JPS6232130B2 - - Google Patents
Info
- Publication number
- JPS6232130B2 JPS6232130B2 JP17884283A JP17884283A JPS6232130B2 JP S6232130 B2 JPS6232130 B2 JP S6232130B2 JP 17884283 A JP17884283 A JP 17884283A JP 17884283 A JP17884283 A JP 17884283A JP S6232130 B2 JPS6232130 B2 JP S6232130B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- carbon dioxide
- reaction
- basic calcium
- lime
- 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.)
- Expired
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 112
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 76
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000001569 carbon dioxide Substances 0.000 claims description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 38
- 239000000920 calcium hydroxide Substances 0.000 claims description 35
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 20
- 238000007664 blowing Methods 0.000 description 20
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 235000012255 calcium oxide Nutrition 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000008267 milk Substances 0.000 description 4
- 210000004080 milk Anatomy 0.000 description 4
- 235000013336 milk Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000276425 Xiphophorus maculatus Species 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005406 washing 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
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】
本発明は、組成式2CaCO3・Ca（OH）2・
nH2O，ｎ＝１〜1.5を有する板状塩基性炭酸カル
シウムを、石灰乳に特定条件下で二酸化炭素を吹
き込む事で製造する方法に関するものである。[Detailed Description of the Invention] The present invention has the compositional formula 2CaCO 3・Ca(OH) 2・
The present invention relates to a method for producing plate-like basic calcium carbonate having nH 2 O, n=1 to 1.5, by blowing carbon dioxide into milk of lime under specific conditions.
従来、石灰乳と二酸化炭素又は二酸化炭素含有
ガスとの反応によつて、立方状、連鎖状、ぼうす
い状、柱状などの形状を有する沈降性炭酸カルシ
ウムを製造する方法はよく知られている。しかし
ながら、この炭酸カルシウムの製造過程における
中間生成物である組成式2CaCO3・Ca（OH）2・
nH2Oを有する板状塩基性炭酸カルシウムは、古
くからその存在が推定されていたものの、生成条
件が複雑であるため、これまでその製造方法が見
出されておらず、実際に得られていない。 BACKGROUND ART Conventionally, a method for producing precipitated calcium carbonate having shapes such as cubic, chain, bladder, and columnar shapes by reacting milk of lime with carbon dioxide or carbon dioxide-containing gas is well known. However, an intermediate product in the production process of calcium carbonate, which has the composition formula 2CaCO 3・Ca(OH) 2・
Although the existence of plate-like basic calcium carbonate containing nH 2 O has been presumed to exist for a long time, due to the complicated production conditions, no method for its production has been found until now, and it has never been actually obtained. do not have.
本発明者らは、石灰乳と二酸化炭素とを反応さ
せて、組成式2CaCO3・Ca（OH）2・nH2Oを有す
る板状塩基性炭酸カルシウムを製造することにつ
いて、鋭意研究を重ねた結果、反応の進行に伴
い、反応液の電気伝導度曲線及びPH曲線に特有の
降下現象が現われることに着目し、この現象を利
用して二酸化炭素の吹込速度を制御することによ
り、その目的を達成しうることを見出し、この知
見に基づいて本発明をなすに至つた。 The present inventors have conducted intensive research on producing plate-like basic calcium carbonate having the composition formula 2CaCO 3 .Ca(OH) 2 .nH 2 O by reacting milk of lime with carbon dioxide. As a result, we focused on the fact that as the reaction progressed, a characteristic drop phenomenon appeared in the electrical conductivity curve and PH curve of the reaction solution, and by utilizing this phenomenon to control the blowing rate of carbon dioxide, we were able to achieve this goal. We have discovered that this can be achieved, and based on this knowledge, we have completed the present invention.
すなわち、本発明は、組成式2CaCO3・Ca
（OH）2，nH2Oを有する板状塩基性炭酸カルシウ
ムの製造方法を提供するものである。 That is, the present invention has the compositional formula 2CaCO 3 ·Ca
The present invention provides a method for producing plate-like basic calcium carbonate having (OH) 2 , nH 2 O.
このような板状塩基性炭酸カルシウムは、本発
明方法に従い、20℃以下の温度に維持した、CaO
としての濃度４〜12ｇ／100c.c.の石灰乳の中へ、
二酸化炭素を一定速度で導入し、かきまぜながら
反応させることにより炭酸カルシウムを製造する
に当り、反応液の電気伝導度又はPHを継続的に測
定し、反応開始からその二次降下が終了するまで
の時間ｔと二次降下終了点から三次降下が終了す
るまでの時間t2との間で比t2／t1値が0.40〜0.50の
範囲になるように二酸化炭素の導入速度を制御す
ることによつて得ることができる。 Such plate-like basic calcium carbonate is prepared according to the method of the present invention by CaO2 maintained at a temperature below 20°C.
into milk of lime with a concentration of 4 to 12 g/100 c.c.
When producing calcium carbonate by introducing carbon dioxide at a constant rate and reacting while stirring, the electrical conductivity or pH of the reaction solution is continuously measured and the temperature from the start of the reaction until the end of the secondary drop is measured. The introduction rate of carbon dioxide is controlled so that the ratio t 2 /t 1 value between time t and time t 2 from the end point of secondary descent to the end of tertiary descent is in the range of 0.40 to 0.50. You can get it by twisting it.
本発明方法の原料として、用いられる石灰乳
は、生石灰又は消石灰を水に懸濁させたものであ
り、この生石灰及び消石灰について特に制限はな
いが、それらの粒径が200メツシユふるいを通過
するような大きさであり、かつ強固に凝集した粗
粒の少ないものが好ましい。 The milk of lime used as a raw material in the method of the present invention is made by suspending quicklime or slaked lime in water, and there are no particular restrictions on the quicklime or slaked lime, but the milk of lime should be such that the particle size passes through a 200 mesh sieve. It is preferable that the particles have a large size and have few strongly agglomerated coarse particles.
また、石灰乳の濃度はCaO換算で４〜12ｇ／
100c.c.、好ましくは５〜10ｇ／100c.c.の範囲であ
る。その濃度が４ｇ／100c.c.未満では、濃度が低
すぎて経済的でなく、また12ｇ／100c.c.を超える
と、石灰乳の粘度が高すぎて作業性が悪く、その
上反応熱による石灰乳の温度上昇が大きく、反応
温度の調節が困難となる。 In addition, the concentration of milk of lime is 4 to 12 g/CaO equivalent.
100 c.c., preferably in the range of 5 to 10 g/100 c.c. If the concentration is less than 4g/100c.c., the concentration is too low and uneconomical; if it exceeds 12g/100c.c., the viscosity of the milk of lime is too high and workability is poor, and furthermore, the reaction heat is The temperature of the milk of lime increases significantly, making it difficult to control the reaction temperature.
本発明において石灰乳の炭酸化に用いる二酸化
炭素は純粋なものでもよいし、二酸化炭素を含有
したガスでもよい。この二酸化炭素含有ガスを用
いる場合、二酸化炭素の濃度については、特に制
限はないが、低すぎると反応終了までに長時間を
要するので、好ましくは10容量％以上、より好ま
しくは20容量％以上である。 In the present invention, the carbon dioxide used for carbonating the milk of lime may be pure or a gas containing carbon dioxide. When using this carbon dioxide-containing gas, there are no particular restrictions on the concentration of carbon dioxide, but if it is too low, it will take a long time to complete the reaction, so it is preferably 10% by volume or more, more preferably 20% by volume or more. be.
次に、本発明方法における二酸化炭素又は二酸
化炭素含有ガスの吹き込み速度について、添付図
面に従つて説明すると、第１図は、石灰乳に二酸
化炭素又は二酸化炭素含有ガスをかきまぜながら
一定速度で吹き込んで塩基性炭酸カルシウムを生
成させる際の、反応液の典型的な電気伝導度曲線
及びPH曲線の１例である。この図から明らかなよ
うに、両曲線とも反応過程において３種の降下現
象を有することが分る。これらの降下現象を反応
開始点から順に一次降下、二次降下及び三次降下
と呼ぶことにする。石灰乳と二酸化炭素との主反
応は液相反応であり、反応系に導入した二酸化炭
素がまず水に溶解し、次いで溶存している水酸化
カルシウムと反応するものと考えられる。したが
つて、反応に伴う液相中の水酸カルシウムの濃度
変化は、ただちに電気伝導度やPH変化となつて検
知できる。前記の一次降下は反応生成物の結晶核
生成に伴う溶存水酸化カルシウムの濃度降下に対
応するものと推定できる。この一次降下は、懸濁
している水酸化カルシウムが水に溶解し、溶存水
酸化カルシウムを補給するので、しばらくすると
回復する。また二次降下は塩基性炭酸カルシウム
に特有のものであつて、該塩基性炭酸カルシウム
が存在しないときは現われず、塩基性炭酸カルシ
ウム生成の有無の指標となりうる。この二次降下
は、水酸化カルシウムが塩基性炭酸カルシウムに
変化し終るときの溶存水酸化カルシウムの濃度変
化に対応する。さらに三次降下は、中間生成した
塩基性炭酸カルシウムが炭酸化の継続によつて炭
酸カルシウムに変化し終るときの溶液中の塩基性
炭酸カルシウムの濃度変化に対応する。 Next, the blowing rate of carbon dioxide or carbon dioxide-containing gas in the method of the present invention will be explained with reference to the attached drawings. This is an example of a typical electrical conductivity curve and PH curve of a reaction solution when producing basic calcium carbonate. As is clear from this figure, both curves have three types of descending phenomena during the reaction process. These descent phenomena will be referred to as primary descent, secondary descent, and tertiary descent in order from the reaction starting point. It is thought that the main reaction between milk of lime and carbon dioxide is a liquid phase reaction, in which carbon dioxide introduced into the reaction system first dissolves in water and then reacts with dissolved calcium hydroxide. Therefore, changes in the concentration of calcium hydroxide in the liquid phase accompanying the reaction can be immediately detected as changes in electrical conductivity and pH. It can be assumed that the above-mentioned first-order drop corresponds to a drop in the concentration of dissolved calcium hydroxide accompanying crystal nucleation of the reaction product. This primary drop recovers after a while as the suspended calcium hydroxide dissolves in the water and replenishes the dissolved calcium hydroxide. Further, quadratic depression is unique to basic calcium carbonate and does not appear when basic calcium carbonate is not present, and can be an indicator of the presence or absence of basic calcium carbonate formation. This quadratic drop corresponds to the change in concentration of dissolved calcium hydroxide as calcium hydroxide finishes converting to basic calcium carbonate. Furthermore, the third-order drop corresponds to the change in the concentration of basic calcium carbonate in the solution when the intermediately formed basic calcium carbonate finishes being converted to calcium carbonate by continuing carbonation.
本発明者らは、反応開始点より二次降下終了点
までに要した反応時間をt1とし、二次降下終了点
から三次降下終了点（ただし、PH曲線ではPH約10
の点）までに要した時間t2として、t2とt1との比
t2／t1を求めると、二次降下終了点までに塩基性
炭酸カルシウムがほぼ100％生成しているとき
は、その値は常に約0.45となり、一方炭酸カルシ
ウムが混じつているときは、その量に応じて最小
０までになることを見出した。 The present inventors set the reaction time required from the reaction start point to the end point of secondary descent as t 1 , and determined that the reaction time from the end point of secondary descent to the end point of tertiary descent (however, in the PH curve, the PH is approximately 10
As the time t 2 required to reach the point), the ratio of t 2 and t 1
When calculating t 2 / t 1 , if almost 100% of basic calcium carbonate has been produced by the end of the secondary descent, the value will always be approximately 0.45, whereas if calcium carbonate is mixed, the value will be approximately 0.45. It has been found that the value decreases to a minimum of 0 depending on the amount.
この知見により、板状塩基性炭酸カルシウムの
最適生成条件の探索が可能となつた。すなわち、
二酸化炭素又は二酸化炭素含有ガスの吹き込み速
度以外の条件、例えば反応開始温度、石灰乳濃
度、かきまぜ速度などを一定にし、t2／t1値が約
0.45となるようなガス吹き込み速度を系統的に探
索すればよい。このようにして最適なガス吹き込
み速度を見出せば、前と同様な条件で反応を行
い、二次降下終了点でガス吹き込みを止めると、
ほぼ純度100％の板状塩基性炭酸カルシウムを得
ることができる。なお二次降下進行中の各点で炭
酸化を中断しその後の電気伝導度変化を基に塩基
性炭酸カルシウムの生成が完了する点につき検討
した結果、この生成反応は二次降下終了点よりも
やゝ早い時点、第１図に於いて電気伝導度が約
6.0ms／cm位の時点、で完了しそれ以後もある時
間はなお二次降下が進行するという事が判つた。
従つて二酸化炭素ガスの吹き込みは電気伝導度が
約6.0ms／cmの値を示す時点で止めるのが最も好
ましいものであるが、実際上は二次降下開始から
同終了までの時間が短いので多少の収率の違いを
無視すれば二次降下進行中（終了点を含む）の任
意の点で二酸化炭素ガスの吹き込みを止めればよ
い。 This knowledge has made it possible to search for the optimal production conditions for plate-like basic calcium carbonate. That is,
Conditions other than the blowing rate of carbon dioxide or carbon dioxide-containing gas, such as reaction initiation temperature, milk of lime concentration, stirring speed, etc., are kept constant, and the t 2 /t 1 value is approximately
It is sufficient to systematically search for a gas blowing rate that gives a value of 0.45. Once the optimal gas injection rate is found in this way, the reaction is carried out under the same conditions as before, and the gas injection is stopped at the end of the secondary descent.
Platy basic calcium carbonate with almost 100% purity can be obtained. In addition, as a result of interrupting carbonation at each point during the secondary descent and examining the point at which the production of basic calcium carbonate is completed based on the subsequent change in electrical conductivity, it was found that this production reaction is longer than the point at which the secondary descent ends. At a very early point, the electrical conductivity in Figure 1 is approximately
It was found that the secondary descent was completed at about 6.0 ms/cm, and continued to progress for some time thereafter.
Therefore, it is most preferable to stop the injection of carbon dioxide gas when the electrical conductivity shows a value of approximately 6.0 ms/cm, but in reality, the time from the start of the secondary descent to the end is short, so it may take some time. Ignoring the difference in yield, it is sufficient to stop blowing carbon dioxide gas at any point during the progress of the secondary descent (including the end point).
この二酸化炭素又は二酸化炭素含有ガスの最適
吹き込み速度は、反応開始温度、原料の生石灰又
は消石灰の粒径と凝集状態、石灰乳濃度、かきま
ぜ速度、ガスの気泡径や反応装置形状などによつ
て異なる。これは塩基性炭酸カルシウムの結晶核
の生成が溶液中の溶存水酸化カルシウムや溶存二
酸化炭素の濃度、懸濁水酸化カルシウムの溶解速
度などとの微妙なバランスの上で起るためと考え
られる。ガス吹き込み速度が最適値より大きすぎ
ると、反応液の電気伝導度やPH値が急激に大きく
降下したのち再び急に回復するが、そのときゲル
化を経て糸状体と呼ばれるものを核生成し、板状
塩基性炭酸カルシウムは生成しない。また、ガス
吹き込み速度をあまり遅くすると、反応の不均等
化が起るためか炭酸カルシウムをも核生成し、塩
基性炭酸カルシウムと炭酸カルシウムとの混合物
が得られる。したがつて、本発明においては、二
酸化炭素又は二酸化炭素含有ガスの吹き込み速度
を前記のt2／t1値が0.40〜0.50の範囲、好ましく
は約0.45になるように調整することが重要であ
る。 The optimum blowing speed of carbon dioxide or carbon dioxide-containing gas varies depending on the reaction starting temperature, the particle size and aggregation state of the raw material quicklime or slaked lime, the concentration of milk of lime, the stirring speed, the gas bubble size, the shape of the reactor, etc. . This is thought to be because the formation of crystal nuclei of basic calcium carbonate occurs in a delicate balance with the concentration of dissolved calcium hydroxide and dissolved carbon dioxide in the solution, the dissolution rate of suspended calcium hydroxide, etc. If the gas blowing rate is too high than the optimum value, the electrical conductivity and PH value of the reaction solution will suddenly drop significantly and then suddenly recover again, but at that time, things called filaments will be nucleated through gelation. Platy basic calcium carbonate is not produced. Furthermore, if the gas blowing rate is too slow, calcium carbonate is also nucleated, probably due to uneven reaction, resulting in a mixture of basic calcium carbonate and calcium carbonate. Therefore, in the present invention, it is important to adjust the blowing rate of carbon dioxide or carbon dioxide-containing gas so that the t 2 /t 1 value is in the range of 0.40 to 0.50, preferably about 0.45. .
また、本発明においては、反応開始温度はガス
吹き込み速度とともに板状塩基性炭酸カルシウム
の生成にとつて極めて重要な要因であり、該塩基
性炭酸カルシウムを収率よく得るためには、反応
開始温度を20℃以下にする必要がある。好ましい
反応開始温度は10〜18℃の範囲である。その温度
が10℃未満でも板状塩基性炭酸カルシウムは生成
するが、石灰乳の冷却の点から経済的でない。一
方、20℃を超えて22℃位までは一部板状な塩基性
炭酸カルシウムも生成するが、他の形状の炭酸カ
ルシウムとの混合物となり、100％近い高純度の
塩基性炭酸カルシウムは得られない。また25℃以
上ではもはや板状塩基性炭酸カルシウムは生成し
ない。 In addition, in the present invention, the reaction start temperature is an extremely important factor for the production of plate-like basic calcium carbonate, as well as the gas blowing rate. must be kept below 20℃. A preferred reaction initiation temperature is in the range of 10 to 18°C. Platy basic calcium carbonate can be produced even if the temperature is below 10°C, but this is not economical from the standpoint of cooling the milk of lime. On the other hand, when the temperature exceeds 20°C and reaches around 22°C, some plate-like basic calcium carbonate is also formed, but it becomes a mixture with other forms of calcium carbonate, and basic calcium carbonate with nearly 100% purity cannot be obtained. do not have. Further, at temperatures above 25°C, plate-like basic calcium carbonate is no longer produced.
反応中は反応熱により反応液の温度が上昇する
ので、20℃近辺の反応開始温度で炭酸化する場合
は、少なくとも結晶核生成段階終了後、しばらく
は冷却する必要がある。 During the reaction, the temperature of the reaction solution increases due to the heat of reaction, so if carbonation is carried out at a reaction initiation temperature of around 20° C., it is necessary to cool the solution for at least a while after the completion of the crystal nucleation stage.
さらに、均一な反応を行うためには、石灰乳を
かきまぜながら二酸化炭素又は二酸化炭素含有ガ
スを吹き込む必要がある。このかきまぜ速度は
400〜1000rpm、好ましくは500〜700rpmの範囲
である。 Furthermore, in order to carry out a uniform reaction, it is necessary to blow carbon dioxide or carbon dioxide-containing gas into the milk of lime while stirring it. This stirring speed is
The range is 400-1000 rpm, preferably 500-700 rpm.
このようにして得られた板状塩基性炭酸カルシ
ウムは、例えば40℃以下の低温乾燥か、あるいは
噴霧乾燥やアルコール乾燥のような急速な乾燥法
によつて乾燥される。40℃以上の高温乾燥を行う
場合は、予め水切りを十分に行わないと、乾燥過
程中に高温水の作用によつて形状が変化すること
がある。この傾向は粒径の小さな塩基性炭酸カル
シウムにおいて特に著しい。 The plate-like basic calcium carbonate thus obtained is dried, for example, by low-temperature drying at 40° C. or lower, or by a rapid drying method such as spray drying or alcohol drying. When drying at a high temperature of 40°C or higher, if the water is not drained sufficiently in advance, the shape may change due to the action of the high temperature water during the drying process. This tendency is particularly remarkable in basic calcium carbonate, which has a small particle size.
本発明方法で得られる板状塩基性炭酸カルシウ
ムは、形状が板状であるため、塗料や製紙用塗被
顔料としての用途があり、また塩基性であること
から、塩基性触媒としての用途もある。さらに樹
脂混合複合建材の素材としての用途もあり、各種
プラスターへの充てん材、可塑剤としても利用し
うる。 The plate-like basic calcium carbonate obtained by the method of the present invention has a plate-like shape, so it can be used as a coating pigment for paints and paper manufacturing, and since it is basic, it can also be used as a basic catalyst. be. It can also be used as a material for resin-mixed composite building materials, and as a filler and plasticizer for various types of plaster.
次に実施例によつて本発明をさらに詳細に説明
する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
試薬沈降炭酸カルシウムを1000℃で10時間焼成
して得た生石灰56ｇを800c.c.の蒸留水とともに容
量１のジユサーに入れ、３分間強力な混合水和
を行う。このようにして得た石灰乳２バツチ分を
容量３の反応容器にとり、さらに蒸留水を加え
全量を２としたのち、室温で30分間、600rpm
でかきまぜながら熟成した。次にこの容器を10℃
の恒温水槽に移し、石灰乳温度が10℃になつてか
ら、600rpmでかきまぜながら濃度100％の二酸化
炭素ガスを２／分で吹き込み炭酸化反応を行つ
た。この間、反応過程を電気伝導度の変化でチエ
ツクし、t2／t1値を求めると0.45の値が得られ
た。次に同一条件で調製した石灰乳を同一条件で
炭酸化し、電気伝導度曲線の二次降下終了点でた
だちに炭酸ガスの吹き込みを止め、ろ過、脱水、
メチルアルコール洗浄を行つたのち、100℃で乾
燥し板状な塩基性炭酸カルシウム約184ｇを得
た。第２図にこの物質のＸ線回折の結果を示す。
比較のために消石灰と炭酸カルシウムの結果も示
している。この物質が結晶学的に消石灰や炭酸カ
ルシウムとは異なることは明らかである。第３図
に熱重量分折の結果を示す。３つの重量減少が認
められる。ガス分析の結果との減量は水蒸気
によりの減量は二酸化炭素によることが分つた
ので、各減量値から計算すると、この物質の示性
式は2CaCO3・Ca（OH）2・H2Oで表示できるこ
とが分つた。第４図にこの物質の走査電子顕微鏡
写真を示す。厚さ約0.05μｍ、直径約0.35μｍの
板状体であることが分る。Example 1 Reagent: 56 g of quicklime obtained by calcining precipitated calcium carbonate at 1000° C. for 10 hours is placed in a 1 capacity juicer together with 800 c.c. of distilled water, and vigorously mixed and hydrated for 3 minutes. Two batches of milk of lime thus obtained were placed in a reaction vessel with a capacity of 3, and distilled water was added to bring the total volume to 2, and the mixture was heated at room temperature for 30 minutes at 600 rpm.
It was aged while stirring. Next, heat this container to 10℃.
After the lime milk temperature reached 10°C, carbon dioxide gas with a concentration of 100% was blown in at 2/min while stirring at 600 rpm to perform a carbonation reaction. During this time, the reaction process was checked by changes in electrical conductivity, and the t 2 /t 1 value was found to be 0.45. Next, milk of lime prepared under the same conditions was carbonated under the same conditions, and the blowing of carbon dioxide gas was immediately stopped at the end of the quadratic descent of the electrical conductivity curve, followed by filtration, dehydration,
After washing with methyl alcohol, the mixture was dried at 100°C to obtain about 184 g of plate-like basic calcium carbonate. Figure 2 shows the results of X-ray diffraction of this substance.
The results for slaked lime and calcium carbonate are also shown for comparison. It is clear that this substance is crystallographically distinct from slaked lime and calcium carbonate. Figure 3 shows the results of thermogravimetric analysis. Three weight losses are observed. It was found that the weight loss due to water vapor was due to carbon dioxide, so when calculated from each weight loss value, the formula for this substance was expressed as 2CaCO 3 · Ca (OH) 2 · H 2 O. I found out what I can do. FIG. 4 shows a scanning electron micrograph of this material. It can be seen that it is a plate-shaped body with a thickness of about 0.05 μm and a diameter of about 0.35 μm.
実施例 ２
容量３の反応容器に20℃の地下水1.8をと
り、これに市販工業用生石灰粉（200メツシユ以
下）120ｇを入れ、室温下、600rpmでかきまぜら
がら30分間水和反応を行つた。次にこれに水を加
え全量２としたのち、18℃の恒温水槽に入れ、
恒温になつてから二酸化炭素濃度10容量％の空気
と二酸化炭素の混合ガスを毎分５の速度で吹き
込んだ。この間、電気伝導度で反応過程をチエツ
クし、t2／t1値を求めると0.45の値が得られた。
次に同一条件で調製した石灰乳に同一条件で10％
二酸化炭素含有ガスを吹き込み、約90分後に電気
伝導度曲線に現われた二次降下終了点でガス吹き
込みを止め、ただちに噴霧乾燥により板状な塩基
性炭酸カルシウム約196ｇを得た。第５図に得ら
れた塩基性炭酸カルシウムの走査電子顕微鏡写真
を示す。Example 2 1.8 g of groundwater at 20° C. was placed in a reaction vessel with a capacity of 3, and 120 g of commercially available industrial quicklime powder (200 mesh or less) was added thereto, and a hydration reaction was carried out at room temperature for 30 minutes while stirring at 600 rpm. Next, add water to make the total volume 2, then put it in a constant temperature water bath at 18℃.
After the temperature reached a constant temperature, a mixed gas of air and carbon dioxide with a carbon dioxide concentration of 10% by volume was blown in at a rate of 5 per minute. During this time, the reaction process was checked by electrical conductivity, and the t 2 /t 1 value was found to be 0.45.
Next, add 10% to lime milk prepared under the same conditions.
Carbon dioxide-containing gas was blown into the mixture, and after about 90 minutes, the gas injection was stopped at the end point of the secondary drop that appeared on the electrical conductivity curve, and about 196 g of plate-shaped basic calcium carbonate was immediately obtained by spray drying. FIG. 5 shows a scanning electron micrograph of the basic calcium carbonate obtained.
実施例 ３
石灰乳の調製を実施例２と同様にして行つたあ
と、水分調節をし全量２とした。次に容器を10
〜22℃範囲の所定温度の恒温水槽に入れ、恒温に
なつてから600rpmでかきまぜながら濃度100％の
二酸化炭素を所定速度（250，500，100c.c.／分）
で吹き込み炭酸化反応を行つた。この間、電気伝
導度とPHの連続測定を行い、それぞれの場合の
t2／t1値を求め、塩基性炭酸カルシウムの生成に
及ぼす反応開始温度の効果を調べた。その結果を
第６図に示す。この図から、反応開始温度と二酸
化炭素吹き込み速度が塩基性炭酸カルシウムの生
成に大きな影響を与えることが分る。Example 3 Milk of lime was prepared in the same manner as in Example 2, and then the moisture content was adjusted to a total amount of 2. Then add 10 containers
Place in a constant temperature water bath with a specified temperature in the range of ~22℃, and after reaching constant temperature, add carbon dioxide at a concentration of 100% at a specified rate (250, 500, 100 c.c./min) while stirring at 600 rpm.
The carbonation reaction was carried out by blowing with water. During this time, continuous measurements of electrical conductivity and PH were carried out, and in each case
The t 2 /t 1 value was determined and the effect of reaction initiation temperature on the production of basic calcium carbonate was investigated. The results are shown in FIG. This figure shows that the reaction initiation temperature and carbon dioxide blowing rate have a large effect on the production of basic calcium carbonate.
実施例 ４
３の反応容器に20℃の地下水1.8をとり、
これに市販工業用生石灰粉（200メツシユ以下）
を所定量入れ、室温下、600rpmでかきまぜなが
ら30分間水和反応を行つた。次に水分調節をし全
量２としたのち、18℃の恒温水槽に入れ恒温に
なつてから、600rpmでかきまぜながら濃度100％
の二酸化炭素を所定速度（250，500，1000c.c.／
分）で吹き込み炭酸化反応を行つた。この間、電
気伝導度とPHの連続測定を行いそれぞれのt2／t1
値を求め塩基性炭酸カルシウムの生成に及ぼす石
灰乳濃度の効果を調べた。その結果を第７図に示
す。Example 4 1.8 of groundwater at 20°C was placed in the reaction vessel of 3.
Add this to commercially available industrial quicklime powder (200 mesh or less)
A predetermined amount of was added, and a hydration reaction was carried out for 30 minutes at room temperature while stirring at 600 rpm. Next, adjust the moisture content to make the total amount 2, then put it in a constant temperature water tank at 18℃ and after it reaches a constant temperature, stir at 600 rpm until the concentration is 100%.
of carbon dioxide at a specified rate (250, 500, 1000 c.c./
The carbonation reaction was carried out by blowing at 100 min). During this time, continuous measurements of electrical conductivity and PH were performed at each t 2 /t 1
The effect of lime milk concentration on the production of basic calcium carbonate was determined. The results are shown in FIG.
実施例 ５
３の反応容器に20℃から80℃の所定温度に加
温した地下水1.8をとり、これに市販工業用生
石灰粉（200メツシユ以下）120ｇを入れ、
600rpmでかきまぜながら30分間水和反応を行つ
た。次に水分調節をし全量２としたのち、実施
例４と同様条件で炭酸化反応を行つた。この間、
電気伝導度とPHの連続測定を行い、それぞれt2／
t1値を求め、塩基性炭酸カルシウムの生成に及ぼ
す生石灰の水和温度差に由来する性状差の効果に
ついて検討した。その結果を第８図に示す。この
炭酸化条件では20〜40℃で水和した石灰からはガ
ス吹き込み速度の調節により塩基性炭酸カルシウ
ムを生成できるが、水和温度50℃以上ではガス吹
き込み速度を調節してもほぼ100％の塩基性炭酸
カルシウムは生成できないことが分る。Example 5 Take 1.8 g of groundwater heated to a predetermined temperature of 20°C to 80°C in the reaction vessel of 3, add 120 g of commercially available industrial quicklime powder (200 mesh or less),
The hydration reaction was carried out for 30 minutes while stirring at 600 rpm. Next, after adjusting the water content to a total amount of 2, a carbonation reaction was carried out under the same conditions as in Example 4. During this time,
Perform continuous measurements of electrical conductivity and PH, respectively at t2 /
The t 1 value was determined, and the effect of property differences resulting from differences in hydration temperature of quicklime on the formation of basic calcium carbonate was investigated. The results are shown in FIG. Under these carbonation conditions, basic calcium carbonate can be produced from lime hydrated at 20 to 40°C by adjusting the gas blowing rate, but at hydration temperatures of 50°C or higher, almost 100% is produced even if the gas blowing rate is adjusted. It turns out that basic calcium carbonate cannot be produced.
第１図は石灰乳の炭酸化反応過程における電気
伝導度曲線とPH曲線の１例、第２図は板状塩基性
炭酸カルシウム、消石灰及び炭酸カルシウム（カ
ルサイト）のＸ線回折図の１例、第３図は板状塩
基性炭酸カルシウムの熱重量分析における温度と
重量変化との関係を示すグラフの１例、第４図及
び第５図は、それぞれ実施例１及び２で得た板状
塩基性炭酸カルシウムの走査電子顕微鏡写真（倍
率２万倍）、第６図は板状塩基性炭酸カルシウム
の生成に及ぼす反応開始温度の効果をガス吹き込
み速度との関係で示すグラフの１例、第７図は板
状塩基性炭酸カルシウムの生成に及ぼす石灰乳濃
度の効果をガス吹き込み速度との関係で示すグラ
フの１例、及び第８図は板状塩基性炭酸カルシウ
ムの生成に及ぼす生石灰の水和温度の効果をガス
吹き込み速度との関係で示すグラフの１例であ
る。
Figure 1 is an example of the electrical conductivity curve and PH curve during the carbonation reaction process of milk of lime, and Figure 2 is an example of the X-ray diffraction diagram of plate-like basic calcium carbonate, slaked lime, and calcium carbonate (calcite). , FIG. 3 is an example of a graph showing the relationship between temperature and weight change in thermogravimetric analysis of plate-shaped basic calcium carbonate, and FIGS. 4 and 5 are graphs of plate-shaped basic calcium carbonate obtained in Examples 1 and 2, respectively. Scanning electron micrograph of basic calcium carbonate (20,000x magnification), Figure 6 is an example of a graph showing the effect of reaction initiation temperature on the formation of plate-like basic calcium carbonate in relation to gas blowing rate. Figure 7 is an example of a graph showing the effect of lime milk concentration on the formation of plate-like basic calcium carbonate in relation to the gas blowing rate, and Figure 8 shows the effect of quicklime water on the formation of plate-like basic calcium carbonate. This is an example of a graph showing the effect of sum temperature in relation to gas blowing speed.
Claims (1)
度４〜12ｇ／100c.c.の石灰乳の中へ、二酸化炭素
を一定速度で導入し、かきまぜながら反応させる
ことにより炭酸カルシウムを製造するに当り、反
応液の電気伝導度又はPHを継続的に測定し、反応
開始からその二次降下が終了するまでの時間をt1
とし、二次降下終了点から三次降下が終了するま
での時間をt2としたとき、t2／t1値が0.40〜0.50の
範囲になるように二酸化炭素の導入速度を制御
し、二次降下進行中の任意の点で二酸化炭素の導
入を停止することを特徴とする、組成式
2CaCO3・Ca（OH）2・nH2O，ｎ＝１〜1.5を有す
る板状塩基性炭酸カルシウムの製造方法。1 Calcium carbonate is produced by introducing carbon dioxide at a constant rate into milk of lime with a CaO concentration of 4 to 12 g/100 c.c., maintained at a temperature below 20°C, and reacting while stirring. Continuously measure the electrical conductivity or PH of the reaction solution, and measure the time from the start of the reaction until the end of the secondary drop, t 1
The introduction rate of carbon dioxide is controlled so that the t 2 / t 1 value is in the range of 0.40 to 0.50, and the time from the end of the secondary descent to the end of the tertiary descent is t 2 . compositional formula, characterized by stopping the introduction of carbon dioxide at any point during the descent progress
A method for producing plate-like basic calcium carbonate having 2CaCO 3 .Ca(OH) 2 .nH 2 O, n=1 to 1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17884283A JPS6071523A (en) | 1983-09-26 | 1983-09-26 | Plate-like basic calcium carbonate and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17884283A JPS6071523A (en) | 1983-09-26 | 1983-09-26 | Plate-like basic calcium carbonate and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6071523A JPS6071523A (en) | 1985-04-23 |
| JPS6232130B2 true JPS6232130B2 (en) | 1987-07-13 |
Family
ID=16055616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17884283A Granted JPS6071523A (en) | 1983-09-26 | 1983-09-26 | Plate-like basic calcium carbonate and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6071523A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007012441A2 (en) | 2005-07-26 | 2007-02-01 | Ertecee B.V. | Method for manufacturing a fire retardant composite and composite thus obtained |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055585B (en) * | 2017-06-21 | 2019-11-15 | 杭州杭钢三江矿业有限公司 | A kind of preparation method of flame retardant type major diameter flaky calcium carbonate |
-
1983
- 1983-09-26 JP JP17884283A patent/JPS6071523A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007012441A2 (en) | 2005-07-26 | 2007-02-01 | Ertecee B.V. | Method for manufacturing a fire retardant composite and composite thus obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6071523A (en) | 1985-04-23 |
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