JP2003300725A - Manufacture of highly activated slaked lime - Google Patents
Manufacture of highly activated slaked limeInfo
- Publication number
- JP2003300725A JP2003300725A JP2002099779A JP2002099779A JP2003300725A JP 2003300725 A JP2003300725 A JP 2003300725A JP 2002099779 A JP2002099779 A JP 2002099779A JP 2002099779 A JP2002099779 A JP 2002099779A JP 2003300725 A JP2003300725 A JP 2003300725A
- Authority
- JP
- Japan
- Prior art keywords
- slaked lime
- mass
- water
- amount
- digestion
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高活性消石灰と、
その製造方法に関する。TECHNICAL FIELD The present invention relates to a highly active slaked lime,
The manufacturing method is related.
【０００２】[0002]
【従来の技術】消石灰（水酸化カルシウム：Ｃａ（Ｏ
Ｈ）2）の工業的な製法としては、生石灰（酸化カルシ
ウム：ＣａＯ）を過剰量の水と接触させることによっ
て、消化を行ない、同時に、あるいはその後に、消化に
より発生する熱を利用して、過剰の水を蒸発させて乾燥
を行ない、含水率が１質量％以下の粉末状の消石灰製品
を製造する方法が一般的である。この消石灰の製法は通
常、「乾式法」と呼ばれている。この乾式法は、消化に
より生成する含水消石灰の乾燥に、外部からの熱エネル
ギーの補給を必要としないため、製造コストの面から
は、有利な方法である。しかしながら、この乾式法で得
られる消石灰粉末は、比表面積が小さいため、反応性が
低く、たとえば、ごみ焼却炉から排出される排ガスの処
理（酸性物質の除去）などに用いる消石灰としては不利
になる。2. Description of the Related Art Slaked lime (calcium hydroxide: Ca (O
H) 2 ) is industrially produced by contacting quick lime (calcium oxide: CaO) with an excess amount of water to perform digestion, and at the same time or after that, utilizing heat generated by digestion, A general method is to evaporate excess water and perform drying to produce a powdered slaked lime product having a water content of 1% by mass or less. This method of producing slaked lime is usually called "dry method". This dry method is an advantageous method from the viewpoint of manufacturing cost because it does not require external heat energy supply to dry the hydrous slaked lime produced by digestion. However, since the slaked lime powder obtained by this dry method has a small specific surface area, it has low reactivity, and is disadvantageous as slaked lime used for, for example, treating exhaust gas discharged from a refuse incinerator (removal of acidic substances). .
【０００３】乾式法により得られる消石灰の比表面積を
高めるための研究は既に多くの研究者によって行なわれ
ており、その結果、生石灰の消化に用いる水（消化水）
に、オキシカルボン酸、オキシカルボン酸塩、糖類、一
価アルコール、多価アルコール（エチレングリコール、
プロピレングリコール、グリセリンなど）、非イオン性
界面活性剤、アルコールアミン、コハク酸、金属コハク
酸塩、リグニンスルホン酸塩、一級アミン、あるいは二
級アミンなどの水溶性化合物を添加して、これらの水溶
性化合物の存在下に消化反応を進行させる方法が開発さ
れている。これらの水溶性化合物（すなわち、比表面積
向上剤）を添加した消化水を利用することにより、従来
の通常の水を消化水と用いる方法と比較すると、顕著に
高い比表面積を持つ消石灰を得ることができるようにな
っている。しかしながら、これらの比表面積向上剤を用
いた場合でも、達成される消石灰の比表面積（ＢＥＴ比
表面積）は通常、４０ｍ2／ｇ程度であり、現在、さま
ざまな用途にて求められている比表面積５０ｍ2／ｇ以
上の消石灰製品を得ることは容易ではない。なお、上記
の比表面積向上剤のうちで、プロピレングリコールを消
化水に５質量％添加して、消化を実施することによっ
て、比表面積が５０ｍ2／ｇ以上の消石灰を得たと云う
報告はあるが、生石灰からの消化による消石灰の製造に
際して、このような多量の比表面積向上剤を用いること
は、その製造コストを大きく上昇させることになるた
め、実用的には有利ではない。Many researchers have already conducted researches for increasing the specific surface area of slaked lime obtained by the dry method, and as a result, water used for digesting quicklime (digested water)
Oxycarboxylic acid, oxycarboxylic acid salt, saccharide, monohydric alcohol, polyhydric alcohol (ethylene glycol,
Propylene glycol, glycerin, etc.), nonionic surfactants, alcohol amines, succinic acid, metal succinates, lignin sulfonates, primary amines, or secondary amines. A method has been developed in which the digestive reaction proceeds in the presence of a volatile compound. By using digested water with addition of these water-soluble compounds (that is, specific surface area improver), slaked lime with a remarkably high specific surface area can be obtained as compared with the conventional method of using ordinary water with digested water. You can do it. However, even when these specific surface area improvers are used, the specific surface area of slaked lime (BET specific surface area) that is achieved is usually about 40 m 2 / g, and the specific surface area currently required for various applications is high. It is not easy to obtain a slaked lime product of 50 m 2 / g or more. Among the above-mentioned specific surface area improvers, it is reported that propylene glycol was added to digested water in an amount of 5% by mass and digested to obtain slaked lime having a specific surface area of 50 m 2 / g or more. In the production of slaked lime by digestion from quick lime, it is not practically advantageous to use such a large amount of specific surface area improver because the production cost thereof is greatly increased.
【０００４】上記の公知技術を記載した刊行物の例とし
ては、次のようなものがある。特開平９−２７８４３５
号公報には、生石灰の消化による消石灰の製造に際し
て、消化水として、水にオキシカルボン酸、オキシカル
ボン酸塩、糖類、エチレングリコール類、エタノールア
ミン類、グリセリン、コハク酸、金属コハク酸塩、ある
いはリグニンスルホン酸塩を、生石灰の量に対して０．
１〜１０質量％添加したものを用いることにより、微粒
で比表面積が大きく、反応性が改善された消石灰を得る
方法が記載されている。ただし、この方法で得られる消
石灰は、記載されている実施例によれば、その比表面積
が約２３〜３６ｍ2／ｇの範囲のものであって、最近求
められている比表面積が５０ｍ2／ｇ以上の消石灰には
遥かに及ばない。The following are examples of publications describing the above-mentioned known techniques. JP-A-9-278435
In the publication, in the production of slaked lime by digesting quick lime, as digestion water, oxycarboxylic acid, oxycarboxylic acid salt, sugar, ethylene glycols, ethanolamines, glycerin, succinic acid, metal succinate, or The lignin sulfonate was added in an amount of 0.
A method for obtaining slaked lime with fine particles having a large specific surface area and improved reactivity is described by using 1 to 10% by mass added. However, the slaked lime obtained by this method has a specific surface area in the range of about 23 to 36 m 2 / g according to the described examples, and has a recently required specific surface area of 50 m 2 / g. Much less than slaked lime over g.
【０００５】特開平１０−２５１１２号公報には、生石
灰の消化による消石灰の製造に際して、消化水として、
水に一価アルコール類、二価アルコール類、三価アルコ
ール類、一級アミン類、あるいは二級アミン類を代表的
には０．１〜２０質量％添加したものを用いることによ
り、燃焼排ガス中に含まれる有害酸性成分の除去に有用
な、比表面積が大きく、反応性が改善された消石灰を得
る方法が記載されている。そして、この方法を利用する
ことにより、比表面積が２８〜６０ｍ2／ｇの消石灰が
得られる旨の記載がある。そして、明細書に実際に記載
されている実施例によれば、例えば、生石灰から計算さ
れる消石灰の生成量に対して５質量％のプロピレングリ
コールを用いると、その比表面積が５６．０ｍ2／ｇの
消石灰が得られるとされている。Japanese Unexamined Patent Publication No. 10-25112 discloses that when slaked lime is produced by digesting quick lime, it is used as digested water.
By using monohydric alcohols, dihydric alcohols, trihydric alcohols, primary amines, or secondary amines typically added to water in an amount of 0.1 to 20 mass%, A method for obtaining slaked lime having a large specific surface area and improved reactivity, which is useful for removing harmful acidic components contained therein, is described. Then, there is a description that slaked lime having a specific surface area of 28 to 60 m 2 / g can be obtained by utilizing this method. Then, according to the examples actually described in the specification, for example, when 5% by mass of propylene glycol is used with respect to the production amount of slaked lime calculated from quick lime, the specific surface area thereof is 56.0 m 2 / It is said that g of slaked lime can be obtained.
【０００６】しかしながら、本来安価な製品である消石
灰の製造に際して、その生成消石灰に対して、５質量％
という多量の比表面積向上剤を用いることは、その消石
灰の製造コストを考慮すると明らかに不利となる。However, in the production of slaked lime, which is originally an inexpensive product, 5% by mass based on the produced slaked lime.
The use of such a large amount of specific surface area improver is obviously disadvantageous in view of the production cost of the slaked lime.
【０００７】[0007]
【発明が解決しようとする課題】本発明の課題は、生石
灰の消化による消石灰の製造に際して、あまり多量の比
表面積向上剤を用いることなく、現時点で目標とされて
いる５０ｍ2／ｇ以上の比表面積を有する高活性消石灰
を製造する技術を提供することにある。An object of the present invention is to produce a slaked lime by digesting quick lime without using a large amount of a specific surface area improver, and to obtain a ratio of 50 m 2 / g or more which is currently targeted. It is to provide a technique for producing highly active slaked lime having a surface area.
【０００８】[0008]
【課題を解決するための手段】本発明者は、生石灰の消
化による消石灰の製造の際に用いる比表面積向上剤の特
性を調べ、さらにその比表面積向上剤と、消化反応後の
含水消石灰の処理方法との関係を詳細に研究した。その
結果、消化反応後の含水消石灰を、その含水量が５〜３
０質量％の範囲にある間に、消化装置から一旦取り出
し、乾燥器にて乾燥させる方法を利用すると、比表面積
向上剤としてジエチレングリコールを用いる場合には、
その消化水への添加量が０．８〜３．０質量％程度の量
であれば、所望の比表面積５０ｍ2／ｇ以上の高活性の
消石灰が得られることを見い出し、本発明を完成した。
また、上記の消化工程と乾燥工程との間に、水分の若干
の除去を伴う熟成工程を実施することにより、乾燥のた
めに必要な外部熱エネルギーの付加量を低減しながら、
比表面積が５０ｍ2／ｇ以上の高活性消石灰が、安定に
得られることを見い出した。The present inventor investigated the characteristics of a specific surface area improver used in the production of slaked lime by digesting quicklime, and further treated the specific surface area improver and hydrous slaked lime after digestion reaction. The relationship with the method was studied in detail. As a result, the water content of the hydrous slaked lime after the digestion reaction was 5 to 3
When the method of taking out once from the digester and drying in a dryer is used while it is in the range of 0% by mass, when diethylene glycol is used as a specific surface area improver,
It was found that a highly active slaked lime having a desired specific surface area of 50 m 2 / g or more can be obtained when the amount added to the digested water is about 0.8 to 3.0% by mass, and the present invention was completed. .
In addition, by performing an aging step involving some removal of water between the above-mentioned digestion step and drying step, while reducing the amount of external heat energy required for drying,
It has been found that highly active slaked lime having a specific surface area of 50 m 2 / g or more can be stably obtained.
【０００９】従って、本発明は、粉末状または粒状の生
石灰を、その消化後に生成する消石灰の量に対して０．
８〜３質量％（好ましくは、１．０〜２．５質量％、さ
らに好ましくは、１．１〜２．０質量％）に相当する量
のジエチレングリコールを含む、消化に必要な理論量の
１．５質量倍以上の水に接触させることにより、消化を
行ない、含水率が５〜３０質量％（好ましくは、１０〜
２５質量％、さらに好ましくは１５〜２０質量％）の含
水消石灰を得た後、該含水消石灰を乾燥することを特徴
とする、好ましくは、含水率が３質量％以下、特に１質
量％以下であって、ＢＥＴ比表面積が５０ｍ2／ｇ以上
（特に、５０〜６０ｍ2／ｇの範囲、さらには、５１〜
５５ｍ2／ｇの範囲）の高活性消石灰の製造方法にあ
る。Therefore, according to the present invention, powdery or granular quicklime is added to the amount of slaked lime produced after its digestion to 0.
1 to 3 of the theoretical amount necessary for digestion, containing an amount of diethylene glycol corresponding to 8 to 3% by mass (preferably 1.0 to 2.5% by mass, more preferably 1.1 to 2.0% by mass). The water content is 5 to 30% by mass (preferably, 10 to 10% by mass) by bringing it into contact with water in an amount of 0.5 mass times or more.
25% by mass, more preferably 15 to 20% by mass) is obtained, and then the hydrated slaked lime is dried, preferably, the water content is 3% by mass or less, particularly 1% by mass or less. there are, BET specific surface area of 50 m 2 / g or more (in particular, the range of 50 to 60 m 2 / g, further, 51 to
55 m 2 / g range).
【００１０】本発明はまた、粉末状または粒状の生石灰
を、その消化後に生成する消石灰の量に対して０．８〜
３質量％（好ましくは、１．０〜２．５質量％、さらに
好ましくは、１．１〜２．０質量％）に相当する量のジ
エチレングリコールを含む、消化に必要な理論量の１．
５質量倍以上の水に接触させることにより、消化を行な
い、含水率が１０〜３０質量％（好ましくは、１０〜２
５質量％、さらに好ましくは、１５〜２０質量％）の含
水消石灰を得た後、該含水消石灰を熟成することによっ
て、含水消石灰よりも含水率が３〜１５質量％（好まし
くは、３〜１２質量％、さらに好ましくは５〜１０質量
％）の範囲で低下した低含水消石灰を得て、次いで、該
低含水消石灰を乾燥することを特徴とする、好ましく
は、含水率が３質量％以下、特に１質量％以下であっ
て、ＢＥＴ比表面積が５０ｍ2／ｇ以上（特に、５０〜
６０ｍ2／ｇの範囲、さらには、５１〜５５ｍ2／ｇの範
囲）の高活性消石灰の製造方法にもある。The present invention also provides a powdery or granular quicklime to 0.8 to the amount of slaked lime produced after its digestion.
1. The theoretical amount of 1. necessary for digestion, which contains diethylene glycol in an amount corresponding to 3% by mass (preferably 1.0 to 2.5% by mass, more preferably 1.1 to 2.0% by mass).
Digestion is carried out by contacting with 5 times by mass or more of water, and the water content is 10 to 30% by mass (preferably 10 to 2%).
5% by mass, more preferably 15 to 20% by mass) of hydrous slaked lime is obtained, and then the hydrated slaked lime is aged to have a water content of 3 to 15% by mass (preferably 3 to 12%). % By mass, more preferably 5 to 10% by mass) to obtain a low hydrous slaked lime reduced, then characterized by drying the low hydrous slaked lime, preferably, the water content is 3% by mass or less, In particular, it is 1 mass% or less and the BET specific surface area is 50 m 2 / g or more (in particular, 50 to 2
60 m 2 / g range, further also provides the method for producing a highly active slaked lime 51~55m range 2 / g).
【００１１】本発明はまた、好ましくは、含水率が３質
量％以下、特に含水率が１質量％以下であって、３質量
％以下（好ましくは、０．８〜３質量％、好ましくは、
１．０〜２．５質量％、さらに好ましくは、１．１〜
２．０質量％の範囲）の量のジエチレングリコールを含
み、かつＢＥＴ比表面積が５０〜６０ｍ2／ｇ（特に、
５１〜５５ｍ2／ｇ）の範囲にある高活性消石灰にもあ
る。The present invention also preferably has a water content of 3% by mass or less, particularly 1% by mass or less, and 3% by mass or less (preferably 0.8 to 3% by mass, preferably,
1.0-2.5% by mass, more preferably 1.1-
And a BET specific surface area of 50 to 60 m 2 / g (particularly, 2.0% by mass).
It is also found in highly active slaked lime in the range of 51-55 m 2 / g).
【００１２】[0012]
【発明の実施の形態】本発明は、比表面積向上剤として
ジエチレングリコールを少量用い、かつ消化反応が進行
した後、水分を一定範囲の量で含有する生成消石灰を取
り出し、これを乾燥機を利用して乾燥することにより、
消石灰製品を製造することを特徴としている。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a small amount of diethylene glycol is used as a specific surface area improver, and after the digestion reaction has proceeded, the produced slaked lime containing water in a certain range is taken out and dried using a drier. By drying
It is characterized by manufacturing slaked lime products.
【００１３】原料として用いる生石灰は、通常の消石灰
の製造のために用いられる生石灰と基本的な相違はな
い。すなわち、一般的には、通常の焼成生石灰の塊状物
を適宜粉砕して、粉末状もしくは粒状としたのち、これ
を原料生石灰として用いる。The quicklime used as a raw material is basically the same as the quicklime used for the production of ordinary slaked lime. That is, generally, an ordinary lump of calcined quick lime is appropriately crushed into powder or granules, and this is used as the raw quick lime.
【００１４】生石灰の消化のために用いる水（消化水）
の量も、生石灰の使用量に対して、その消化のために必
要な水の理論量の約１．５倍以上であって（通常は約５
倍以下、いずれも質量倍）、この点についても、従来か
ら知られている生石灰の消化条件とは相違がない。Water used for digestion of quicklime (digested water)
The amount of water used is about 1.5 times the theoretical amount of water required for digesting the amount of quicklime (usually about 5%).
This is no different from the conventionally known quick lime digestion conditions.
【００１５】本発明で用いる消化水は、少量（消化後に
生成する消石灰の量に対して０．８〜３質量％、好まし
くは、１．０〜２．５質量％、さらに好ましくは、１．
１〜２．０質量％に相当する量）のジエチレングリコー
ルを含む。所望により、このジエチレングリコールに共
に、他の比表面積向上剤を併用してもよい。ジエチレン
グリコールは水との混和性にも優れており、容易に消化
水の調製ができる。なお、消化水は、生石灰と接触する
前に、ジエチレングリコールが添加されていることが好
ましい。The amount of digested water used in the present invention is small (0.8 to 3% by mass, preferably 1.0 to 2.5% by mass, and more preferably 1.
1 to 2.0% by mass) of diethylene glycol. If desired, other specific surface area improver may be used together with this diethylene glycol. Diethylene glycol has excellent miscibility with water, and digested water can be easily prepared. In addition, it is preferable that diethylene glycol is added to the digested water before it comes into contact with quicklime.
【００１６】消化反応は、通常は、混合機を用いて、攪
拌下にて実施する。攪拌は比較的高速で実施することが
好ましい。The digestion reaction is usually carried out with stirring using a mixer. The stirring is preferably performed at a relatively high speed.
【００１７】混合機内で消化反応が充分に進み、生石灰
が消石灰に転換した時点で、かつ生成消石灰に水分が充
分に含まれている状態、具体的には、消石灰に、５〜３
０質量％、好ましくは１０〜２５質量％、さらに好まし
くは１５〜２０質量％の水が含まれている状態（これら
を含水消石灰と呼ぶ）を混合機から取り出し、乾燥機に
て乾燥させることにより、目的のＢＥＴ比表面積が５０
ｍ2／ｇ以上の消石灰粉末を得ることができる。混合機
と乾燥機とは、分離して設置してもよく、あるいは連続
作業ができるように、混合機と乾燥機とを連結して使用
してもよい。乾燥機での乾燥は、消化反応により発生す
る熱エネルギーを用いて行なうこともできるが、さらに
外部から熱エネルギーを追加して行なうことが望まし
い。また、乾燥は減圧状態にて行なうことが好ましい
が、大気圧条件で実施することもできる。When the digestion reaction has proceeded sufficiently in the mixer and the quicklime has been converted into slaked lime, and the produced slaked lime contains a sufficient amount of water, more specifically, 5 to 3% of the slaked lime.
By removing a state containing 0% by mass, preferably 10 to 25% by mass, and more preferably 15 to 20% by mass of water (these are referred to as hydrous slaked lime) from the mixer and drying with a dryer. , The target BET specific surface area is 50
It is possible to obtain slaked lime powder of m 2 / g or more. The mixer and the dryer may be installed separately, or the mixer and the dryer may be connected and used so that continuous operations can be performed. The drying in the dryer can be performed by using the heat energy generated by the digestion reaction, but it is preferable that the heat energy is further added from the outside. Further, the drying is preferably carried out under reduced pressure, but it can also be carried out under atmospheric pressure conditions.
【００１８】本発明では、消化工程と乾燥工程との間
に、含水消石灰を乾燥させながら、その熟成を行なう熟
成工程を介在させてもよい。この方法は、外部から付与
する熱エネルギーの量を低減させることができ、さらに
高活性消石灰を、より再現性良く製造することが可能に
なるため、好ましい方法である。In the present invention, an aging step for aging the hydrous slaked lime may be interposed between the digestion step and the drying step. This method is a preferable method because the amount of heat energy applied from the outside can be reduced and highly active slaked lime can be produced with higher reproducibility.
【００１９】熟成工程では、消化工程で生成した、含水
率が１０〜３０質量％、好ましくは１０〜２５質量％、
さらに好ましくは１５〜２０質量％の含水消石灰を、乾
燥機能を有する熟成容器内で、水分を徐々に蒸発除去さ
せて実施する。この熟成工程は、３０〜３５０の温度範
囲（特に、３０〜２００℃の温度範囲、いずれも含水消
石灰の温度）で実施することが望ましい。熟成工程は通
常、消化工程に用いる混合機に連結して設置した熟成容
器内で行なうが、熟成容器を混合機と分離して設置し
て、消化工程とは独立に熟成を行なうこともできる。In the aging step, the water content produced in the digestion step is 10 to 30% by mass, preferably 10 to 25% by mass,
More preferably, 15 to 20% by mass of hydrous slaked lime is carried out by gradually evaporating and removing water in an aging container having a drying function. This aging step is preferably carried out in a temperature range of 30 to 350 (in particular, a temperature range of 30 to 200 ° C., both of which are temperatures of hydrous slaked lime). The aging step is usually carried out in an aging container connected to a mixer used for the digestion step, but the aging container may be installed separately from the mixer to perform aging independently of the digestion step.
【００２０】本発明の方法により得られる消石灰は、Ｂ
ＥＴ比表面積が５０ｍ2／ｇ以上（通常は、５０〜６０
ｍ2／ｇ）の微粉末状の高活性消石灰であって、消化水
に添加して使用したジエチレングリコールの大部分の量
が蒸発することなく、消石灰微粉末に含まれている。Slaked lime obtained by the method of the present invention is B
ET specific surface area of 50 m 2 / g or more (usually 50 to 60
m 2 / g) finely powdered highly active slaked lime, and most of the amount of diethylene glycol used by adding it to digested water is contained in the slaked lime fine powder without evaporating.
【００２１】[0021]
【実施例】［実施例１］
（１）原料生石灰の調製
生石灰焼成物（粒径：４０〜７０ｍｍ）を、２００メッ
シュ篩８０％以上パスとなるまで粉砕した。その活性度
は５分値で２０５ｍＬ、１０分値で２１３ｍＬであっ
た。なお、活性度は下記の方法（日本石灰協会参考試験
方法の粗粒滴定法を参考にした方法）により測定した。
活性度測定法：３０℃の純水５００ｍＬを２Ｌの容器に
入れ、少量のフェノールフタレイン指示薬を加え、攪拌
機にて攪拌を、３５０ｒｐｍにて続ける。試料の生石灰
２５ｇを正確に計り取り、純水中に投入する。投入と同
時に、その時間を計測し、指示薬の色が消えないよう
に、４Ｎ塩酸をビュレットから滴下し続ける。５分間お
よび１０分間に消費した４Ｎ塩酸の量を求める。Examples [Example 1] (1) Preparation of raw material quicklime The quicklime burned material (particle size: 40 to 70 mm) was crushed to a pass of 200% mesh sieve of 80% or more. The activity was 205 mL at 5 minutes and 213 mL at 10 minutes. The activity was measured by the following method (a method in which the coarse particle titration method of the Japan Lime Association reference test method was referred to). Activity measurement method: Put 500 mL of 30 ° C. pure water in a 2 L container, add a small amount of phenolphthalein indicator, and continue stirring with a stirrer at 350 rpm. 25 g of quicklime as a sample is accurately measured and put into pure water. Simultaneously with the charging, the time is measured and 4N hydrochloric acid is continuously dripped from the buret so that the color of the indicator does not disappear. Determine the amount of 4N hydrochloric acid consumed in 5 and 10 minutes.
【００２２】（２）生石灰の消化工程と含水消石灰の乾
燥工程
混合機（ダルトン社製万能混合機、５ＡＭＶ−Ｒ型、攪
拌羽根ビダー型）に、生石灰５００質量部、そして純水
４０２質量部（生石灰の消化に必要な理論量の約２．５
倍）に、消化後に生成する消石灰の量に対し１．２質量
％に相当するジエチレングリコールを溶解させた消化水
を投入し、高速回転の条件にて消化反応を行なった。消
化反応の後、含水消石灰を取り出し、乾燥機で乾燥させ
ることにより、水分が１質量％以下の乾燥消石灰粉体を
得た。消化反応ののち取り出した含水消石灰の含水量
と、得られた乾燥消石灰粉末のＢＥＴ比表面積の値を第
１表に示す。(2) Quick lime digestion process and hydrous slaked lime drying process In a mixer (universal mixer manufactured by Dalton Co., 5 AMV-R type, stirring blade bider type), 500 parts by mass of quick lime and 402 parts by mass of pure water ( About 2.5 of the theoretical amount required to digest quicklime
Distilled water in which 1.2 mass% of diethylene glycol corresponding to the amount of slaked lime produced after digestion was dissolved was added to the mixture), and the digestion reaction was performed under the condition of high speed rotation. After the digestion reaction, the hydrous slaked lime was taken out and dried by a drier to obtain a dry slaked lime powder having a water content of 1% by mass or less. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００２３】［実施例２］混合機（マルタニ試工（株）
製のホバート型ソイルミキサ、ＬＳ−４１８型）に、実
施例１で調製した生石灰５００質量部、そして純水４８
２質量部（生石灰の消化に必要な理論量の約３．０倍）
に、消化後に生成する消石灰の量に対して１．８質量％
に相当するジエチレングリコールを溶解させた消化水を
投入し、低速回転の条件にて消化反応を行なった。消化
反応の後、含水消石灰を取り出し、乾燥機で乾燥させる
ことにより、水分が１質量％以下の乾燥消石灰粉体を得
た。消化反応ののち取り出した含水消石灰の含水量と、
得られた乾燥消石灰粉末のＢＥＴ比表面積の値を第１表
に示す。[Embodiment 2] Mixer (Martani Senko Co., Ltd.)
Hobart type Soil mixer (LS-418 type) manufactured by K.K., with 500 parts by mass of quicklime prepared in Example 1 and 48 pure water.
2 parts by mass (about 3.0 times the theoretical amount required to digest quicklime)
In addition, 1.8% by mass relative to the amount of slaked lime produced after digestion
Digestion water in which diethylene glycol corresponding to was dissolved was added, and the digestion reaction was performed under the condition of low speed rotation. After the digestion reaction, the hydrous slaked lime was taken out and dried by a drier to obtain a dry slaked lime powder having a water content of 1% by mass or less. The water content of hydrous slaked lime taken out after the digestion reaction,
The values of the BET specific surface area of the obtained dried slaked lime powder are shown in Table 1.
【００２４】［実施例３］混合機（ダルトン社製万能混
合機、２５ＡＭＶ−ＲＲ型、攪拌羽根ビダー型）に、実
施例１で調製した生石灰３０００質量部、そして純水２
４１０質量部（生石灰の消化に必要な理論量の約２．５
倍）に、消化後に生成する消石灰の量に対して１．５質
量％に相当するジエチレングリコールを溶解させた消化
水を投入し、回転速度を２００ｒｐｍとして消化反応を
行なった。消化反応の後、含水消石灰を取り出し、乾燥
機で乾燥させることにより、水分が１質量％以下の乾燥
消石灰粉体を得た。消化反応ののち取り出した含水消石
灰の含水量と、得られた乾燥消石灰粉末のＢＥＴ比表面
積の値を第１表に示す。[Example 3] 3000 parts by mass of quicklime prepared in Example 1 and 2 parts of pure water were added to a mixer (universal mixer manufactured by Dalton Co., 25 AMV-RR type, stirring blade vider type).
410 parts by mass (about 2.5 of the theoretical amount required to digest quicklime)
2 times), digested water in which diethylene glycol corresponding to 1.5 mass% with respect to the amount of slaked lime produced after digestion was dissolved was added, and the digestion reaction was performed at a rotation speed of 200 rpm. After the digestion reaction, the hydrous slaked lime was taken out and dried by a drier to obtain a dry slaked lime powder having a water content of 1% by mass or less. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００２５】［実施例４］混合機（二軸混合機、有効容
積：３８Ｌ）内に、実施例１で調製した生石灰を１９０
ｋｇ／時間の条件で供給し、同時に消化後に生成する消
石灰の量に対して１．５質量％に相当するジエチレング
リコールを溶解させた消化水（工業用水）を１５３ｋｇ
／時間の条件（生石灰の消化に必要な理論量の約２．５
倍）で供給し、両者を接触させて消化反応を実施した。
消化反応が進行した後、含水消石灰を取り出し、乾燥機
で乾燥させることにより、水分が１質量％以下の乾燥消
石灰粉体を得た。消化反応ののち取り出した含水消石灰
の含水量と、得られた乾燥消石灰粉末のＢＥＴ比表面積
の値を第１表に示す。[Example 4] 190 of the quicklime prepared in Example 1 was placed in a mixer (biaxial mixer, effective volume: 38 L).
153 kg of digested water (industrial water) in which diethylene glycol corresponding to 1.5 mass% with respect to the amount of slaked lime produced after digestion is supplied at the same time is supplied under the condition of kg / hour.
/ Hour condition (about 2.5 of the theoretical amount required for quicklime digestion)
The reaction was carried out by bringing the two into contact with each other to carry out the digestion reaction.
After the digestion reaction proceeded, the hydrated slaked lime was taken out and dried in a dryer to obtain a dry slaked lime powder having a water content of 1% by mass or less. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００２６】［比較例１］純水に、ジエチレングリコー
ルの代わりに、消化後に生成する消石灰の量に対して
１．２質量％に相当する量のエチレングリコールを溶解
させて得た消化水を用いる以外は、実施例１の条件と同
一条件にて、生石灰の消化と乾燥とを行なった。消化反
応ののち取り出した含水消石灰の含水量と、得られた乾
燥消石灰粉末のＢＥＴ比表面積の値を第１表に示す。Comparative Example 1 Except for using diethylene glycol, instead of diethylene glycol, digested water obtained by dissolving ethylene glycol in an amount corresponding to 1.2 mass% with respect to the amount of slaked lime produced after digestion is used. The quicklime was digested and dried under the same conditions as in Example 1. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００２７】［比較例２］純水に、ジエチレングリコー
ルの代わりに、消化後に生成する消石灰の量に対して
１．５質量％に相当する量のショ糖を溶解させて得た消
化水を用いる以外は、実施例１の条件と同一条件にて、
生石灰の消化と乾燥とを行なった。消化反応ののち取り
出した含水消石灰の含水量と、得られた乾燥消石灰粉末
のＢＥＴ比表面積の値を第１表に示す。[Comparative Example 2] Digested water obtained by dissolving sucrose in an amount corresponding to 1.5% by mass with respect to the amount of slaked lime produced after digestion was used in place of diethylene glycol in pure water. Under the same conditions as in Example 1,
The quicklime was digested and dried. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００２８】［比較例３］純水に、ジエチレングリコー
ルの代わりに、消化後に生成する消石灰の量に対して
１．５質量％に相当する量のソルビットを溶解させて得
た消化水を用いる以外は、実施例１の条件と同一条件に
て、生石灰の消化と乾燥とを行なった。消化反応ののち
取り出した含水消石灰の含水量と、得られた乾燥消石灰
粉末のＢＥＴ比表面積の値を第１表に示す。COMPARATIVE EXAMPLE 3 Except that diethylene glycol was used instead of diethylene glycol, digested water obtained by dissolving sorbitol in an amount corresponding to 1.5% by mass relative to the amount of slaked lime produced after digestion was used. The quicklime was digested and dried under the same conditions as in Example 1. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００２９】［比較例４］生石灰５００質量部に対し
て、純水の量を３２０質量部（生石灰の消化に必要な理
論量の約２．０倍）に変え、ジエチレングリコールの使
用量を、消化後に生成する消石灰の量に対して１．５質
量％に相当する量にて使用する以外は、実施例２の条件
と同一の条件にて生石灰の消化反応を行なった。消化反
応の後、そのまま消化熱を利用して乾燥し、水分が１質
量％以下の乾燥消石灰粉体を得た。消化反応ののち取り
出した含水消石灰の含水量と、得られた乾燥消石灰粉末
のＢＥＴ比表面積の値を第１表に示す。[Comparative Example 4] With respect to 500 parts by mass of quick lime, the amount of pure water was changed to 320 parts by mass (about 2.0 times the theoretical amount required for digesting quick lime), and the amount of diethylene glycol used was digested. The quicklime digestion reaction was carried out under the same conditions as in Example 2 except that the amount of slaked lime produced later was used in an amount corresponding to 1.5% by mass. After the digestion reaction, it was dried by utilizing the heat of digestion as it was to obtain a dry slaked lime powder having a water content of 1% by mass or less. Table 1 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００３０】[0030]
【表１】 第１表 ──────────────────────────────────── 添加化合物（添加量：質量％） 含水消石灰の 消石灰粉末の 含水量（質量％） 比表面積（m2/g） ──────────────────────────────────── 実施例１ ジエチレングリコール（１．２） ２０．１ ５１．９ 実施例２ ジエチレングリコール（１．８） １９．２ ５３．７ 実施例３ ジエチレングリコール（１．５） １９．７ ５３．６ 実施例４ ジエチレングリコール（１．５） １８．８ ５１．６ ──────────────────────────────────── 比較例１ エチレングリコール（１．５） ２０．８ ３６．１ 比較例２ ショ糖（１．５） ２１．２ ４３．７ 比較例３ ソルビット（１．５） １９．８ ４８．１ 比較例４ ジエチレングリコール（１．５） ０．８ ４０．８ ────────────────────────────────────[Table 1] Table 1 ──────────────────────────────────── Addition compound (addition amount: mass %) Water content of hydrated slaked lime hydrated lime powder (mass%) Specific surface area (m 2 / g) ───────────────────────────── ──────── Example 1 Diethylene glycol (1.2) 20.1 51.9 Example 2 Diethylene glycol (1.8) 19.2 53.7 Example 3 Diethylene glycol (1.5) 19.7 53.6 Example 4 Diethylene glycol (1.5) 18.8 51.6 ───────────────────────────────── Comparative Example 1 Ethylene glycol (1.5) 20.8 36.1 Comparative Example 2 Sucrose (1.5) 21.2 43.7 Comparative Example 3 Sorbit (1 .5) 19.8 48.1 Comparative Example 4 Diethylene glycol (1.5) 0.8 40.8 ─────────────────────────── ──────────
【００３１】注：含水消石灰の含水量の測定方法（水分
含量５質量％以上の場合に適用）：試料１０ｇを採取
し、２００℃の棚型真空乾燥機にて、１．５時間乾燥し
た後、乾燥原料を測定し、含水量とした。水分含量５質
量％未満の消石灰の水分測定方法：試料１０ｇを採取
し、１１０℃にてケット水分計（メトラー・トレド社
製、ＬＪ１６）にて恒量となるまで測定した。比表面積
（ＢＥＴ比表面積）の測定方法：島津製作所製ＢＥＴ比
表面積計（フローソープ II２３００）を用いた。試料
量は０．２〜０．３ｇとし、前処理として、窒素を導入
しながら、１時間、２００℃で脱気乾燥した。Note: Method for measuring water content of hydrous slaked lime (applied when water content is 5% by mass or more): 10 g of a sample is taken and dried in a shelf vacuum dryer at 200 ° C. for 1.5 hours. Then, the dry raw material was measured to obtain the water content. Method for measuring water content of slaked lime having a water content of less than 5% by mass: 10 g of a sample was collected and measured at 110 ° C. with a Ket moisture meter (LJ16 manufactured by METTLER TOLEDO) until a constant weight was obtained. Measurement method of specific surface area (BET specific surface area): A BET specific surface area meter (Flow Soap II 2300) manufactured by Shimadzu Corporation was used. The sample amount was 0.2 to 0.3 g, and as a pretreatment, deaeration and drying was performed at 200 ° C. for 1 hour while introducing nitrogen.
【００３２】［実施例５］混合機（二軸混合機、有効容
積：３８Ｌ）に、乾燥機能を持つ熟成機（有効容積：５
４Ｌ）が連結した消化・熟成装置の混合機内に、実施例
１で調製した生石灰を１９０ｋｇ／時間の条件で供給
し、同時に消化後に生成する消石灰の量に対して１．５
質量％に相当するジエチレングリコールを溶解させた消
化水（工業用水）を１５３ｋｇ／時間の条件（生石灰の
消化に必要な理論量の約２．５倍）で供給し、混合機の
回転速度を１５０ｒｐｍに調整して、約４分間両者を接
触させて消化反応を実施した。ついで、消化反応生成物
（含水量：１８質量％）を熟成機に移動させ、熟成機内
で１００ｒｐｍの回転速度で攪拌しながら、約５分間熟
成させて、含水量が１０質量％の含水消石灰を得た。そ
の後、含水消石灰を取り出し、乾燥機で乾燥させること
により、水分が１質量％以下の乾燥消石灰粉体を得た。
上記の消化工程、熟成工程、そして乾燥工程からなる消
石灰の製造方法を同一条件にて三回繰り返した。消化反
応ののち取り出した含水消石灰の含水量と、得られた乾
燥消石灰粉末のＢＥＴ比表面積の値を第２表に示す。[Embodiment 5] A aging machine having a drying function (effective volume: 5) was added to a mixer (biaxial mixer, effective volume: 38 L).
4 L) is connected to the mixer of the digestion / maturation apparatus, and the quick lime prepared in Example 1 is supplied under the condition of 190 kg / hour, and at the same time, the amount of slaked lime produced after digestion is 1.5.
Digestion water (industrial water) in which diethylene glycol corresponding to mass% was dissolved was supplied under the condition of 153 kg / hour (about 2.5 times the theoretical amount required for digesting quicklime), and the rotation speed of the mixer was set to 150 rpm. The digestion reaction was performed by adjusting and contacting both for about 4 minutes. Then, the digestion reaction product (water content: 18% by mass) was transferred to an aging machine, and aged for about 5 minutes while stirring at a rotation speed of 100 rpm in the aging machine, to obtain a hydrated slaked lime having a water content of 10% by mass. Obtained. Then, the hydrated slaked lime was taken out and dried by a drier to obtain a dry slaked lime powder having a water content of 1% by mass or less.
The method for producing slaked lime, which comprises the digestion step, the aging step, and the drying step, was repeated three times under the same conditions. Table 2 shows the water content of the hydrated slaked lime taken out after the digestion reaction and the value of the BET specific surface area of the obtained dried slaked lime powder.
【００３３】[0033]
【表２】 第２表 ──────────────────────────────────── 含水消石灰（熟成前） 含水消石灰（熟成後） 消石灰粉末の の含水量（質量％） の含水量（質量％） 比表面積（m2/g） ──────────────────────────────────── 第１回目 １９．１ １１．６ ５１．７ 第２回目 １８．１ １０．４ ５１．４ 第３回目 １８．３ １０．６ ５１．７ ────────────────────────────────────[Table 2] Table 2 ──────────────────────────────────── Hydrated hydrated lime (before aging) Hydrated Slaked lime (after aging) Water content (mass%) of slaked lime powder (mass%) Specific surface area (m 2 / g) ───────────────────── ──────────────── 1st 19.1 11.6 51.7 2nd 18.1 10.4 51.4 3rd 18.3 10.6 51 7 ─────────────────────────────────────
【００３４】[0034]
【発明の効果】本発明を利用することによって、生石灰
の消化による消石灰の製造に際して、あまり多量の比表
面積向上剤を用いることなく、現時点で目標とされてい
る５０ｍ2／ｇ以上の比表面積を有する高活性消石灰
を、比較的低コストで、再現性よく製造することができ
る。EFFECTS OF THE INVENTION By utilizing the present invention, when producing slaked lime by digesting quicklime, the target specific surface area of 50 m 2 / g or more at present is used without using a large amount of specific surface area improver. The highly active slaked lime it has can be produced at a relatively low cost and with good reproducibility.
Claims (10)
化後に生成する消石灰の量に対して０．８〜３質量％に
相当する量のジエチレングリコールを含む、消化に必要
な理論量の１．５質量倍以上の水に接触させることによ
り、消化を行ない、含水率が５〜３０質量％の含水消石
灰を得た後、該含水消石灰を乾燥することを特徴とす
る、ＢＥＴ比表面積が５０ｍ2／ｇ以上の高活性消石灰
の製造方法。1. A theoretical amount of 1.5 required for digestion, which comprises powdered or granular quicklime containing an amount of diethylene glycol corresponding to 0.8 to 3% by mass relative to the amount of slaked lime produced after the digestion. The water-containing slaked lime having a water content of 5 to 30% by mass is obtained by contacting with water in an amount equal to or more than the mass of water, and then the water-containing slaked lime is dried, and the BET specific surface area is 50 m 2 / A method for producing highly active slaked lime of g or more.
比表面積が５０〜６０ｍ2／ｇの高活性消石灰の製造方
法。2. A BET manufactured by the manufacturing method according to claim 1.
A method for producing highly active slaked lime having a specific surface area of 50 to 60 m 2 / g.
グリコールの量が、消化後に生成する消石灰の量に対し
て１．０〜２．５質量％の範囲にある請求項１もしくは
２に記載の高活性消石灰の製造方法。3. The high activity according to claim 1 or 2, wherein the amount of diethylene glycol contained in the water used for digestion is in the range of 1.0 to 2.5 mass% with respect to the amount of slaked lime produced after digestion. Method for producing slaked lime.
化後に生成する消石灰の量に対して０．８〜３質量％に
相当する量のジエチレングリコールを含む、消化に必要
な理論量の１．５質量倍以上の水に接触させることによ
り、消化を行ない、含水率が１０〜３０質量％の含水消
石灰を得た後、該含水消石灰を熟成することによって、
含水消石灰よりも含水率が３〜１５質量％低下した低含
水消石灰を得て、次いで、該低含水消石灰を乾燥するこ
とを特徴とする、ＢＥＴ比表面積が５０ｍ2／ｇ以上の
高活性消石灰の製造方法。4. A theoretical amount of 1.5 required for digestion, which comprises powdered or granular quicklime containing an amount of diethylene glycol corresponding to 0.8 to 3% by mass relative to the amount of slaked lime produced after the digestion. By contacting with more than mass times water, digestion is carried out, after obtaining a hydrated slaked lime having a water content of 10 to 30% by mass, by aging the hydrated slaked lime,
A high activity slaked lime having a BET specific surface area of 50 m 2 / g or more, characterized in that a low water content slaked lime having a water content lower than that of the water content slaked lime by 3 to 15% by mass is obtained, and then the low water content slaked lime is dried. Production method.
比表面積が５０〜６０ｍ2／ｇの高活性消石灰の製造方
法。5. A BET produced by the manufacturing method according to claim 4.
A method for producing highly active slaked lime having a specific surface area of 50 to 60 m 2 / g.
グリコールの量が、消化後に生成する消石灰の量に対し
て１．０〜２．５質量％の範囲にある請求項４もしくは
５に記載の高活性消石灰の製造方法。6. The high activity according to claim 4 or 5, wherein the amount of diethylene glycol contained in the water used for digestion is in the range of 1.0 to 2.5 mass% with respect to the amount of slaked lime produced after digestion. Method for producing slaked lime.
量で含有し、かつＢＥＴ比表面積が５０〜６０ｍ2／ｇ
の範囲にある高活性消石灰。7. A content of diethylene glycol in an amount of 3% by mass or less and a BET specific surface area of 50 to 60 m 2 / g.
Highly active slaked lime in the range of.
範囲にある請求項７に記載の高活性消石灰。8. The highly active slaked lime according to claim 7, which has a BET specific surface area in the range of 51 to 55 m 2 / g.
〜２．５質量％の範囲にある請求項７もしくは８に記載
の高活性消石灰。9. The content of diethylene glycol is 1.0.
The highly active slaked lime according to claim 7 or 8, which is in the range of 2.5 mass%.
１〜２．０質量％の範囲にある請求項９に記載の高活性
消石灰。10. The content of diethylene glycol is 1.
The highly active slaked lime according to claim 9, which is in the range of 1 to 2.0% by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002099779A JP2003300725A (en) | 2002-04-02 | 2002-04-02 | Manufacture of highly activated slaked lime |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002099779A JP2003300725A (en) | 2002-04-02 | 2002-04-02 | Manufacture of highly activated slaked lime |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007073128A Division JP2007197319A (en) | 2007-03-20 | 2007-03-20 | High-activity slaked lime |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003300725A true JP2003300725A (en) | 2003-10-21 |
Family
ID=29388239
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002099779A Pending JP2003300725A (en) | 2002-04-02 | 2002-04-02 | Manufacture of highly activated slaked lime |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169062A (en) * | 2004-12-17 | 2006-06-29 | Ube Material Industries Ltd | Porous particulate containing calcium oxide |
| WO2007142192A1 (en) | 2006-06-02 | 2007-12-13 | National University Corporation Tohoku University | Porous calcium oxide particulate and porous calcium hydroxide particulate |
| JP2008290940A (en) * | 2004-05-14 | 2008-12-04 | Ube Material Industries Ltd | Porous slaked lime |
| KR100880128B1 (en) | 2008-07-24 | 2009-01-23 | 주식회사 서울아이씨 | Method for making lime slurry with high-speed agitation |
| JP2018527273A (en) * | 2015-08-14 | 2018-09-20 | エス．ア．ロイスト ルシェルシュ エ デヴロップマン | Method for producing highly porous slaked lime and product obtained thereby |
-
2002
- 2002-04-02 JP JP2002099779A patent/JP2003300725A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008290940A (en) * | 2004-05-14 | 2008-12-04 | Ube Material Industries Ltd | Porous slaked lime |
| JP2006169062A (en) * | 2004-12-17 | 2006-06-29 | Ube Material Industries Ltd | Porous particulate containing calcium oxide |
| WO2007142192A1 (en) | 2006-06-02 | 2007-12-13 | National University Corporation Tohoku University | Porous calcium oxide particulate and porous calcium hydroxide particulate |
| KR100880128B1 (en) | 2008-07-24 | 2009-01-23 | 주식회사 서울아이씨 | Method for making lime slurry with high-speed agitation |
| JP2018527273A (en) * | 2015-08-14 | 2018-09-20 | エス．ア．ロイスト ルシェルシュ エ デヴロップマン | Method for producing highly porous slaked lime and product obtained thereby |
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