystal particle structure of the aragonite-based igaguri calcium carbonate obtained in Example 3.
【図5】比較例1で得られたアラゴナイト系針状炭酸カ
ルシウムの結晶粒子構造を示す走査型電子顕微鏡写真で
ある。FIG. 5 is a scanning electron micrograph showing a crystal particle structure of an aragonite-based acicular calcium carbonate obtained in Comparative Example 1.
【図6】比較例1で得られた生成物についてのX線回折
の結果を示す図である。FIG. 6 is a view showing the result of X-ray diffraction of the product obtained in Comparative Example 1.
【図7】比較例3で得られた炭酸カルシウムの結晶粒子
構造を示す走査型電子顕微鏡写真である。FIG. 7 is a scanning electron micrograph showing the crystal particle structure of calcium carbonate obtained in Comparative Example 3.
【図8】比較例3で得られた生成物についてのX線回折
の結果を示す図である。FIG. 8 is a view showing the result of X-ray diffraction of the product obtained in Comparative Example 3.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金井 清 山口県岩国市飯田町2丁目8番1号 日本 製紙株式会社岩国技術研究所内 (72)発明者 南里 泰徳 山口県岩国市飯田町2丁目8番1号 日本 製紙株式会社岩国技術研究所内 Fターム(参考) 4G076 AA16 AC02 BA15 BA43 BD01 BD02 CA02 CA05 CA26 DA02 DA30 4L055 AG12 AG27 AG48 AG63 AG76 AG94 AG97 AH01 AH02 AH37 AJ04 BC07 EA16 EA20 EA25 EA31 EA32 FA08 FA10 FA12 FA15 GA19 GA34 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kiyoshi Kanai 2-81-1, Iida-cho, Iwakuni-shi, Yamaguchi Japan Japan Paper Manufacturing Co., Ltd. Iwakuni Technical Research Laboratory (72) Inventor Yasunori Minato 2--8, Iida-cho, Iwakuni-shi, Yamaguchi No. 1 Nippon Paper Industries Co., Ltd. Iwakuni Technical Research Laboratory F-term (reference) 4G076 AA16 AC02 BA15 BA43 BD01 BD02 CA02 CA05 CA26 DA02 DA30 4L055 AG12 AG27 AG48 AG63 AG76 AG94 AG97 AH01 AH02 AH37 AJ04 BC07 EA16 EA20 EA25 FA10 FA10 FA10 GA19 GA34
Claims (7)
造工程の苛性化工程において炭酸カルシウムを製造する
方法であって、消石灰生成時の生石灰と水のモル比が、
生石灰:水=1:1〜1:5であり、かつ消石灰の重量
を基準として0.05〜8重量%の炭酸カルシウムを含
有する前記消石灰に対して、前記消石灰の濃度が10〜
60重量%になるようにpH5.5〜13.5を有する
液を添加し、攪拌あるいは捏和しながらスラリー化させ
て消石灰乳及び/又は消石灰泥を生成する第1段工程、 ついで該消石灰乳及び/又は消石灰泥に対して、前記苛
性化工程で発生し、白液を製造するに必要な緑液を0.
02〜0.4cc(緑液)/min/g(消石灰の生石灰
換算値)の添加速度で所定量逐次添加し、反応温度25
〜75℃にて苛性化反応を行う第2段工程よりなる、製
紙用に有用なアラゴナイト系イガグリ状炭酸カルシウム
の製造方法。1. A method for producing calcium carbonate in a causticizing step of a pulp producing step by a sulfate method or a soda method, wherein the molar ratio of quicklime and water at the time of slaked lime production is:
Quick lime: water = 1: 1 to 1: 5, and the concentration of the slaked lime is 10 to the slaked lime containing 0.05 to 8% by weight of calcium carbonate based on the weight of slaked lime.
A first step of adding a liquid having a pH of 5.5 to 13.5 so as to be 60% by weight and slurrying while stirring or kneading to produce slaked lime milk and / or slaked lime mud; And / or slaked lime mud contains green liquor generated in the causticizing step and required for producing white liquor.
A predetermined amount was sequentially added at an addition rate of 02 to 0.4 cc (green liquor) / min / g (calculated value of slaked lime), and the reaction temperature was 25.
A method for producing an aragonite-based limestone-like calcium carbonate useful for papermaking, comprising a second step of performing a caustic reaction at -75 ° C.
が、苛性化工程で発生する弱液である、請求項1記載の
アラゴナイト系イガグリ状炭酸カルシウムの製造方法。2. The method for producing aragonite-based lime-like calcium carbonate according to claim 1, wherein the liquid having a pH of 5.5 to 13.5 is a weak liquid generated in a causticizing step.
た、短径が0.1〜1.5μmで、長径が0.3〜6.
0μmの一次粒子から構成される、平均粒子径が2.5
〜10.0μmのアラゴナイト系イガグリ状の炭酸カル
シウム3. The method according to claim 1, wherein the minor axis is 0.1 to 1.5 μm and the major axis is 0.3 to 6.
The average particle diameter is 2.5 μm, composed of primary particles of 0 μm.
Aragonite-type calcium carbonate in the form of aragonite of up to 10.0 μm
た、製紙用填料及び塗工紙用塗工顔料として有用なアラ
ゴナイト系イガグリ状炭酸カルシウム。4. An aragonite-based limestone-like calcium carbonate useful as a filler for papermaking and a coating pigment for coated paper, produced by the method according to claim 1. Description:
リ状炭酸カルシウムを塗工顔料として用いることを特徴
とする塗工組成物。5. A coating composition characterized by using the aragonite-based calcium carbonate according to claim 4 as a coating pigment.
リ状炭酸カルシウムを製紙用填料として用いることを特
徴とする紙又は塗工顔料として用いることを特徴とする
塗工紙6. Coated paper characterized by using the aragonite-based calcium carbonate according to claim 4 as a filler for papermaking or using as a coating pigment.
いて使用する生石灰が、炭酸カルシウムを主成分とする
石灰石、及び/又は硫酸塩法またはソーダ法によるパル
プ製造の苛性化工程において炭酸ナトリウムを水酸化ナ
トリウムに転化する際に生成する炭酸カルシウムを焼成
したものである請求項1記載のアラゴナイト系イガグリ
状炭酸カルシウムの製造方法。7. The quicklime used in the production of slaked lime used in the first step is limestone mainly containing calcium carbonate and / or sodium carbonate in a causticizing step of pulp production by a sulfate method or a soda method. 2. The method for producing aragonite-based igakigari-like calcium carbonate according to claim 1, wherein the calcium carbonate produced upon conversion to sodium hydroxide is calcined.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002293537A (en) * | 2001-04-02 | 2002-10-09 | Okutama Kogyo Co Ltd | Method for manufacturing calcium carbonate |
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1999
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JP2002293537A (en) * | 2001-04-02 | 2002-10-09 | Okutama Kogyo Co Ltd | Method for manufacturing calcium carbonate |
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