JP3781500B2 - Dispersion stabilizer for carbonaceous powder slurry - Google Patents

Description

ここで、Ｒ_１ ：炭素数１〜２０のアルキル基、フェニル基
ＡＯ、ＢＯ：炭素数２〜５のオキシアルキレン基
ＡＯ、ＢＯは、ブロック及び／またはランダム
ｍ、ｎ：０〜１００の整数。但し、１００≧ｍ＋ｎ≧４
に関する。
【０００６】
【発明の実施の形態】
以下に、本発明を詳細に説明する。
本発明で用いるのは下記、一般式（Ｉ）で示すポリオキシアルキレンモノグリシジルエーテル（Ａ）である。
一般式（Ｉ）

ここで、Ｒ_１ ：炭素数１〜２０のアルキル基、フェニル基
ＡＯ、ＢＯ：炭素数２〜５のオキシアルキレン基
ＡＯ、ＢＯは、ブロック及び／またはランダム
ｍ、ｎ：０〜１００の整数。但し、１００≧ｍ＋ｎ≧４
一般式（Ｉ）ポリオキシアルキレンモノグリシジルエーテル（Ａ）で示される化合物には、フェノールポリオキシエチレングリシジルエーテル、フェノールポリオキシプロピレングリシジルエーテル、フェノールポリオキシエチレンオキシプロピレングリシジルエーテル、ラウリルアルコールポリオキシエチレングリシジルエーテル、ラウリルアルコールポリオキシプロピレングリシジルエーテル、ラウリルアルコールポリオキシエチレンオキシプロピレングリシジルエーテル等のポリオキシアルキレングリシジルエーテル類である。
このオキシアルキレン基は炭素数２〜５である。このオキシアルキレンは１種類でも良いが、２種類以上のオキシアルキレンがブロックまたはランダムに結合しているものでも良い。繰り返し単位としては、４〜１００個であり、さらに好ましくは７〜７０個である。
【０００７】
この一般式（Ｉ）で示す化合物の添加する工程は、本発明の共縮合物を合成するどの工程でも良い。すなわち、反応開始時に予め反応装置内に仕込んでおいても良いし、ｐＨを弱酸性領域の条件でホルムアルデヒド共縮合反応させる場合はｐＨ調整する直前及び直後のどちらに添加しても良い。
【０００８】
また、一般式（Ｉ）で示す化合物は１種類以上組み合わせて使用することができる。さらには、その添加量は、ポリオキシアルキレンモノグリシジルエーテル（Ａ）とホルムアルデヒド共縮合が可能な単量体（Ｂ）１モルに対して、０．００５〜０．５モルが好ましく、更に好ましくは０．０１〜０．３５モルが好適である。
【０００９】
ポリオキシアルキレンモノグリシジルエーテル（Ａ）とホルムアルデヒド共縮合が可能な単量体（Ｂ）としては、
一般式（ＩＩ）

ここで、Ｘ_１Ｘ_２Ｘ_３：Ｈ、ＣＨ_２ＯＨ又はＣＨ_２ＳＯ_３Ｙ
Ｙ：アルカリ金属、アルカリ土類金属、アンモニウム、アミン、置換アミン
で示す化合物、すなわち、メラミン、メチロール基含有メラミン、スルホメチル基含有メラミン等を用いることができる。スルホメチル基含有メラミンの場合は、その塩類も用いることができる。塩類としては、無機塩類、すなわち、カリウム、ナトリウム、マグネシウム等のアルカリ金属塩類またはアルカリ土類金属塩類、または有機塩類、すなわち、アンモニウム塩、モノエタノールアミン塩、ジエタノールアミン塩等も用いることができる。なかでも、メラミン及びスルホメチル基含有メラミンが経済的にも反応性からも好ましい。
【００１０】
また、その他として、
一般式（ＩＩＩ）

ここで、Ｘ_４：Ｈ、ＣＨ_２ＯＨ又はＣＨ_２ＳＯ_３Ｙ、アンモニウム塩、アミン塩、置換アミン塩
Ｙ：アルカリ金属、アルカリ土類金属、アンモニウム、アミン、置換アミンスルホン基、又はそのアルカリ金属塩、アルカリ土類金属、
Ｒ_３：Ｈ又は炭素数１〜６のアルキル基
で示す化合物、すなわち、フェノール、クレゾール、ｐ−ｔ−ブチルフェノール、ｐ−ｔ−アミルフェノール等のアルキルフェノール類、またはそのスルホン酸類もしくはスルホン酸の塩類等も用いることができる。塩類としては、一般式（ＩＩ）と同様に、その無機塩類や有機塩類も用いることができる。
【００１１】
さらには、
一般式（ＩＶ）

ここで、Ｘ_５、Ｘ_６：Ｈ、ＣＨ_２ＯＨ又はＣＨ_２ＳＯ_３Ｙ
Ｙ：アルカリ金属、アルカリ土類金属、アンモニウム、アミン、置換アミン
で示す化合物、すなわち、尿素、メチロール基含有尿素、スルホメチル基含有尿素も用いることができる。また、スルホメチル基含有尿素の場合は、一般式（ＩＩ）と同様に、その無機塩類や有機塩類も用いることができる。
【００１２】
さらには、
一般式（Ｖ）

ここで、Ｘ_７：Ｈ、アルカリ金属、アルカリ土類金属、アンモニウム、アミン、置換アミン
Ｒ_３：Ｈ又は炭素数１〜６のアルキル基
で示す化合物、すなわち、スルファニル酸、メタニン酸、オルタニン酸等のアミノベンゼンスルホン酸類、またはその塩類を用いることができる。塩類としては、一般式（ＩＩ）と同様に、その無機塩類や有機塩類も用いることができる。なかでも、スルファニル酸やメタニン酸及びその塩類が経済的にも反応性からも好ましい。
【００１３】
尚、本発明においては、一般式（ＩＩ）、一般式（ＩＩＩ）、一般式（ＩＶ）、及び一般式（Ｖ）の１種類以上の単量体を組み合わせて用いることができるが、一般式（ＩＩ）を用いることが経済的にも反応性からも好ましい。
【００１４】
スルホン基を生成する化合物としては、亜硫酸ナトリウム、重亜硫酸ナトリウム、ピロ亜硫酸ナトリウム、二酸化硫黄、発煙硫酸等の公知のスルホン化剤を用いることができる。
これらのスルホン化剤は、予め一般式（ＩＩ）、一般式（ＩＩＩ）及び一般式（ＩＶ）の相当する原料にスルホメチル基を導入する際に用いても良いし、ホルムアルデヒドによる共縮合体を合成したのちに作用させて、共縮合体に直接スルホメチル基を導入しても良い。
【００１５】
メラミンにスルホメチル基を導入する方法は、公知の方法で行うことができる。すなわち、メラミンにホルムアルデヒドを付加縮合させ、メチロールメラミンとしたのちに、スルホン化剤を作用させ、水酸基と入れ換えることにより導入することが可能である。メラミン１モルには６モルのホルムアルデヒドがメチロール基として付加縮合することが知られている。本発明においては、２モル分のメチロール基は共縮合に用いられる可能性が高いので、最大は残りの４モル分のメチロール基にスルホメチル基の導入が可能である。経済的な面及び得られる共縮合物の分散効果を考慮すると、スルホメチル基の導入量は０．３〜４モルが好ましく、さらに好ましくは０．５〜２モルの導入が好適である。
【００１６】
また、フェノールにスルホメチル基を導入する場合も同様であり、フェノール１モル当たり０．３〜２モルの導入量が好ましく、さらに好ましくは０．５〜１．５モルの導入が好適である。
さらには、尿素にスルホメチル基を導入する場合も同様であり、尿素１モル当たり０．３〜２モルの導入量が好ましく、さらに好ましくは０．５〜１．５モルの導入が好適である。
【００１７】
これらのホルムアルデヒド共縮合体を合成するにあたって用いられるホルムアルデヒドは、通常３０〜６０重量％の濃度のものが用いることが可能である。さらには、必要に応じて、パラホルムを併用することも可能である。このホルムアルデヒドの使用量は、ポリオキシアルキレンモノグリシジルエーテル（Ａ）とホルムアルデヒド共縮合が可能な単量体（Ｂ）の総モル数の１〜６倍モル用いることが好ましい。経済性や縮合反応の容易さ等を考慮すると１．５〜４倍モルを用いることがより好ましい。
ホルムアルデヒド共縮合反応はｐＨ４〜１２の範囲、いわゆる弱酸性領域から塩基性領域の通常の方法で行う。ホルムアルデヒドの添加は、予め反応装置内に仕込んでおいても良いし、反応途中に滴下して反応させても良い。
【００１８】
本発明における炭素質粉末スラリー用分散安定剤（以下、単に分散安定剤と略す）を構成する化合物の組成は重要である。すなわち、ポリオキシアルキレンモノグリシジルエーテル（Ａ）：ポリオキシアルキレンモノグリシジルエーテル（Ａ）とホルムアルデヒド共縮合が可能な単量体（Ｂ）：スルホン基を生成する化合物（Ｃ）：ホルムアルデヒドのモル比率は、（０．００５〜０．５）：１：（０．３〜４）：（１〜６）であることが好ましい。さらに好ましくは、（０．０１〜０．３５）：１：（０．５〜２）：（１．５〜４）が好適である。
【００１９】
本発明における分散安定剤の添加量は、炭素質粉末の種類で変動するが、一般的には炭素質粉末に対して固形分量で０．０５〜３．０重量％が好ましい。さらに好ましくは、０．５〜２．０重量％が好適である。
【００２０】
本発明の分散安定剤の使用方法に関しては、単独で用いても良いが、公知の他の１種類以上の分散剤と組み合わせて使用することもできる。公知の他の分散剤としては、例えばナフタレンスルホン酸ホルムアルデヒド縮合物塩（以下、ナフタレン系と称す）、メラミンスルホン酸ホルムアルデヒド重縮合物塩（以下、メラミン系と称す）、リグニンスルホン酸塩（以下、リグニン系と称す）、ポリスチレンスルホン酸塩（以下、ポリスチレン系と称す）、ポリオキシエチレンアルキルフェニルエーテル、ポリ（メタ）アクリル酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、（メタ）アクリル酸とビニルモノマーの共重合体塩、（メタ）アクリル酸と分子内にポリオキシアルキレングリコール鎖を有するビニルモノマーとの共重合体塩、ヒドロキシエタンジホスホン酸塩、ノニルフェノール縮合物エチレンオキサイド付加物、ポリエチレンポリアミンとアルキレンオキサイドの付加重合物等が挙げられる。
【００２１】
さらには、本発明の分散安定剤は、分散安定性をさらに向上させるために、公知の他の１種類以上の水溶性高分子と併用して使用することができる。公知の他の水溶性高分子としては、メチルセルロース、カルボキシメチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、スルホエチルセルロースアルカリ金属塩等のセルロース誘導体、ポリビニルアルコール及びその誘導体、澱粉及びその誘導体類、アルギン酸ソーダ、カゼイン、キサンタンガム、タマリンドガム、グアーガム等の天然高分子及びその誘導体類、カードラン、パラミロン等のβ−１，３−グルカン及びウエランガム等の微生物生産多糖類、アクリル酸または不飽和多塩基酸と他のビニルモノマーとの共重合体類の高分子量物、ポリアクリルアミドまたはアクリルアミドと他のビニルモノマーとの共重合体類の高分子量物等が挙げられる。
【００２２】
本発明の分散安定剤が、炭素質粉末スラリーに優れた流動性を与え、長期に亘ってハードパックを形成することなく分散安定性を維持し、スラリーの高濃度化を可能にする理由は明かではないが、次のように推測される。
すなわち、本発明の分散安定剤は分子中にスルホン基を有しているため、その電気的反発力によって炭素質微粒子の分散性を高める。また、本発明の分散安定剤が炭素質微粒子に吸着した際に、分子内に有するポリオキシアルキレン基が粒子の外側に伸びると考えられる。この外側に伸びたポリオキシアルキレン基のまわりに水和層が形成され、これに伴う立体障害効果によって炭素質微粒子の分散性を長時間保持し、ハードパックを引き起こさないのではないかと予想される。
【００２３】
本発明の分散安定剤について、以下の実施例にてさらに詳しく説明するが、本発明はこれに限定されるものではない。また、以下に数値の単位として記載する％または部は、特に記載がなければ、全て重量％または重量部である。
【００２４】
【実施例】
製造例１
メラミン０．５２モル（６５．５部）、３７％ホルマリン３．０モル（２４３．２部）、水２５０．０部を撹拌機、温度計、還流管、滴下漏斗のついた４つ口フラスコに仕込み、撹拌混合した。これを６５℃まで昇温した後に２５％水酸化ナトリウム水溶液でｐＨ１１．５とし、６５℃で１時間反応させた。これに尿素０．２モル（１２．０部）及びスルファニル酸０．１５モル（２６．０部）を添加し、７０℃でさらに１時間反応させた。次に水１３１．４部を投入すると同時に４５℃まで冷却した後、フェノール０．１３モル（１２．２部）を滴下漏斗を用いて３０分かけて投入した。投入終了後、６０℃で１時間反応させた。続いて、ラウリルアルコール（ＥＯ）１５グリシジルエーテルであるデナコールＥＸ−１７１（ナガセ化成工業（株）社製）を０．０３モル（２７．１部）、無水重亜硫酸ナトリウム０．５３モル（５５．１部）を投入し、８０℃で１時間反応させた。６０℃まで冷却した後、４０％硫酸でｐＨ６．０にし、６５℃に昇温して反応させ、反応溶液の粘度が４０ｃｐ／２５℃になった時点で、２５％水酸化ナトリウム水溶液で中和して反応を停止させ、得られた生成物を縮合物１とした。この組成及び物性値を表１に示す。
【００２５】
製造例２
水６４７．８部、３７％ホルマリン３．１モル（２５１．４部）を撹拌機、温度計、還流管のついた４つ口フラスコに仕込み、撹拌混合した。このフラスコ中にメラミン０．７モル（８８．２部）、尿素０．１モル（６．０部）、スルファニル酸０．２モル（３４．６部）、ピロ亜硫酸ナトリウム０．５モル（９５．０部）を撹拌下で添加した。このものを７５℃まで昇温し、透明液体となったことを確認した後に、製造例１で使用したデナコールＥＸ−１７１を０．１３モル（１１７．３部）添加後、２５％水酸化ナトリウム水溶液でｐＨ１１とし、７５℃で２時間反応させた。フリーの亜硫酸イオンが消失したことを確認した後に、６０℃まで冷却した。次に４０％硫酸でｐＨ６．０にし、６０℃で反応を進め、反応溶液の粘度が５０ｃｐ／２５℃になった時点で、２５％水酸化ナトリウム水溶液で中和して反応を停止させ、得られた生成物を縮合物２とした。この組成及び物性値を表１に示す。
【００２６】
製造例３
水３５２．３部、３７％ホルマリン２．８モル（２２７．０部）を撹拌機、温度計、還流管のついた４つ口フラスコに仕込み、撹拌混合した。このフラスコ中にメラミン１．０モル（１２６．０部）を撹拌下で添加する。このものを７０℃まで昇温し、透明液体となったことを確認した後に、フェノール（ＥＯ）５グリシジルエーテルであるデナコールＥＸ−１４５（ナガセ化成工業（株）社製）０．１モル（３７．０部）２５％水酸化ナトリウム水溶液でｐＨ１１とし、７０℃で１時間反応させた。次に５５℃まで冷却し、無水重亜硫酸ナトリウム０．８（８３．２部）を添加した。無水重亜硫酸ナトリウムの添加により内温は上昇するが、さらに８０℃まで昇温した。８０℃で反応を続行し、フリーの亜硫酸イオンが消失したことを確認した後に、６０℃まで冷却した。次に４０％硫酸でｐＨ６．０にし、６０℃で反応を進め、反応溶液の粘度が１１５ｃｐ／２５℃になった時点で、２５％水酸化ナトリウム水溶液で中和して反応を停止させ、得られた生成物を縮合物３とした。この組成及び物性値を表１に示す。
【００２７】
製造例４〜５
製造例１と同様の方法で、表１に示すように化合物の組成と最終粘度を変えて、縮合した。その結果、縮合物４〜５を得た。
【００２８】
製造例６〜７
製造例２と同様の方法で、表１に示すように化合物の組成と最終粘度を変えて縮合した。その結果、縮合物６〜７を得た。
【００２９】
製造例８〜９
製造例３と同様の方法で、表１に示すように化合物の組成と最終粘度を変えて縮合した。その結果、縮合物８〜９を得た。
【００３０】
製造例１０
一般式（ｌ）で表せられる化合物を用いなかった以外は、製造例１と同様の方法で、表１に示すように化合物の組成と最終粘度を変えて縮合した。その結果、縮合物１０を得た。
【００３１】
製造例１１〜１２
合成例１で用いたデナコールＥＸ−１７１を用い、製造例１と同様の方法で、表１に示すように化合物の組成と最終粘度を変えて縮合した。その結果、縮合物１１〜１２を得た。
【００３２】
【表１】

【００３３】
実施例１
以下に記述するように炭素質粉末スラリーとして、製造例１で合成した縮合物１を用いて石炭粉末の水スラリー及びオイルコークス粉末の水スラリーを調製し、分散性及び分散安定性の評価を行った。結果を表２に示す。
【００３４】
１．炭素質粉末スラリーの調製
石炭は２００メッシュパス分を９５％含有するオーストラリア産のものを用いた。予め所定量の本発明の分散安定剤、または比較分散安定剤、または比較分散剤を水中に入れ、その中に所定量の石炭粉末を徐々に添加し、ホモミキサーで３０００ｒｐｍにて２５分間分散させて、石炭スラリーとした。
オイルコークスは宇部アンモニア工業有限会社から入手したオイルコークス塊をジョークラッシャーで粗粉砕した後、奈良式自由粉砕機で粉砕し、５０％粒径が２７μｍ、９０％粒径が９５μｍのものを得た。これを石炭スラリーと同様の方法でオイルコークススラリーとした。
【００３５】
２．流動性の評価
上記調製方法で得られた炭素質粉末スラリーを所定の温度にし、ブルックフィールド型粘度計で粘度を測定した。また、７日後の粘度測定も実施した。
【００３６】
３．分散安定性の評価
炭素質粉末スラリー調製後に１００ｃｃ容のポリカップに底から４５ｍｍの高さになるようにスラリーを移液した。そのものをＪＩＳ Ｒ５２０１に規定されているビガー針を用い、自重による１０秒間の針の落下距離を測定した。また、７日間静置しておいたスラリーを測定することで、分散安定性の指標とした。ちなみに落下距離が短い物ほど、分散安定性が悪いことを示す。
【００３７】
実施例２〜１２
製造例２〜９で得られた縮合物２〜９を用いた以外は、実施例１と同様の試験を行った。結果は表２に示す。
【００３８】
比較例１〜３
製造例１０〜１２で得られた縮合物１０〜１２を用いた以外は、実施例１と同様の試験を行った。結果は表２に示す。
【００３９】
比較例４〜７
比較対照用の分散剤として、市販のメルフロー４０（三井東圧化学（株）：メラミン系）、マイティー１５０（花王（株）：ナフタレン系）、グラリオン（ライオン（株）：ポリスチレン系）、ＷＥＳＣＨＥＭ Ｎａ−１（ジョージア・パシフィック（株）：リグニン系）を用いて、実施例１と同様の操作を行った。結果を表２に示す。
【００４０】
【表２】

【００４１】
【発明の効果】
実施例及び比較例から明らかであるように、本発明によって得られる炭素質粉末用分散安定剤は、既存の分散剤に比較して、低添加量で高い分散効果を示し、且つ分散安定性に優れる。すなわち、容易にスラリーの高濃度化が可能となり、発熱量の向上、輸送費用の低減、及び貯蔵性の改善等の大きなメリットが期待される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dispersant for a carbonaceous powder slurry. More specifically, the present invention relates to a dispersion stabilizer for dispersing, for example, coal powder or oil coke powder in water and obtaining a high-concentration slurry that is stable for a long period of time while being capable of pipeline transportation.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, oil has been used the most in the world as an energy source. However, since the resources are unevenly distributed and the reserves are feared to be exhausted, sometimes there is a global supply insecurity. Therefore, early development of petroleum alternative energy is desired to reduce the dependence on oil. Among them, coal which is widely present all over the world and is inexpensive and can be stably supplied is being reviewed. It is also conceivable to use oil coke generated as a distillation residue when pyrolyzing heavy fractions during petroleum refining as an energy source. The problem in this case is that coal and oil coke are solid, so they are poor in handling and cannot be transported by pipeline like oil, which is extremely disadvantageous in handling. In order to solve this problem, various methods have been studied in which coal or oil coke is pulverized, dispersed in a liquid such as water, oil or methanol, and transported and stored as a slurry. Among them, the one in which coal or oil coke powder is dispersed in water is currently most promising.
[0003]
Here, when coal powder or oil coke powder is dispersed in water, it is desired to increase the concentration as much as possible because of a decrease in calorific value and an increase in transportation costs. However, when the concentration of these slurries is increased, the viscosity is remarkably increased and the fluidity is lost. Thus, attempts have been made to use various dispersants when dispersing these powders in water. Examples of various dispersants include naphthalene sulfonic acid formaldehyde condensate salt (Japanese Patent Publication No. 60-6395), melamine sulfonic acid formaldehyde polycondensate salt (Japanese Patent Laid-Open No. 57-133192), and lignin sulfonate (Japanese Patent Publication No. 2005-126). 01-28798), polystyrene sulfonate (Japanese Patent Laid-Open No. 03-200893), copolymer salt of (meth) acrylic acid and vinyl monomer (Japanese Patent Publication No. 62-52791), hydroxyethane diphosphonate And nonylphenol condensate etherene oxide adduct (Japanese Patent Laid-Open No. 59-80320), addition polymer of polyethylene polyamine and alkylene oxide (Japanese Patent Publication No. 4-43957), and the like. However, these dispersants are not sufficiently satisfactory for practical use with respect to fluidity and dispersion stability.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to improve the flowability and dispersion stability at high concentrations, which are the disadvantages of carbonaceous powder slurries such as coal and oil coke, the present inventors have found compounds having a specific structure. When used as a dispersant, it has been found to have an excellent dispersing effect, and the present invention has been made.
[0005]
That is, the present invention relates to a polyoxyalkylene monoglycidyl ether (A) represented by the following general formula (I), a monomer (B) capable of formaldehyde cocondensation with the polyoxyalkylene monoglycidyl ether (A), and a sulfone. Dispersion stabilizer for carbonaceous powder slurry which consists of formaldehyde cocondensate of compound (C) which produces | generates group.
Formula (I)

Here, R ₁ : an alkyl group having 1 to 20 carbon atoms, a phenyl group AO, BO: an oxyalkylene group AO or BO having 2 to 5 carbon atoms is a block and / or random m, and n is an integer of 0 to 100. However, 100 ≧ m + n ≧ 4
About.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The polyoxyalkylene monoglycidyl ether (A) represented by the following general formula (I) is used in the present invention.
Formula (I)

Here, R ₁ : an alkyl group having 1 to 20 carbon atoms, a phenyl group AO, BO: an oxyalkylene group AO or BO having 2 to 5 carbon atoms is a block and / or random m, and n is an integer of 0 to 100. However, 100 ≧ m + n ≧ 4
The compound represented by the general formula (I) polyoxyalkylene monoglycidyl ether (A) includes phenol polyoxyethylene glycidyl ether, phenol polyoxypropylene glycidyl ether, phenol polyoxyethyleneoxypropylene glycidyl ether, lauryl alcohol polyoxyethylene glycidyl. Polyoxyalkylene glycidyl ethers such as ether, lauryl alcohol polyoxypropylene glycidyl ether, and lauryl alcohol polyoxyethyleneoxypropylene glycidyl ether.
This oxyalkylene group has 2 to 5 carbon atoms. One oxyalkylene may be used, but two or more oxyalkylenes may be combined in a block or randomly. The number of repeating units is 4 to 100, and more preferably 7 to 70.
[0007]
The step of adding the compound represented by the general formula (I) may be any step of synthesizing the cocondensate of the present invention. That is, it may be charged in the reaction apparatus in advance at the start of the reaction, or when the formaldehyde co-condensation reaction is carried out under a weakly acidic condition, it may be added either immediately before or after pH adjustment.
[0008]
Moreover, the compound shown by general formula (I) can be used in combination of 1 or more types. Furthermore, the addition amount is preferably 0.005 to 0.5 mol, more preferably 1 mol with respect to 1 mol of polyoxyalkylene monoglycidyl ether (A) and monomer (B) capable of formaldehyde cocondensation. 0.01 to 0.35 mol is preferred.
[0009]
As a polyoxyalkylene monoglycidyl ether (A) and a monomer (B) capable of formaldehyde cocondensation,
Formula (II)

Here, X ₁ X ₂ X ₃ : H, CH ₂ OH or CH ₂ SO ₃ Y
Y: A compound represented by alkali metal, alkaline earth metal, ammonium, amine, substituted amine, that is, melamine, methylol group-containing melamine, sulfomethyl group-containing melamine, or the like can be used. In the case of sulfomethyl group-containing melamine, salts thereof can also be used. As the salts, inorganic salts, that is, alkali metal salts or alkaline earth metal salts such as potassium, sodium, and magnesium, or organic salts, that is, ammonium salts, monoethanolamine salts, diethanolamine salts, and the like can be used. Among these, melamine and sulfomethyl group-containing melamine are preferable from the viewpoint of economy and reactivity.
[0010]
In addition,
Formula (III)

Here, X ₄ : H, CH ₂ OH or CH ₂ SO ₃ Y, ammonium salt, amine salt, substituted amine salt Y: alkali metal, alkaline earth metal, ammonium, amine, substituted amine sulfone group, or alkali metal thereof Salt, alkaline earth metal,
R ₃ : a compound represented by H or an alkyl group having 1 to 6 carbon atoms, that is, alkylphenols such as phenol, cresol, pt-butylphenol, pt-amylphenol, sulfonic acids or salts of sulfonic acids, etc. Can also be used. As the salts, inorganic salts and organic salts thereof can be used as in the general formula (II).
[0011]
Moreover,
Formula (IV)

_{Here, X 5, X 6: H} , CH 2 OH or _CH 2 _SO 3 Y
Y: Compounds represented by alkali metals, alkaline earth metals, ammonium, amines, substituted amines, that is, urea, methylol group-containing urea, sulfomethyl group-containing urea can also be used. In the case of a sulfomethyl group-containing urea, inorganic salts and organic salts thereof can be used as in the general formula (II).
[0012]
Moreover,
General formula (V)

Here, X ₇ : H, alkali metal, alkaline earth metal, ammonium, amine, substituted amine R ₃ : H or a compound represented by an alkyl group having 1 to 6 carbon atoms, that is, sulfanilic acid, metanic acid, alternic acid, etc. Aminobenzenesulfonic acids or salts thereof can be used. As the salts, inorganic salts and organic salts thereof can be used as in the general formula (II). Of these, sulfanilic acid, methanoic acid and salts thereof are preferable from the viewpoint of economy and reactivity.
[0013]
In the present invention, one or more monomers of general formula (II), general formula (III), general formula (IV), and general formula (V) can be used in combination. Use of (II) is preferred from the economical and reactive viewpoints.
[0014]
As a compound which produces | generates a sulfone group, well-known sulfonating agents, such as sodium sulfite, sodium bisulfite, sodium pyrosulfite, sulfur dioxide, fuming sulfuric acid, can be used.
These sulfonating agents may be used in advance when a sulfomethyl group is introduced into the corresponding raw materials of the general formula (II), general formula (III), and general formula (IV), or a co-condensate of formaldehyde is synthesized. Thereafter, a sulfomethyl group may be directly introduced into the cocondensate by acting.
[0015]
The method for introducing a sulfomethyl group into melamine can be carried out by a known method. That is, after formaldehyde is added and condensed to melamine to form methylolmelamine, it can be introduced by acting a sulfonating agent and replacing it with a hydroxyl group. It is known that 6 mol of formaldehyde is added and condensed as a methylol group to 1 mol of melamine. In the present invention, 2 moles of methylol groups are likely to be used for co-condensation, so the maximum is that a sulfomethyl group can be introduced into the remaining 4 moles of methylol groups. Considering the economical aspect and the dispersion effect of the resulting cocondensate, the introduction amount of the sulfomethyl group is preferably 0.3 to 4 mol, more preferably 0.5 to 2 mol.
[0016]
The same applies when a sulfomethyl group is introduced into phenol, and an introduction amount of 0.3 to 2 mol per mol of phenol is preferred, and introduction of 0.5 to 1.5 mol is more preferred.
Further, the same applies when a sulfomethyl group is introduced into urea, and an introduction amount of 0.3 to 2 mol per mol of urea is preferable, and introduction of 0.5 to 1.5 mol is more preferable.
[0017]
The formaldehyde used in synthesizing these formaldehyde cocondensates can be used usually at a concentration of 30 to 60% by weight. Furthermore, paraform can be used in combination as necessary. The amount of formaldehyde used is preferably 1 to 6 times the total number of moles of polyoxyalkylene monoglycidyl ether (A) and monomer (B) capable of formaldehyde cocondensation. In view of economy, ease of condensation reaction, etc., it is more preferable to use 1.5 to 4 moles.
The formaldehyde co-condensation reaction is carried out by a usual method in the range of pH 4 to 12, so-called weakly acidic region to basic region. Addition of formaldehyde may be previously charged in the reaction apparatus, or may be dropped during the reaction to cause the reaction.
[0018]
The composition of the compound constituting the dispersion stabilizer for carbonaceous powder slurry in the present invention (hereinafter simply referred to as dispersion stabilizer) is important. That is, a polyoxyalkylene monoglycidyl ether (A): a polyoxyalkylene monoglycidyl ether (A) and a monomer capable of cocondensation with formaldehyde (B): a compound that forms a sulfone group (C): a molar ratio of formaldehyde is , (0.005-0.5): 1: (0.3-4) :( 1-6). More preferably, (0.01-0.35): 1: (0.5-2) :( 1.5-4) is suitable.
[0019]
The addition amount of the dispersion stabilizer in the present invention varies depending on the type of carbonaceous powder, but generally 0.05 to 3.0% by weight in solid content with respect to the carbonaceous powder is preferable. More preferably, 0.5 to 2.0% by weight is suitable.
[0020]
The method for using the dispersion stabilizer of the present invention may be used alone or in combination with one or more other known dispersants. Other known dispersants include, for example, naphthalene sulfonic acid formaldehyde condensate salt (hereinafter referred to as naphthalene), melamine sulfonic acid formaldehyde polycondensate salt (hereinafter referred to as melamine), lignin sulfonate (hereinafter referred to as Lignin), polystyrene sulfonate (hereinafter referred to as polystyrene), polyoxyethylene alkylphenyl ether, poly (meth) acrylate, polyoxyethylene alkyl ether sulfate, (meth) acrylic acid and vinyl monomer Copolymer salt of (meth) acrylic acid and vinyl monomer having polyoxyalkylene glycol chain in the molecule, hydroxyethane diphosphonate, nonylphenol condensate ethylene oxide adduct, polyethylene polyamine and alkylene Of oxide Pressurized polymer and the like.
[0021]
Furthermore, the dispersion stabilizer of the present invention can be used in combination with one or more other known water-soluble polymers in order to further improve the dispersion stability. Other known water-soluble polymers include cellulose derivatives such as methylcellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, sulfoethylcellulose alkali metal salts, polyvinyl alcohol and derivatives thereof, starch and derivatives thereof. Natural polymers such as sodium alginate, casein, xanthan gum, tamarind gum and guar gum and their derivatives, β-1,3-glucan such as curdlan and paramylon and polysaccharides produced by microorganisms such as welan gum, acrylic acid or unsaturated poly High molecular weight products of copolymers of basic acid and other vinyl monomers, high molecular weight products of copolymers of polyacrylamide or acrylamide and other vinyl monomers, etc. .
[0022]
The reason why the dispersion stabilizer of the present invention gives excellent flowability to the carbonaceous powder slurry, maintains the dispersion stability without forming a hard pack over a long period of time, and makes it possible to increase the concentration of the slurry. However, it is presumed as follows.
That is, since the dispersion stabilizer of the present invention has a sulfone group in the molecule, the dispersibility of the carbonaceous fine particles is enhanced by the electric repulsive force. Moreover, when the dispersion stabilizer of this invention adsorb | sucks to carbonaceous fine particles, it is thought that the polyoxyalkylene group which has in a molecule | numerator extends to the outer side of particle | grains. It is expected that a hydration layer is formed around the polyoxyalkylene group extending outside, and the dispersibility of the carbonaceous fine particles is maintained for a long time due to the accompanying steric hindrance effect, thereby causing no hard pack. .
[0023]
The dispersion stabilizer of the present invention will be described in more detail in the following examples, but the present invention is not limited thereto. Moreover,% or part described below as a unit of numerical values is all by weight or part by weight unless otherwise specified.
[0024]
【Example】
Production Example 1
Melamine 0.52 mol (65.5 parts), 37% formalin 3.0 mol (243.2 parts), water 250.0 parts with a stirrer, thermometer, reflux tube and dropping funnel The mixture was stirred and mixed. The mixture was heated to 65 ° C., adjusted to pH 11.5 with a 25% aqueous sodium hydroxide solution, and reacted at 65 ° C. for 1 hour. To this, 0.2 mol (12.0 parts) of urea and 0.15 mol (26.0 parts) of sulfanilic acid were added and reacted at 70 ° C. for an additional hour. Next, after 131.4 parts of water was added and simultaneously cooled to 45 ° C., 0.13 mol (12.2 parts) of phenol was added over 30 minutes using a dropping funnel. After completion of the addition, the reaction was carried out at 60 ° C. for 1 hour. Subsequently, 0.03 mol (27.1 parts) of Denacol EX-171 (manufactured by Nagase Kasei Kogyo Co., Ltd.), which is lauryl alcohol (EO) 15 glycidyl ether, and 0.53 mol (55. mol) of anhydrous sodium bisulfite. 1 part) was added and reacted at 80 ° C. for 1 hour. After cooling to 60 ° C., the pH is adjusted to 6.0 with 40% sulfuric acid, the temperature is raised to 65 ° C. and the reaction is performed. When the viscosity of the reaction solution reaches 40 cp / 25 ° C., the solution is neutralized with 25% aqueous sodium hydroxide. Thus, the reaction was stopped, and the resulting product was designated as condensate 1. The composition and physical property values are shown in Table 1.
[0025]
Production Example 2
647.8 parts of water and 3.1 mol (251.4 parts) of 37% formalin were charged into a four-necked flask equipped with a stirrer, thermometer, and reflux tube, and mixed with stirring. Melamine 0.7 mol (88.2 parts), urea 0.1 mol (6.0 parts), sulfanilic acid 0.2 mol (34.6 parts), sodium pyrosulfite 0.5 mol (95%) 0.0 part) was added under stirring. After heating this to 75 ° C. and confirming that it became a transparent liquid, after adding 0.13 mol (117.3 parts) of Denacol EX-171 used in Production Example 1, 25% sodium hydroxide The solution was adjusted to pH 11 with an aqueous solution and reacted at 75 ° C. for 2 hours. After confirming that free sulfite ions disappeared, the mixture was cooled to 60 ° C. Next, the pH is adjusted to 6.0 with 40% sulfuric acid, and the reaction proceeds at 60 ° C. When the viscosity of the reaction solution reaches 50 cp / 25 ° C., the reaction is stopped by neutralization with a 25% aqueous sodium hydroxide solution. The resulting product was designated as condensate 2. The composition and physical property values are shown in Table 1.
[0026]
Production Example 3
352.3 parts of water and 2.8 mol (227.0 parts) of 37% formalin were charged into a four-necked flask equipped with a stirrer, thermometer, and reflux tube, and mixed with stirring. 1.0 mol (126.0 parts) of melamine is added to the flask under stirring. After heating this to 70 ° C. and confirming that it became a transparent liquid, Denacol EX-145 (manufactured by Nagase Kasei Kogyo Co., Ltd.) 0.1 mol (37 0.0 part) The pH was adjusted to 11 with a 25% aqueous sodium hydroxide solution, and the mixture was reacted at 70 ° C. for 1 hour. It was then cooled to 55 ° C. and anhydrous sodium bisulfite 0.8 (83.2 parts) was added. Although the internal temperature increased by addition of anhydrous sodium bisulfite, the temperature was further increased to 80 ° C. The reaction was continued at 80 ° C., and after confirming that free sulfite ions had disappeared, the mixture was cooled to 60 ° C. Next, the pH is adjusted to 6.0 with 40% sulfuric acid and the reaction proceeds at 60 ° C. When the viscosity of the reaction solution reaches 115 cp / 25 ° C., the reaction is stopped by neutralization with a 25% aqueous sodium hydroxide solution. The resulting product was designated as condensate 3. The composition and physical property values are shown in Table 1.
[0027]
Production Examples 4-5
In the same manner as in Production Example 1, the composition of the compound and the final viscosity were changed as shown in Table 1, and condensation was performed. As a result, condensates 4 to 5 were obtained.
[0028]
Production Examples 6-7
In the same manner as in Production Example 2, the composition and final viscosity of the compound were changed as shown in Table 1 for condensation. As a result, condensates 6 to 7 were obtained.
[0029]
Production Examples 8-9
In the same manner as in Production Example 3, the composition and final viscosity of the compound were changed as shown in Table 1 for condensation. As a result, condensates 8 to 9 were obtained.
[0030]
Production Example 10
Except that the compound represented by the general formula (l) was not used, condensation was carried out in the same manner as in Production Example 1 while changing the composition and final viscosity of the compound as shown in Table 1. As a result, a condensate 10 was obtained.
[0031]
Production Examples 11-12
Using Denacol EX-171 used in Synthesis Example 1, the composition and final viscosity of the compound were changed and condensed in the same manner as in Production Example 1, as shown in Table 1. As a result, condensates 11 to 12 were obtained.
[0032]
[Table 1]

[0033]
Example 1
As described below, as the carbonaceous powder slurry, a water slurry of coal powder and an oil coke powder are prepared using the condensate 1 synthesized in Production Example 1, and the dispersibility and dispersion stability are evaluated. It was. The results are shown in Table 2.
[0034]
1. Preparation of Carbonaceous Powder Slurry Coal from Australia containing 95% of 200 mesh pass was used. A predetermined amount of the dispersion stabilizer of the present invention, the comparative dispersion stabilizer, or the comparative dispersant is put in water in advance, and a predetermined amount of coal powder is gradually added thereto, and dispersed with a homomixer at 3000 rpm for 25 minutes. A coal slurry was obtained.
Oil coke was obtained by roughly crushing an oil coke lump obtained from Ube Ammonia Co., Ltd. with a jaw crusher and then crushing with a Nara free grinder to obtain a 50% particle size of 27 μm and a 90% particle size of 95 μm. . This was made into an oil coke slurry in the same manner as the coal slurry.
[0035]
2. Evaluation of fluidity The carbonaceous powder slurry obtained by the above preparation method was brought to a predetermined temperature, and the viscosity was measured with a Brookfield viscometer. Moreover, the viscosity measurement after 7 days was also implemented.
[0036]
3. Evaluation of Dispersion Stability After preparing the carbonaceous powder slurry, the slurry was transferred to a 100 cc polycup so that the height was 45 mm from the bottom. Using the bigger needle prescribed | regulated to JISR5201, the fall distance of the needle for 10 second by own weight was measured. Moreover, it was set as the parameter | index of dispersion stability by measuring the slurry left still for 7 days. Incidentally, the shorter the drop distance, the worse the dispersion stability.
[0037]
Examples 2-12
The same test as in Example 1 was performed except that the condensates 2 to 9 obtained in Production Examples 2 to 9 were used. The results are shown in Table 2.
[0038]
Comparative Examples 1-3
The same test as in Example 1 was performed except that the condensates 10-12 obtained in Production Examples 10-12 were used. The results are shown in Table 2.
[0039]
Comparative Examples 4-7
As a comparative dispersant, commercially available Melflow 40 (Mitsui Toatsu Chemical Co., Ltd .: Melamine), Mighty 150 (Kao Corporation: Naphthalene), Glarion (Lion Corporation: Polystyrene), WESCHEM Na -1 (Georgia Pacific Co., Ltd .: Lignin system) was used to carry out the same operation as in Example 1. The results are shown in Table 2.
[0040]
[Table 2]

[0041]
【The invention's effect】
As is clear from the examples and comparative examples, the dispersion stabilizer for carbonaceous powder obtained by the present invention exhibits a high dispersion effect at a low addition amount as compared with the existing dispersants, and also has good dispersion stability. Excellent. That is, it is possible to easily increase the concentration of the slurry, and great merits such as an improvement in heat generation, a reduction in transportation costs, and an improvement in storage properties are expected.

Claims (11)

A polyoxyalkylene monoglycidyl ether (A) represented by the following general formula (I), a monomer (B) capable of formaldehyde co-condensation with the polyoxyalkylene monoglycidyl ether (A), and a compound producing a sulfone group ( Dispersion stabilizer for carbonaceous powder slurry comprising a formaldehyde cocondensate with C).
Formula (I)

Here, R ₁ : an alkyl group having 1 to 20 carbon atoms, a phenyl group AO, BO: an oxyalkylene group AO or BO having 2 to 5 carbon atoms is a block and / or random m, and n is an integer of 0 to 100. However, 100 ≧ m + n ≧ 4 Monomers (B) capable of formaldehyde co-condensation with polyoxyalkylene monoglycidyl ether (A) are melamine or derivatives thereof, phenol or derivatives thereof, urea or derivatives thereof, aminobenzenesulfonic acid or derivatives thereof, or alkylamino The dispersion stabilizer for carbonaceous powder slurry according to claim 1, comprising one or more compounds selected from the group consisting of benzenesulfonic acid or derivatives thereof. 2. The carbonaceous powder according to claim 1, wherein the compound (C) that generates a sulfone group comprises one or more compounds selected from the group consisting of sodium sulfite, sodium bisulfite, sodium pyrosulfite, fuming sulfuric acid, and sulfur dioxide. Dispersion stabilizer for slurry. The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein melamine or a derivative thereof is represented by the following general formula (II).
Formula (II)

Here, X ₁ X ₂ X ₃ : H, CH ₂ OH or CH ₂ SO ₃ Y
Y: alkali metal, alkaline earth metal, ammonium, amine, substituted amine The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein phenol or a derivative thereof is represented by the following general formula (III).
Formula (III)

Here, X ₄ : H, CH ₂ OH or CH ₂ SO ₃ Y, a sulfone group, or its alkali metal, alkaline earth metal, ammonium, amine, substituted amine Y: alkali metal, alkaline earth metal, ammonium, amine , Substituted amine R ₃ : H or an alkyl group having 1 to 6 carbon atoms The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein urea or a derivative thereof is represented by the following general formula (IV).
Formula (IV)

_{Here, X 5, X 6: H} , CH 2 OH or _CH 2 _SO 3 Y
Y: alkali metal, alkaline earth metal, ammonium, amine, substituted amine The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein aminobenzenesulfonic acid or a derivative thereof, or alkylaminobenzenesulfonic acid or a derivative thereof is represented by the following general formula (V).
General formula (V)

Here, X ₇ : H, alkali metal, alkaline earth metal, ammonium, amine, substituted amine R ₃ : H or an alkyl group having 1 to 6 carbon atoms The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein the polyoxyalkylene monoglycidyl ether (A) and the monomer (B) capable of formaldehyde cocondensation are melamine. The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein the polyoxyalkylene monoglycidyl ether (A) and the monomer (B) capable of formaldehyde cocondensation are phenol. The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein the polyoxyalkylene monoglycidyl ether (A) and the monomer (B) capable of formaldehyde cocondensation are urea. The dispersion stabilizer for carbonaceous powder slurry according to claim 2, wherein the polyoxyalkylene monoglycidyl ether (A) and the monomer (B) capable of formaldehyde cocondensation are sulfanilic acid.