JPH1036110A - Production of dicalcium silicate - Google Patents
Production of dicalcium silicateInfo
- Publication number
- JPH1036110A JPH1036110A JP19736996A JP19736996A JPH1036110A JP H1036110 A JPH1036110 A JP H1036110A JP 19736996 A JP19736996 A JP 19736996A JP 19736996 A JP19736996 A JP 19736996A JP H1036110 A JPH1036110 A JP H1036110A
- Authority
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- Japan
- Prior art keywords
- raw material
- water
- mixed
- silica
- calcareous
- 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.)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、セメント鉱物の一
種であり、接着剤や補修剤として使用される珪酸二カル
シウム（以下、Ｃ2 Ｓと称する。）を、安価に且つ短時
間で製造し得る方法に関する。BACKGROUND OF THE INVENTION The present invention is a kind of cement minerals, dicalcium silicate for use as an adhesive or a repair agent (hereinafter, referred to as C 2 S.) And prepared inexpensively and in a short time How to get.
【０００２】[0002]
【従来の技術】Ｃ2 Ｓは、ポルトランドセメントの重要
な構成化合物であり、セメントの長期強度と密接な関係
を持つビーライトの基本組成である。また、水和過程の
発熱が低い中庸熱ポルトランドセメントでは、Ｃ2 Ｓの
含有比率が高くなっている。 2. Description of the Related Art C 2 S is an important constituent compound of Portland cement, and is a basic composition of belite having a close relationship with the long-term strength of cement. Moreover, in the moderate heat Portland cement in which the heat generation during the hydration process is low, the content ratio of C 2 S is high.
【０００３】このような観点から、Ｃ2 Ｓはポルトラン
ドセメントの性質調節のための添加剤として使用され
る。また、Ｃ2 Ｓ自体が水硬性を有しているので、接着
剤や補修剤などとして単独に用いられることもある。[0003] From such a viewpoint, C 2 S is used as an additive for controlling the properties of Portland cement. Further, since C 2 S itself has hydraulic properties, it may be used alone as an adhesive or a repair agent.
【０００４】従来のＣ2 Ｓ製造プロセスは、１４００〜
１５００°Ｃの高温固相反応で合成したあと、さらに粉
砕を経て得るというものである。しかしながら、この方
法では粒子が焼結し、水和活性が劣る。また、高温焼成
と、後工程としての粉砕工程とが必要となるため、省エ
ネルギーの観点からも好ましくない。[0004] The conventional C 2 S manufacturing process is 1400
It is obtained by synthesizing by a high-temperature solid-state reaction at 1500 ° C. and further pulverizing. However, in this method, the particles are sintered and the hydration activity is poor. In addition, since high-temperature sintering and a pulverizing step as a subsequent step are required, it is not preferable from the viewpoint of energy saving.
【０００５】前記課題を解決する手段として、特願平６
−１１０４６４号（特開平７−２９１６１８号公報参
照）に記載のＣ2 Ｓの製造方法が提案されている。これ
を説明すると、まず、シリカ原料と消石灰とを、シリカ
原料に対する消石灰のモル比が１．８〜２．２の範囲と
なるように混合し、次いで当該混合物を、消石灰が反応
して完全に消失するまで乾式磨砕処理する。この乾式磨
砕処理により、上記混合物は、非晶質状化合物であるＣ
−Ｓ−Ｈゲルへ変化する。引き続き、生成されたＣ−Ｓ
−Ｈゲルを４００〜１０００°Ｃの温度で焼成すると、
Ｃ−Ｓ−Ｈゲルから水分子が離脱してＣ2 Ｓ粉末を得る
ことができる。As means for solving the above problems, Japanese Patent Application No.
C 2 S production method described in JP -110464 (see JP-A-7-291618) have been proposed. To explain this, first, a silica raw material and slaked lime are mixed such that the molar ratio of slaked lime to the silica raw material is in the range of 1.8 to 2.2, and then the mixture is completely reacted by slaked lime to react. Dry milling until disappearance. By this dry grinding treatment, the above-mentioned mixture is converted into an amorphous compound C
Changes to -SH gel. Subsequently, the generated CS
When the -H gel is fired at a temperature of 400 to 1000 ° C,
C-S-H water molecules from the gel can be obtained C 2 S powder disengaged.
【０００６】[0006]
【発明が解決しようとする課題】前記先願に記載される
Ｃ2 Ｓの製造方法（以下、先願方法と言う）では、シリ
カ原料と消石灰との混合物から非晶質のＣ−Ｓ−Ｈゲル
を生成するために、長時間（実施例によれば約９時間）
の乾式磨砕処理を行っている。このように前記先願方法
は、磨砕処理工程に多量のエネルギーと処理時間とを要
するという欠点を有している。In the method for producing C 2 S described in the prior application (hereinafter referred to as the prior application method), an amorphous C—S—H is prepared from a mixture of a silica raw material and slaked lime. Long time to produce gel (about 9 hours according to examples)
Of dry grinding. As described above, the prior application method has a disadvantage that a large amount of energy and processing time are required for the grinding process.
【０００７】[0007]
【課題を解決するための手段】本発明は、長時間の磨砕
処理工程を行わずにＣ2 Ｓを製造し得る方法を提供する
ものであって、その要旨とするところは、珪質原料と石
灰質原料とを、Ｃａ／Ｓi のモル比が１．８〜２．２の
範囲となるように調整して混合し、この混合原料に水を
加えて湿式細磨した後、これを５００〜１０００°Ｃの
温度で焼成することである。SUMMARY OF THE INVENTION The present invention provides a method for producing C 2 S without performing a prolonged grinding treatment step. And the calcareous raw material were adjusted and mixed so that the molar ratio of Ca / Si was in the range of 1.8 to 2.2. Water was added to the mixed raw material, and the mixture was wet-polished. Firing at a temperature of 1000 ° C.
【０００８】なお、本発明方法を実施するにあたり、前
記混合原料に加える水の量は、望ましくは、原料粉体の
単位表面積当たり１０〜５０ｍｇ／ｍ2 とする。In carrying out the method of the present invention, the amount of water added to the mixed raw material is desirably 10 to 50 mg / m 2 per unit surface area of the raw material powder.
【０００９】また本発明方法によれば、前記混合原料の
湿式細磨工程は、原料粒子表面に適当な厚みの水膜が形
成される程度で充分であり、短時間で済む。Further, according to the method of the present invention, the wet fine polishing step of the mixed raw material is sufficient if a water film having an appropriate thickness is formed on the surface of the raw material particles, and can be performed in a short time.
【００１０】[0010]
【発明の実施の形態】本発明に基づくＣ2 Ｓの製造工程
は、以下に説明するようにして実行される。はじめに、
珪質原料と石灰質原料とを、Ｃａ／Ｓi のモル比が１．
８〜２．２の範囲となるように混合する。Ｃａ／Ｓi の
モル比を上記範囲に限定する理由は、Ｃ2 Ｓの組成（Ｃ
ａ／Ｓi ＝２．０）にできるだけ近くして、製造される
Ｃ2 Ｓの純度を高めるためである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The manufacturing process of C 2 S according to the present invention is performed as described below. First,
The siliceous raw material and the calcareous raw material are mixed at a Ca / Si molar ratio of 1.
Mix so as to be in the range of 8 to 2.2. The reason for limiting the molar ratio of Ca / Si to the above range is that the composition of C 2 S (C
a / Si = 2.0) as much as possible to increase the purity of the produced C 2 S.
【００１１】珪質原料としては、珪砂，珪石のような結
晶質シリカ原料のほか、コロイダルシリカ，シリカゲ
ル，シリカゾル，シリカヒューム，ホワイトカーボンそ
の他市販の非晶質シリカ原料を用いることができる。な
お、シリカ純度がなるべく高いものが望ましい。As the siliceous raw material, besides crystalline silica raw materials such as silica sand and silica stone, colloidal silica, silica gel, silica sol, silica fume, white carbon and other commercially available amorphous silica raw materials can be used. It is desirable that the silica purity be as high as possible.
【００１２】一方、石灰質原料としては、生石灰，消石
灰，水酸化カルシウム，石灰石などを使用できる。特に
本発明では、前記先願方法において使用が好ましくない
とされている生石灰を、出発原料として用いることが可
能である。On the other hand, as the calcareous raw material, quick lime, slaked lime, calcium hydroxide, limestone and the like can be used. In particular, in the present invention, quicklime, which is considered to be unfavorable in the prior application method, can be used as a starting material.
【００１３】続いて、珪質原料と石灰質原料との混合物
に適量の水を加えて湿式細磨する。湿式細磨の手段は特
に制限されないが、粉砕容器に粉砕媒体を充填し、相互
の粉砕・摩擦エネルギーで粉砕，細磨を行う粉砕機全般
が利用可能である。粉砕機の例としては、転動ミル・振
動ミル・遠心ミル・アジテータミル等が挙げられる。Subsequently, an appropriate amount of water is added to a mixture of the siliceous raw material and the calcareous raw material, and the mixture is wet-finished. The means of wet polishing is not particularly limited, but any pulverizer capable of filling a pulverizing medium into a pulverizing container and performing pulverization and polishing by mutual pulverization / frictional energy can be used. Examples of the crusher include a rolling mill, a vibration mill, a centrifugal mill, and an agitator mill.
【００１４】また、混合原料に加える水の量は、混合し
た原料粉体の単位表面積当たり１０〜５０ｍｇ／ｍ2 と
するのが望ましい。１０ｍｇ／ｍ2 未満であると、原料
粒子の表面全体に均一な水膜を形成するのが困難にな
る。反対に５０ｍｇ／ｍ2 を越えると、水膜が厚くなり
過ぎ、珪質原料と石灰質原料との接触を妨げると共に、
後述するメカノケミカル的作用が水膜によって吸収され
るため、反応の進行が阻害される。The amount of water added to the mixed raw material is desirably 10 to 50 mg / m 2 per unit surface area of the mixed raw material powder. If it is less than 10 mg / m 2 , it becomes difficult to form a uniform water film on the entire surface of the raw material particles. On the other hand, if it exceeds 50 mg / m 2 , the water film becomes too thick, preventing the contact between the siliceous raw material and the calcareous raw material,
Since the mechanochemical action described below is absorbed by the water film, the progress of the reaction is inhibited.
【００１５】珪質原料粒子と石灰質原料粒子とに水を加
え湿式細磨処理を行うことにより、両原料粒子が均一に
混合されると共に、機械的応力によって通常の混合では
得られない極めて密な状態で両原料粒子を接触させるこ
とが可能となる。また、湿式細磨処理に基づく機械的応
力によって、両原料粒子間にメカノケミカル効果が作用
すると考えられる。本効果は、外部から受けた機械的エ
ネルギーが、物質の歪みや構造欠陥等の形で蓄積され、
化学的反応性を高める効果である。By adding water to the siliceous raw material particles and the calcareous raw material particles and performing a wet polishing treatment, the raw material particles are uniformly mixed, and extremely dense, which cannot be obtained by ordinary mixing due to mechanical stress. In this state, both raw material particles can be brought into contact. In addition, it is considered that a mechanochemical effect acts between both raw material particles due to the mechanical stress based on the wet fine polishing treatment. This effect is due to the fact that mechanical energy received from the outside is accumulated in the form of material distortion, structural defects, etc.
This is an effect of increasing chemical reactivity.
【００１６】本発明では原料混合物に適量の水を加え、
湿式で細磨処理を行う結果、メカノケミカル効果が高ま
り、化学的反応性が高まる。水の存在によりメカノケミ
カル反応が促進される理由の詳細は明らかでないが、乾
式細磨の場合には機械的応力が主に粒子表面にしか作用
しないのに対し、水を添加したことにより適当な厚みの
水膜が原料粒子表面に形成され、この水膜を介して機械
的応力が原料粒子内部にまで影響するためと推測され
る。In the present invention, an appropriate amount of water is added to the raw material mixture,
As a result of the wet polishing, the mechanochemical effect is enhanced and the chemical reactivity is enhanced. The reason why the mechanochemical reaction is accelerated by the presence of water is not clear, but in the case of dry polishing, mechanical stress mainly acts only on the particle surface. It is presumed that a water film having a thickness is formed on the surface of the raw material particles, and mechanical stress affects the inside of the raw material particles through the water film.
【００１７】なお、本発明では、水の添加によりメカノ
ケミカル反応が促進されるので、細磨処理工程を短時間
（通常３０分以内）とすることができる。但し、原料粉
体の性状などに応じて、細磨処理時間を適宜延長するこ
とを妨げない。In the present invention, since the mechanochemical reaction is promoted by the addition of water, the polishing step can be shortened (usually within 30 minutes). However, it does not prevent the polishing time from being appropriately extended according to the properties of the raw material powder.
【００１８】次いで、湿式細磨処理を終えた混合原料
を、５００〜１０００°Ｃの温度で焼成すると、中間の
Ｃ−Ｓ−Ｈをほとんど経ることなく、Ｃ2 Ｓが製造され
る。Next, when the mixed raw material after the wet polishing treatment is fired at a temperature of 500 to 1000 ° C., C 2 S is produced with almost no intermediate CSH.
【００１９】このように、本発明に規定する湿式細磨処
理によって得られる混合粉末は、従来の固相反応ではＣ
2 Ｓ単相を得ることの困難な５００〜１０００°Ｃとい
う低温での焼成によって、また、前記先願方法では必要
であった長時間の細磨処理を要することなく、Ｃ2 Ｓ単
相製品の合成が可能である。As described above, the mixed powder obtained by the wet polishing treatment specified in the present invention is a C powder in the conventional solid phase reaction.
By sintering at a low temperature of 500 to 1000 ° C., at which it is difficult to obtain a 2 S single phase, and without the need for a long-time fine polishing treatment required in the prior application method, a C 2 S single phase product is obtained. Can be synthesized.
【００２０】[0020]
【実施例】珪質原料及び石灰質原料として非晶質シリカ
（Ｓi Ｏ2 ）と生石灰（ＣａＯ）とを用い、これらの混
合原料から、どのような条件であればＣ2 Ｓが合成され
るかを調べた。実験は、非晶質シリカと生石灰とを、Ｃ
ａ／Ｓi のモル比が１．８〜２．２に調整した混合原料
を用い、水の添加量・湿式細磨時間・焼成温度をさまざ
まに設定して、焼成後に得られる物質の相組成を調べた
ものである。EXAMPLE Amorphous silica (SiO 2 ) and quicklime (CaO) were used as siliceous and calcareous raw materials, and under what conditions C 2 S was synthesized from these mixed raw materials. Was examined. In the experiment, amorphous silica and quicklime were converted to C
Using a mixed raw material in which the molar ratio of a / Si was adjusted to 1.8 to 2.2, the amount of water added, the wet polishing time and the firing temperature were variously set, and the phase composition of the substance obtained after firing was adjusted. It has been examined.
【００２１】実験手順の概略を説明すると、まず非晶質
シリカと生石灰とを、Ｃａ／Ｓi のモル比が１．８、
２．０又は２．２となるように調整して混合し、この混
合原料に表１に示す分量の水を添加したのち、振動ミル
によって所定時間だけ湿式細磨を行い、引き続き電気炉
にて、１０°Ｃ／分の昇温速度、保持時間６０分間の焼
成を行う。なお表１において、水の添加量は、原料粉体
の表面積１ｍ2 当たりの重量（ｍｇ）を表したものであ
る。実験結果を表１に示す。なお、表１中の各略号は、
以下の相を意味する。Ｌ＝ＣａＯ Ｐ＝Ｃａ（ＯＨ）2
Ｑ＝ＳｉＯ2 C２S ＝２ＣａＯ・ＳｉＯ2 C S ＝ＣａＯ・ＳｉＯ２ The outline of the experimental procedure is as follows. First, amorphous silica and quicklime are mixed at a Ca / Si molar ratio of 1.8.
The mixture was adjusted to 2.0 or 2.2 and mixed. After adding the amount of water shown in Table 1 to the mixed raw material, the mixture was wet-polished for a predetermined period of time by a vibration mill, and then continuously heated in an electric furnace. The baking is performed at a heating rate of 10 ° C./min and a holding time of 60 minutes. In Table 1, the amount of water added represents the weight (mg) per 1 m 2 of the surface area of the raw material powder. Table 1 shows the experimental results. In addition, each abbreviation in Table 1 is:
The following phases are meant. L = CaO P = Ca (OH) 2
Q = SiO 2 C 2 S = 2CaO · SiO 2 CS = CaO · SiO 2
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１から分かるように、本発明方法に従っ
て、水を添加して湿式細磨を行ったのち、所定範囲の温
度で焼成したものは、単相のＣ２ Ｓ相が生成される。As can be seen from Table 1, according to the method of the present invention, a single-phase C 2 S phase is formed in the case where water is added and wet polishing is performed, and then firing is performed at a predetermined temperature range.
【００２４】これに対し、水を原料粉体に添加しなかっ
たものは、細磨工程を長時間行い、且つ高温焼成した場
合であっても、Ｃ2 Ｓ相と他の相との混成相となり、単
相のＣ2 Ｓ相を得ることができない。On the other hand, in the case where water was not added to the raw material powder, the mixed phase of the C 2 S phase and other phases was obtained even when the fine polishing step was performed for a long time and fired at a high temperature. And a single-phase C 2 S phase cannot be obtained.
【００２５】また、水を原料に加えたものであっても、
細磨工程を省略した場合（細磨時間＝０分）には、Ｃ2
Ｓ相が生成しないか、又は仮にＣ2 Ｓ相が生成したとし
ても他の相との混成相となる。焼成温度が低い（４００
°Ｃ）場合にはＣ2 Ｓ相は生成されない。Further, even when water is added to the raw material,
When the fine polishing step is omitted (fine polishing time = 0 minutes), C 2
No S phase is formed, or even if a C 2 S phase is formed, it becomes a hybrid phase with other phases. Low firing temperature (400
° C), no C 2 S phase is produced.
【００２６】このように、本発明が採用する設定条件か
らはずれた製造方法では、目的とする単相のＣ2 Ｓを得
るのが困難となることが表１より理解される。As can be seen from Table 1, it is difficult to obtain the desired single-phase C 2 S in the manufacturing method deviating from the set conditions adopted by the present invention.
【００２７】[0027]
【発明の効果】本発明方法によれば、珪質原料と石灰質
原料との混合物との細磨時間を従来よりもはるかに短時
間で済ますことができ、しかも焼成温度を比較的低く設
定することができる。依って、Ｃ2 Ｓの製造に要するエ
ネルギーコストを格段に引き下げることができると共
に、製造時間の短縮化を図ることができる。According to the method of the present invention, the polishing time for the mixture of the siliceous raw material and the calcareous raw material can be shortened much shorter than before, and the firing temperature can be set relatively low. Can be. Accordingly, the energy cost required for manufacturing C 2 S can be significantly reduced, and the manufacturing time can be shortened.
Claims (3)
のモル比が１．８〜２．２の範囲となるように調整して
混合し、この混合原料に水を加えて湿式細磨した後、こ
れを５００〜１０００°Ｃの温度で焼成することを特徴
とする珪酸二カルシウムの製造方法。1. A method according to claim 1, wherein the siliceous raw material and the calcareous raw material are separated by Ca / Si.
The mixture is adjusted so that the molar ratio of the mixture is in the range of 1.8 to 2.2, mixed with water, wet-polished by adding water, and then fired at a temperature of 500 to 1000 ° C. A method for producing dicalcium silicate, comprising:
体の単位表面積当たり１０〜５０ｍｇ／ｍ2 とする請求
項１に記載の珪酸二カルシウムの製造方法。2. The method for producing dicalcium silicate according to claim 1, wherein the amount of water added to the mixed raw material is 10 to 50 mg / m 2 per unit surface area of the raw material powder.
内とする請求項１又は２に記載の珪酸二カルシウムの製
造方法。3. The method for producing dicalcium silicate according to claim 1, wherein the wet polishing time of the mixed raw material is set to 30 minutes or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19736996A JP3750001B2 (en) | 1996-07-26 | 1996-07-26 | Method for producing dicalcium silicate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19736996A JP3750001B2 (en) | 1996-07-26 | 1996-07-26 | Method for producing dicalcium silicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1036110A true JPH1036110A (en) | 1998-02-10 |
| JP3750001B2 JP3750001B2 (en) | 2006-03-01 |
Family
ID=16373359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19736996A Expired - Fee Related JP3750001B2 (en) | 1996-07-26 | 1996-07-26 | Method for producing dicalcium silicate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3750001B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012105102A1 (en) * | 2011-02-03 | 2012-08-09 | 電気化学工業株式会社 | PROCESS FOR PRODUCING β-2CAO·SIO2 |
| WO2013027704A1 (en) * | 2011-08-25 | 2013-02-28 | 電気化学工業株式会社 | METHOD FOR PRODUCING γ-2CaO·SiO2 |
| CN103209925A (en) * | 2010-11-11 | 2013-07-17 | 电气化学工业株式会社 | Production method for beta-2CaOSiO2 |
| CN106904846A (en) * | 2017-02-28 | 2017-06-30 | 安徽珍珠水泥集团股份有限公司 | A kind of clinker and preparation method thereof |
-
1996
- 1996-07-26 JP JP19736996A patent/JP3750001B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103209925A (en) * | 2010-11-11 | 2013-07-17 | 电气化学工业株式会社 | Production method for beta-2CaOSiO2 |
| WO2012105102A1 (en) * | 2011-02-03 | 2012-08-09 | 電気化学工業株式会社 | PROCESS FOR PRODUCING β-2CAO·SIO2 |
| JPWO2012105102A1 (en) * | 2011-02-03 | 2014-07-03 | 電気化学工業株式会社 | Method for producing β-2CaO · SiO 2 |
| JP5867734B2 (en) * | 2011-02-03 | 2016-02-24 | デンカ株式会社 | Method for producing β-2CaO · SiO 2 |
| WO2013027704A1 (en) * | 2011-08-25 | 2013-02-28 | 電気化学工業株式会社 | METHOD FOR PRODUCING γ-2CaO·SiO2 |
| CN103764562A (en) * | 2011-08-25 | 2014-04-30 | 电气化学工业株式会社 | Method for producing gamma-2CaO*SiO2 |
| JPWO2013027704A1 (en) * | 2011-08-25 | 2015-03-19 | 電気化学工業株式会社 | Method for producing γ-2CaO · SiO 2 |
| CN106904846A (en) * | 2017-02-28 | 2017-06-30 | 安徽珍珠水泥集团股份有限公司 | A kind of clinker and preparation method thereof |
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|---|---|
| JP3750001B2 (en) | 2006-03-01 |
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