JP4328082B2 - Method for producing slaked lime - Google Patents
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- JP4328082B2 JP4328082B2 JP2002336635A JP2002336635A JP4328082B2 JP 4328082 B2 JP4328082 B2 JP 4328082B2 JP 2002336635 A JP2002336635 A JP 2002336635A JP 2002336635 A JP2002336635 A JP 2002336635A JP 4328082 B2 JP4328082 B2 JP 4328082B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、消石灰の製造方法に関する。
【０００２】
【従来の技術】
消石灰（水酸化カルシウム：Ｃａ（ＯＨ）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知られている。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。
【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、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、コハク酸金属塩、あるいはリグニンスルホン酸塩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、次いで、消化反応後の消石灰を水分が含まれている状態（以下、含水消石灰という）で消化装置もしくは熟成装置から取り出し、乾燥器にて乾燥させる方法が開発されている。これらの水溶性化合物（以下、比表面積向上剤という）を添加した消化水を用い、かつ含水消石灰を乾燥機により乾燥させる方法を利用することにより、通常の水を消化水に用い、かつ含水消石灰を消化熱により乾燥させる従来の方法と比較すると、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。
【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。
特許文献１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、コハク酸金属塩、あるいはリグニンスルホン酸塩を、生石灰に対して０．１〜１０質量％添加したものを用い、生成した含水生石灰の含水率が３〜３０質量％となるように、消化水量ないし反応温度を調整し、その含水消石灰を乾燥器にて乾燥することにより、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。この文献には、乾燥機としては、パドルドライヤー、ベルト乾燥機、バンド乾燥機、ロータリ乾燥機、流動乾燥機、気流乾燥機、電磁波乾燥機、赤外（遠赤外）乾燥機等いずれでもよいが、できるだけ炭酸ガスとの接触を避け、消石灰が炭酸カルシウムとなることを避けるため、間接加熱式のものが好ましいとの記載がある。
【０００５】
特許文献２には、生石灰の消化による消石灰の製造に際して、消化装置に、生石灰の消化に必要な量の２．５倍以上の消化水（好ましくは、糖類を添加したもの）を供給すると共に、熟成装置から取り出される熟成物（含水消石灰）を乾燥器にて乾燥させ、かつその乾燥機から取り出される消石灰が６０℃以下となるように乾燥機内で冷却することにより、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。この文献には、乾燥機としては、パドルドライヤー、ベルト乾燥機、バンド乾燥機、ロータリ乾燥機、流動乾燥機、気流乾燥機、電磁波乾燥機、赤外（遠赤外）乾燥機等いずれでもよいが、できるだけ炭酸ガスとの接触を避け、消石灰が炭酸カルシウムとなることを避けるため、水蒸気流通型の撹拌羽根を備えた間接加熱式のものが好ましいとの記載がある。
【０００６】
【特許文献１】
特開平９−２７８４３５号公報
【特許文献２】
特開平１０−１５８０４２号公報
【０００７】
【発明が解決しようとする課題】
上記のように、生石灰を比表面積向上剤の存在下に消化させ、次いで、含水消石灰を乾燥器にて乾燥させる方法を利用することにより、従来の乾式法に比べて高比表面積の消石灰を得ることができるようになっているが、本発明者の研究によれば、同じ条件で生成した含水消石灰であっても、その後の乾燥条件によって、比表面積の異なる消石灰が生成することが判明した。この消石灰の比表面積が異なることの主な要因が、乾燥時に消石灰と炭酸ガスとの接触により炭酸カルシウムが生成するためであるとすれば、真空乾燥機を用いて、減圧下に含水消石灰を乾燥することにより、比表面積の高い消石灰を得ることができる。しかしながら、含水消石灰を真空乾燥機のようなバッチ式の乾燥機を用いて乾燥するのは、その生産性を考慮すると明らかに不利となる。
従って、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行われる含水消石灰の乾燥方法を改良することにより、比表面積の高い消石灰を効率よく製造する技術を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者は、含水消石灰の乾燥条件と乾燥後の消石灰の比表面積との関係を調べた。その結果、意外にも含水率が５〜３０質量％の含水消石灰を、１００〜３５０℃の温度に加熱した空気中に分散させて乾燥する方法を利用すると、加熱空気への含水消石灰の分散量が消石灰量として５００ｋｇ／ｍ3以下であれば、真空乾燥機を用いて、減圧下に乾燥を行なって得た消石灰と同様もしくはそれ以上の高い比表面積を有する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、本発明者は、さらに研究を進めた結果、上記の乾燥方法を利用すると、比表面積向上剤として、ジエチレングリコールもしくはソルビトール又はこれらの混合物を用いる場合には、その消化水への添加量が、その消化後に生成する消石灰の量に対して０．１〜３質量％程度の量であってもＢＥＴ比表面積が４０ｍ2／ｇ以上の消石灰を製造することができ、特に、その添加量を、その消化後に生成する消石灰の量に対して０．８〜３質量％にすることによりＢＥＴ比表面積が５０ｍ2／ｇ以上の消石灰を製造することができることを見い出した。
【０００９】
従って、本発明は、粉末状もしくは粒状の生石灰を、その消化後に生成する消石灰の量に対して０．８〜３質量％に相当する量のジエチレングリコールもしくはジエチレングリコールとソルビトールとの混合物を含む、消化に必要な理論量の１．５〜５質量倍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、温度が１００〜３５０℃の加熱空気中に、消石灰量として５００ｋｇ／ｍ3以下となるように分散させることにより乾燥することを特徴とする、ＢＥＴ比表面積が５０ｍ 2 ／ｇ以上の消石灰の製造方法にある。
【００１０】
含水消石灰は、加熱空気中に消石灰量として３００ｋｇ／ｍ 3 以下で、０．１ｋｇ／ｍ 3 以上となるように分散させることにより乾燥することが好ましい。
【００１１】
含水消石灰は、流動層式乾燥機もしくは気流式乾燥機を用いて乾燥することが好ましい。
【００１２】
【発明の実施の形態】
本発明は、生石灰を過剰量の水と接触させることによって、消化を行ない、消化反応が進行した後、水分を所定の量で含有する含水消石灰を得て、これを、一定範囲の量で加熱空気中に分散させ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する。
【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した後、原料生石灰として用いる。
【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１．５〜５質量倍の範囲であって、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。
【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０．８〜３．０質量％、さらに好ましくは、１〜２．５質量％、特に好ましくは１．１〜２．０質量％に相当する量）のジエチレングリコールもしくはジエチレングリコールとソルビトールとの混合物を含むものである。所望により、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、及びソルビトールは共に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もしくはジエチレングリコールとソルビトールとの混合物が添加されていることが好ましい。
【００１６】
生石灰の消化反応は、通常は、撹拌機能を有する消化装置を用いて、攪拌下にて実施する。撹拌は比較的高速で実施することが好ましい。
【００１７】
本発明では、生石灰の消化により生成した、含水率が５〜３０質量％、好ましくは１０〜３０質量％、さらに好ましくは１５〜２５質量％の含水消石灰を、温度が１００〜３５０℃、好ましくは１１０〜２５０℃、さらに好ましくは１２０〜２３０℃の温度に加熱された加熱空気中に分散することにより乾燥する。加熱空気中への含水消石灰の分散量は、消石灰量（含水消石灰から水分を除いた量）として５００ｋｇ／ｍ3以下、好ましくは３００ｋｇ／ｍ3以下、さらに好ましくは１００ｋｇ／ｍ3以下であって、０．１ｋｇ／ｍ3以上、好ましくは、０．５ｋｇ／ｍ3以上、特に好ましくは１ｋｇ／ｍ3以上とする。含水消石灰の量を多くし過ぎると、その乾燥中に消石灰の粒子と粒子とが互いに固着して塊状物を形成し易くなり、乾燥後の消石灰の比表面積が小さくなる傾向にある。一方、含水消石灰の量を少なくしすぎると、含水消石灰の乾燥効率の観点で不利となる。
【００１８】
加熱空気中への含水消石灰の分散量は、乾燥機内に滞留している消石灰の量（単位：ｋｇ）／乾燥機内の加熱空気量（乾燥機の乾燥有効容積と同じ、単位：ｍ3）である。また、乾燥機内に滞留している消石灰の量は、消石灰が乾燥機内に滞留する時間（乾燥機滞留時間）と、消石灰の乾燥機への供給速度とを乗じた値である。従って、含水消石灰の分散量は、消石灰の乾燥機滞留時間、及び消石灰の供給速度により調整することができる。
【００１９】
含水消石灰の乾燥には、流動層式乾燥機及び気流式乾燥機を用いることができる。これらの乾燥機の内部に伝熱器を設置して、加熱空気による含水消石灰の乾燥と同時に伝熱器による乾燥を行なってもよい。乾燥工程に用いる乾燥機は、消化装置と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、消化装置に連結して使用してもよい。
【００２０】
本発明では、消化工程と乾燥工程との間に熟成工程を介在させてもよい。この方法は、消化工程にて生成した含水消石灰の消化ムラを低減させることができ、含水消石灰の水分を均一にすることができるため、好ましい方法である。熟成工程は、通常は、撹拌機を有する熟成装置を用いて、撹拌下に実施する。
【００２１】
熟成工程では、さらに消化反応により発生する熱エネルギーを利用して含水消石灰を加熱して、その水分を調整してもよい。含水消石灰の加熱は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）で実施することが好ましい。熟成工程は、通常は、消化装置に連結して設置した熟成装置内で行なうが、熟成装置を消化装置と分離して設置して、消化工程とは独立に熟成を行うこともできる。
【００２２】
【実施例】
［実施例１］
（１）原料生石灰の調整
焼成生石灰（粒径：４０〜７０ｍｍ）を、２００メッシュ篩７５％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２１２ｍＬ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。
［活性度測定方法］
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、撹拌機にて撹拌を３５０ｒｐｍにて続ける。試料の生石灰２５ｇを正確に計り取り、純水中に供給する。供給と同時に、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分間及び１０分間に消費した４Ｎ塩酸の量を求める。
【００２３】
（２）生石灰の消化工程と熟成工程
消化装置（二軸混合機、有効容積：３８Ｌ）内に、生石灰を１８０ｋｇ／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１．２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（工業用水）を１６８ｋｇ／時間の条件（生石灰の消化に必要な理論量の約２．９倍）で供給し、両者を接触させて消化反応を実施した。消化反応の後、消化反応生成物を取り出し、熟成装置（有効容積：５４Ｌ）にて熟成した。熟成後の水分は２０質量％であった。
【００２４】
（３）含水消石灰の乾燥工程
気流式乾燥機（乾燥有効容積：０．０３７ｍ3）内に、２００℃の加熱空気を２５０ｍ3／時間の条件で供給しながら、含水消石灰を４０ｋｇ／時間（消石灰として３２ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として１．４ｋｇ／ｍ3となるようにして、含水消石灰を乾燥し、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００２５】
［実施例２］
気流式乾燥機の変わりに、内部に５ｋｇ／ｃｍ2の飽和水蒸気（温度：約１５０℃）が供給されている伝熱器を備えた伝導伝熱流動層式乾燥機（乾燥有効容積：０．０４０ｍ3）を用い、その乾燥機内に１５０℃の加熱空気を７２ｍ3／時間の条件で供給しながら、含水消石灰を４８ｋｇ／時間（消石灰として３８．４ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として９６ｋｇ／ｍ3となるようにして、含水消石灰を乾燥した以外は、実施例１と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００２６】
［実施例３］
気流式乾燥機の変わりに、内部に５ｋｇ／ｃｍ2の飽和水蒸気（温度：約１５０℃）が供給されている伝熱器を備えた伝導伝熱流動層式乾燥機（乾燥有効容積：０．１５ｍ3）を用い、その乾燥機内に１５０℃の加熱空気を４３２ｍ3／時間の条件で供給しながら、含水消石灰を２３０ｋｇ／時間（消石灰として１８４ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として２６０ｋｇ／ｍ3となるようにして、含水消石灰を乾燥した以外は、実施例１と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００２７】
［比較例１］
気流式乾燥機の変わりに、内部に５ｋｇ／ｃｍ2の飽和水蒸気（温度：約１５０℃）が供給されている伝熱器を備えた間接加熱式乾燥機（乾燥有効容積：０．０６０ｍ3）を用い、その乾燥機内に１２０℃の加熱空気を４２ｍ3／時間の条件で供給しながら、含水消石灰を１８０ｋｇ／時間（消石灰として１４４ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として５２０ｋｇ／ｍ3となるようにして、含水消石灰を乾燥した以外は、実施例１と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００２８】
［参考例１］
気流式乾燥機の変わりに、棚型真空乾燥機（乾燥有効容積：０．００８５ｍ3）を用い、その乾燥機内に、含水消石灰６．２５ｋｇ（消石灰として５ｋｇ）を投入して、減圧下、２００℃で１時間加熱して乾燥した以外は、実施例１と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００２９】
【表１】
注２）比較例１では、含水消石灰は加熱空気中に分散させていない。
【００３０】
［実験例４］
消化水に、消化後に生成する消石灰の量に対して０．５質量％に相当するジエチレングリコールを溶解させたものを用いる以外は、実施例１（２）と同一条件にて、生石灰の消化と熟成とを行なって、水分２０質量％の含水消石灰を得た。
次いで、気流式乾燥機（乾燥有効容積：０．０３７ｍ3）内に、２００℃の加熱空気を２５０ｍ3／時間の条件で供給しながら、含水消石灰を４０ｋｇ／時間（消石灰として３２ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として１．４ｋｇ／ｍ3となるようにして、含水消石灰を乾燥し、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００３１】
［実験例５］
気流式乾燥機の変わりに、内部に５ｋｇ／ｃｍ2の飽和水蒸気（温度：約１５０℃）が供給されている伝熱器を備えた伝導伝熱流動層式乾燥機（乾燥有効容積：０．１５ｍ3）を用い、その乾燥機内に１５０℃の加熱空気を４３２ｍ3／時間の条件で供給しながら、含水消石灰を２３０ｋｇ／時間（消石灰として１８４ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として２６０ｋｇ／ｍ3となるようにして、含水消石灰を乾燥した以外は、実験例４と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００３２】
［比較例２］
気流式乾燥機の変わりに、内部に５ｋｇ／ｃｍ2の飽和水蒸気（温度：約１５０℃）が供給されている伝熱器を備えた間接加熱式乾燥機（乾燥有効容積：０．０６０ｍ3）を用い、その乾燥機内に１２０℃の加熱空気を４２ｍ3／時間の条件で供給しながら、含水消石灰を１８０ｋｇ／時間（消石灰として１４４ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として５２０ｋｇ／ｍ3となるようにして、含水消石灰を乾燥した以外は、実験例４と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００３３】
［参考例２］
気流式乾燥機の変わりに、棚型真空乾燥機（乾燥有効容積：０．００８５ｍ3）を用い、その乾燥機内に、含水消石灰６．２５ｋｇ（消石灰として５ｋｇ）を投入して、減圧下、２００℃で１時間加熱して乾燥した以外は、実験例４と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。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。
【００３４】
［表２］
第２表（消化水：ジエチレングリコール０．５質量％添加）
───────────────────────────────────
加熱空気中の消石灰量 ＢＥＴ比表面積
（ｋｇ／ｍ3） （ｍ2／ｇ）
───────────────────────────────────
実験例４ １．４ ４７．０
実験例５ ２６０ ４６．０
───────────────────────────────────
比較例２ ５２０ ３８．８
───────────────────────────────────
参考例２ − ４５．０
───────────────────────────────────
注）比較例２では、含水消石灰は加熱空気中に分散させていない。
【００３５】
［実施例６］
消化水に、消化後に生成する消石灰の量に対して０．５質量％に相当するジエチレングリコールと１．０質量％に相当するＤ−ソルビトールとを溶解させたものを用いる以外は、実施例１（２）と同一条件にて、生石灰の消化と熟成とを行なって、水分２０質量％の含水消石灰を得た。
次いで、内部に５ｋｇ／ｃｍ2の飽和水蒸気（温度：約１５０℃）が供給されている伝熱器を備えた伝導伝熱流動層式乾燥機（乾燥有効容積：０．１５ｍ3）内に、１５０℃の加熱空気を４３２ｍ3／時間の条件で供給しながら、含水消石灰を２３０ｋｇ／時間（消石灰として１８４ｋｇ／時間）の条件で供給し、加熱空気中の消石灰量として２６０ｋｇ／ｍ3となるようにして、含水消石灰を乾燥し、水分１質量％以下の乾燥消石灰粉末を得た。得られた乾燥消石灰粉末のＢＥＴ比表面積の値を第３表に示す。
【００３６】
［参考例３］
伝導伝熱流動層式乾燥機の変わりに、棚型真空乾燥機（乾燥有効容積：０．００８５ｍ3）を用い、その乾燥機内に、含水消石灰６．２５ｋｇ（消石灰として５ｋｇ／時間）を投入して、減圧下、２００℃で１時間加熱して乾燥した以外は、実施例６と同じ操作を行なって、水分１質量％以下の乾燥消石灰粉末を得た。得られた乾燥消石灰粉末のＢＥＴ比表面積の値を第３表に示す。
【００３７】
【表３】
【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行われる含水消石灰の乾燥に真空乾燥機を用いた場合と同様もしくはそれ以上の比表面積を有する消石灰を工業的に有利に製造することができる。従って、本発明によれば、あまり多量の比表面積向上剤を用いることなく、５０ｍ2／ｇ以上の比表面積を有する消石灰を、比較的低コストで、効率よく製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing slaked lime.
[0002]
[Prior art]
As an industrial method for producing slaked lime (calcium hydroxide: Ca (OH) 2 ), digestion is performed by bringing quick lime (calcium oxide: CaO) into contact with an excess amount of water, and at the same time or afterwards by digestion. There is known a method of producing powdery slaked lime product having a moisture content of 1% by mass or less by evaporating excess water by using generated heat and drying. This method of producing slaked lime is usually called “dry method”. This dry method is advantageous from the viewpoint of production cost because it does not require external heat energy supplementation for drying the hydrous slaked lime produced by digestion. However, the slaked lime powder obtained by this dry method has a low specific surface area and therefore has low reactivity, and is disadvantageous as slaked lime used for, for example, treatment of exhaust gas discharged from a waste incinerator (removal of acidic substances). .
[0003]
Research on increasing the specific surface area of slaked lime obtained by the dry method has already been conducted by many researchers, and as a result, water used for digesting quick lime (digested water), oxycarboxylic acid, oxycarboxylate, Add a water-soluble compound such as sugars, ethylene glycols, ethanolamines, glycerin, succinic acid, succinic acid metal salt, or lignin sulfonate, and proceed the digestion reaction in the presence of these water-soluble compounds, Next, a method has been developed in which the slaked lime after the digestion reaction is taken out from the digester or the aging device in a state containing moisture (hereinafter referred to as hydrous slaked lime) and dried in a dryer. By using digested water to which these water-soluble compounds (hereinafter referred to as specific surface area improvers) are added and using a method of drying hydrous slaked lime with a dryer, ordinary water is used as digested water and hydrous slaked lime Compared with the conventional method of drying by digestion heat, slaked lime having a remarkably high specific surface area can be obtained.
[0004]
Examples of publications describing the above-mentioned known techniques include the following.
In patent document 1, when producing slaked lime by digestion of quicklime, as digestion water, oxycarboxylic acid, oxycarboxylate, sugar, ethylene glycols, ethanolamines, glycerin, succinic acid, succinic acid metal salt, Alternatively, the amount of digestion water or the reaction temperature is adjusted so that the water content of the produced hydrated quicklime is 3 to 30% by mass using lignin sulfonate added at 0.1 to 10% by mass relative to quicklime. The method of obtaining the slaked lime by which the hydrous slaked lime was dried with the drier by the fine particle, the specific surface area was large, and the reactivity was improved is described. In this document, as a dryer, any of a paddle dryer, a belt dryer, a band dryer, a rotary dryer, a fluid dryer, an air dryer, an electromagnetic dryer, an infrared (far infrared) dryer, and the like may be used. However, in order to avoid contact with carbon dioxide gas as much as possible and avoid slaked lime becoming calcium carbonate, there is a description that an indirect heating type is preferable.
[0005]
In Patent Document 2, when producing slaked lime by digestion of quicklime, the digester is supplied with digestion water (preferably, with addition of sugar) of 2.5 times or more the amount necessary for digestion of quicklime, The aged product (hydrous slaked lime) taken out from the aging device is dried in a drier, and cooled in the drier so that the slaked lime taken out from the drier becomes 60 ° C. or less, thereby increasing the specific surface area and reactivity. Describes a method for obtaining improved slaked lime. In this document, as a dryer, any of a paddle dryer, a belt dryer, a band dryer, a rotary dryer, a fluid dryer, an air dryer, an electromagnetic dryer, an infrared (far infrared) dryer, and the like may be used. However, in order to avoid contact with carbon dioxide gas as much as possible and avoid slaked lime becoming calcium carbonate, there is a description that an indirect heating type equipped with a water vapor flow type stirring blade is preferable.
[0006]
[Patent Document 1]
JP-A-9-278435 [Patent Document 2]
JP-A-10-158042 [0007]
[Problems to be solved by the invention]
As described above, quick lime is digested in the presence of a specific surface area improver, and then hydrated slaked lime is dried in a dryer to obtain slaked lime with a high specific surface area compared to the conventional dry method. However, according to the inventor's research, it has been found that even hydrated slaked lime produced under the same conditions, slaked lime having a different specific surface area is produced depending on the subsequent drying conditions. If the main reason for the difference in specific surface area of slaked lime is that calcium carbonate is produced by contact between slaked lime and carbon dioxide during drying, the hydrous slaked lime is dried under reduced pressure using a vacuum dryer. By doing, slaked lime with a high specific surface area can be obtained. However, drying hydrous slaked lime using a batch dryer such as a vacuum dryer is clearly disadvantageous in view of its productivity.
Therefore, the subject of this invention is providing the technique which manufactures slaked lime with a high specific surface area efficiently by improving the drying method of the hydrous slaked lime performed at the time of manufacture of slaked lime by digestion of quick lime.
[0008]
[Means for Solving the Problems]
This inventor investigated the relationship between the drying conditions of hydrous slaked lime and the specific surface area of the slaked lime after drying. As a result, surprisingly, when using a method of dispersing and drying hydrous slaked lime having a moisture content of 5 to 30% by mass in air heated to a temperature of 100 to 350 ° C., the amount of hydrous slaked lime dispersed in the heated air If the amount of slaked lime is 500 kg / m 3 or less, it is found that slaked lime having a high specific surface area similar to or higher than slaked lime obtained by drying under reduced pressure using a vacuum dryer can be obtained. Completed the invention. In addition, as a result of further research, the present inventor, when using the above drying method, when using diethylene glycol or sorbitol or a mixture thereof as a specific surface area improver, the amount added to digestion water is Even if the amount is about 0.1 to 3% by mass with respect to the amount of slaked lime generated after the digestion, slaked lime having a BET specific surface area of 40 m 2 / g or more can be produced. It has been found that slaked lime having a BET specific surface area of 50 m 2 / g or more can be produced by adjusting the amount to 0.8 to 3% by mass with respect to the amount of slaked lime generated after the digestion.
[0009]
Therefore, the present invention provides powdery or granular quicklime for digestion containing diethylene glycol or a mixture of diethylene glycol and sorbitol in an amount corresponding to 0.8 to 3% by mass with respect to the amount of slaked lime produced after the digestion. Digestion is performed by contacting with 1.5 to 5 times the required theoretical amount of water to obtain hydrous slaked lime having a moisture content of 5 to 30% by mass, and then the hydrous slaked lime has a temperature of 100 to 350. the heating in air ° C., characterized by drying by dispersing such that 500 kg / m 3 or less under a hydrated lime content, BET specific surface area is in the production method of 50 m 2 / g or more slaked lime.
[0010]
The hydrous slaked lime is preferably dried by dispersing it in the heated air so that the amount of slaked lime is 300 kg / m 3 or less and 0.1 kg / m 3 or more.
[0011]
The hydrous slaked lime is preferably dried using a fluidized bed dryer or an airflow dryer.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, quick lime is brought into contact with an excessive amount of water to perform digestion, and after the digestion reaction proceeds, hydrous slaked lime containing a predetermined amount of water is obtained, and this is heated in a certain range of amounts. It is characterized by producing slaked lime products by dispersing in air and drying.
[0013]
The quicklime used as a raw material is not fundamentally different from the quicklime used for the production of ordinary slaked lime. That is, generally, a mass of ordinary calcined quicklime is appropriately pulverized and powdered or granulated, and then used as raw quicklime.
[0014]
The amount of water (digested water) used for digestion of quicklime is also in the range of 1.5 to 5 times the theoretical amount of water required for digestion with respect to the amount of quicklime used. There is no difference from the conventionally known quick lime digestion conditions.
[0015]
Digestion water used in the present invention, a small amount (generated after digestion with respect to the amount 0.8 to 3.0% by weight of slaked lime, more preferably, 1 to 2.5% by weight, particularly preferably 1.1 to 2 Ru der those comprising a mixture of diethylene glycol or diethylene glycol and sorbitol quantity) corresponding to 2.0 wt%. If desired, other specific surface area improvers may be used in combination. Diethylene glycol, and sorbitol are both excellent in miscibility with water, it can be easily manufactured by adjusting the digestion solution. Digested water is preferably added with diethylene glycol or a mixture of diethylene glycol and sorbitol before contacting with quicklime.
[0016]
The quicklime digestion reaction is usually carried out with stirring using a digester having a stirring function. Stirring is preferably performed at a relatively high speed.
[0017]
In the present invention, a hydrous slaked lime having a water content of 5 to 30% by mass, preferably 10 to 30% by mass, more preferably 15 to 25% by mass, produced by digestion of quick lime, has a temperature of 100 to 350 ° C., preferably It dries by disperse | distributing in the heated air heated to the temperature of 110-250 degreeC, More preferably, 120-230 degreeC. The dispersion amount of the hydrous slaked lime in the heated air is 500 kg / m 3 or less, preferably 300 kg / m 3 or less, more preferably 100 kg / m 3 or less as the amount of slaked lime (amount obtained by removing water from the hydrous slaked lime). 0.1 kg / m 3 or more, preferably 0.5 kg / m 3 or more, particularly preferably 1 kg / m 3 or more. When the amount of the hydrous slaked lime is excessively large, the slaked lime particles and the particles are fixed to each other during the drying to easily form a lump, and the specific surface area of the slaked lime after drying tends to be reduced. On the other hand, if the amount of hydrous slaked lime is too small, it is disadvantageous in terms of the drying efficiency of the hydrous slaked lime.
[0018]
The amount of hydrated slaked lime dispersed in the heated air is the amount of slaked lime retained in the dryer (unit: kg) / the amount of heated air in the dryer (same as the drying effective volume of the dryer, unit: m 3 ). is there. Further, the amount of slaked lime remaining in the dryer is a value obtained by multiplying the time during which the slaked lime stays in the dryer (dryer retention time) and the supply speed of the slaked lime to the dryer. Therefore, the dispersion amount of the hydrous slaked lime can be adjusted by the dwelling time of the slaked lime and the supply rate of the slaked lime.
[0019]
For drying the hydrous slaked lime, a fluidized bed dryer or an airflow dryer can be used. You may install a heat exchanger inside these dryers, and may dry with a heat exchanger simultaneously with drying of the hydrous slaked lime with heated air. The dryer used for the drying process may be installed separately from the digester, or may be used connected to the digester so that continuous operation can be performed.
[0020]
In the present invention, an aging step may be interposed between the digestion step and the drying step. This method is a preferable method because the digestion unevenness of the hydrous slaked lime generated in the digestion step can be reduced and the water content of the hydrous slaked lime can be made uniform. The aging step is usually carried out with stirring using an aging apparatus having a stirrer.
[0021]
In the aging step, the water content may be adjusted by heating the hydrous slaked lime using thermal energy generated by the digestion reaction. It is preferable to carry out the heating of the hydrous slaked lime in the temperature range of 30 to 350 ° C. (particularly, the temperature range of 30 to 200 ° C., both of which are the temperature of the hydrous slaked lime). The ripening step is usually performed in a ripening device connected to a digester, but the ripening device may be installed separately from the digester and ripened independently of the digestion step.
[0022]
【Example】
[Example 1]
(1) Preparation of raw quicklime The calcined quicklime (particle size: 40 to 70 mm) was pulverized until it became a pass of 75% or more of 200 mesh sieve. The activity was 205 mL for the 5-minute value and 212 mL for the 10-minute value. The activity was measured by the following method (method referring to the coarse grain titration method of the Japan Lime Association Reference Test Method).
[Activity measurement method]
Put 500 mL of pure water at 30 ° C. into a 2 L container, add a small amount of phenolphthalein indicator, and continue stirring with a stirrer at 350 rpm. A sample of quick lime 25 g is accurately weighed and fed into pure water. Simultaneously with the supply, the time is measured and 4N hydrochloric acid is continuously dropped from the burette so that the color of the indicator does not disappear. Determine the amount of 4N hydrochloric acid consumed in 5 and 10 minutes.
[0023]
(2) Quick Lime Digestion Process and Aging Process Quick lime is supplied into a digester (biaxial mixer, effective volume: 38 L) at a rate of 180 kg / hour, and at the same time 1. Digestion water (industrial water) in which diethylene glycol equivalent to 2% by mass is dissolved is supplied at a rate of 168 kg / hour (approximately 2.9 times the theoretical amount necessary for digestion of quicklime), and both are brought into contact with each other for digestion reaction. Carried out. After the digestion reaction, the digestion reaction product was taken out and aged with an aging apparatus (effective volume: 54 L). The moisture after aging was 20% by mass.
[0024]
(3) Drying process of hydrous slaked lime While supplying heated air at 200 ° C. under a condition of 250 m 3 / hour in an air flow dryer (dry effective volume: 0.037 m 3 ), hydrous slaked lime is supplied at 40 kg / hr (slaked lime). As 32 kg / hour), and the hydrous slaked lime was dried so that the amount of slaked lime in the heated air was 1.4 kg / m 3 to obtain a dried slaked lime powder having a water content of 1% by mass or less. Table 1 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0025]
[Example 2]
Instead of an air flow dryer, a conduction heat transfer fluidized bed dryer (effective drying volume: 0. 0) having a heat exchanger in which 5 kg / cm 2 of saturated steam (temperature: about 150 ° C) is supplied. 040 m 3 ), supplying heated air at 150 ° C. to the dryer at 72 m 3 / hour, supplying hydrous slaked lime at 48 kg / hour (38.4 kg / hour as slaked lime), and heated air A dry slaked lime powder having a water content of 1% by mass or less was obtained by performing the same operation as in Example 1 except that the hydrous slaked lime was dried so that the amount of slaked lime in the mixture was 96 kg / m 3 . Table 1 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0026]
[Example 3]
Instead of an air flow dryer, a conduction heat transfer fluidized bed dryer (effective drying volume: 0. 0) having a heat exchanger in which 5 kg / cm 2 of saturated steam (temperature: about 150 ° C) is supplied. 15 m 3 ), supplying heated slaked lime at a rate of 230 kg / hour (184 kg / hour as slaked lime) while supplying heated air at 150 ° C. to the dryer at a rate of 432 m 3 / hour. Except for drying the hydrous slaked lime so that the amount of slaked lime was 260 kg / m 3 , the same operation as in Example 1 was performed to obtain a dry slaked lime powder having a moisture content of 1% by mass or less. Table 1 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0027]
[Comparative Example 1]
An indirect heating dryer (effective drying volume: 0.060 m 3 ) equipped with a heat transfer device in which 5 kg / cm 2 of saturated steam (temperature: about 150 ° C.) is supplied instead of an air flow dryer As the amount of slaked lime in the heated air is supplied at a rate of 180 kg / hour (144 kg / hour as slaked lime) while supplying heated air at 120 ° C. to the dryer at 42 m 3 / hour. Except that the hydrous slaked lime was dried at 520 kg / m 3 , the same operation as in Example 1 was performed to obtain a dried slaked lime powder having a moisture content of 1% by mass or less. Table 1 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0028]
[Reference Example 1]
Instead of the air-flow dryer, a shelf-type vacuum dryer (dry effective volume: 0.0085 m 3 ) was used, and 6.25 kg of hydrous slaked lime (5 kg as slaked lime) was introduced into the dryer, Except for heating at 1 ° C. for 1 hour and drying, the same operation as in Example 1 was performed to obtain dry slaked lime powder having a moisture content of 1% by mass or less. Table 1 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0029]
[Table 1]
Note 2) In Comparative Example 1, the hydrous slaked lime is not dispersed in the heated air.
[0030]
[Experimental Example 4]
Digestion and ripening of quicklime under the same conditions as in Example 1 (2) except that diethylene glycol corresponding to 0.5% by mass was dissolved in digested water with respect to the amount of slaked lime generated after digestion. To obtain hydrous slaked lime having a water content of 20% by mass.
Next, while supplying heated air at 200 ° C. under a condition of 250 m 3 / hour into an airflow dryer (dry effective volume: 0.037 m 3 ), hydrous slaked lime was supplied at 40 kg / hour (32 kg / hour as slaked lime). The hydrated slaked lime was dried by supplying it under conditions so that the amount of slaked lime in the heated air was 1.4 kg / m 3 to obtain a dry slaked lime powder having a water content of 1% by mass or less. Table 2 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0031]
[Experimental Example 5]
Instead of an air flow dryer, a conduction heat transfer fluidized bed dryer (effective drying volume: 0. 0) having a heat exchanger in which 5 kg / cm 2 of saturated steam (temperature: about 150 ° C) is supplied. 15 m 3 ), supplying heated slaked lime at a rate of 230 kg / hour (184 kg / hour as slaked lime) while supplying heated air at 150 ° C. to the dryer at a rate of 432 m 3 / hour. as a 260 kg / m 3 as slaked lime amounts, except for drying the water-containing hydrated lime, by performing the same operation as experiment example 4, to give a water content of 1 mass% or less of the dry hydrated lime powder. Table 2 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0032]
[Comparative Example 2]
An indirect heating dryer (effective drying volume: 0.060 m 3 ) equipped with a heat transfer device in which 5 kg / cm 2 of saturated steam (temperature: about 150 ° C.) is supplied instead of an air flow dryer As the amount of slaked lime in the heated air is supplied at a rate of 180 kg / hour (144 kg / hour as slaked lime) while supplying heated air at 120 ° C. to the dryer at 42 m 3 / hour. as a 520 kg / m 3, except for drying the water-containing hydrated lime, by performing the same operation as experiment example 4, to give a water content of 1 mass% or less of the dry hydrated lime powder. Table 2 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0033]
[Reference Example 2]
Instead of the air-flow dryer, a shelf-type vacuum dryer (dry effective volume: 0.0085 m 3 ) was used, and 6.25 kg of hydrous slaked lime (5 kg as slaked lime) was introduced into the dryer, except that dried by heating 1 hour at ℃ is performed the same operation as experiment example 4, to give a water content of 1 mass% or less of the dry hydrated lime powder. Table 2 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0034]
[Table 2]
Table 2 (digested water: 0.5% by weight of diethylene glycol added)
───────────────────────────────────
Amount of slaked lime in heated air BET specific surface area
(Kg / m 3 ) (m 2 / g)
───────────────────────────────────
Experimental Example 4 1.4 47.0
Experimental Example 5 260 46.0
───────────────────────────────────
Comparative Example 2 520 38.8
───────────────────────────────────
Reference Example 2-45.0
───────────────────────────────────
Note) In Comparative Example 2, the hydrous slaked lime is not dispersed in the heated air.
[0035]
[Example 6]
Example 1 except that diethylene glycol corresponding to 0.5% by mass and D-sorbitol corresponding to 1.0% by mass were dissolved in digested water with respect to the amount of slaked lime generated after digestion. Under the same conditions as 2), quick lime was digested and aged to obtain hydrous slaked lime having a water content of 20% by mass.
Next, in a conduction heat transfer fluidized bed dryer (drying effective volume: 0.15 m 3 ) equipped with a heat transfer device in which 5 kg / cm 2 of saturated steam (temperature: about 150 ° C.) is supplied, While supplying heated air at 150 ° C. at a condition of 432 m 3 / hour, supplying hydrous slaked lime at a condition of 230 kg / hour (184 kg / hour as slaked lime) so that the amount of slaked lime in the heated air is 260 kg / m 3. Then, the hydrous slaked lime was dried to obtain a dried slaked lime powder having a moisture content of 1% by mass or less. Table 3 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0036]
[Reference Example 3]
Instead of a conduction heat transfer fluidized bed dryer, a shelf-type vacuum dryer (dry effective volume: 0.0085 m 3 ) was used, and 6.25 kg of hydrous slaked lime (5 kg / hour as slaked lime) was put into the dryer. Then, except for heating at 200 ° C. under reduced pressure for 1 hour and drying, the same operation as in Example 6 was performed to obtain a dry slaked lime powder having a moisture content of 1% by mass or less. Table 3 shows values of the BET specific surface area of the obtained dried slaked lime powder.
[0037]
[Table 3]
【The invention's effect】
By utilizing the present invention, industrially advantageously producing slaked lime having a specific surface area equal to or greater than that when a vacuum dryer is used for drying hydrous slaked lime performed in the production of slaked lime by digestion of quicklime. Can do. Therefore, according to the present invention, without using too much amounts of the specific surface area enhancers, slaked lime with a specific surface area on 5 0 m 2 / g or more, at relatively low cost, it can be efficiently produced.
Claims (4)
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| CN117735863A (en) * | 2024-01-24 | 2024-03-22 | 常熟理工学院 | Lime slaking method for preparing slaked lime with high specific surface area |
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