JP3675766B2 - Environmental improvement cement composition - Google Patents
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- JP3675766B2 JP3675766B2 JP2002028408A JP2002028408A JP3675766B2 JP 3675766 B2 JP3675766 B2 JP 3675766B2 JP 2002028408 A JP2002028408 A JP 2002028408A JP 2002028408 A JP2002028408 A JP 2002028408A JP 3675766 B2 JP3675766 B2 JP 3675766B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/58—Construction or demolition [C&D] waste
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Description
【０００１】
【発明の属する技術分野】
本発明は、焼却灰、汚染土壌、汚泥、工場廃棄物、建設廃土を安定化処理する技術に関するもので、更に詳しくは、重金属類、有機塩素化合物を固化封止する環境改善セメント組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
環境汚染物質として挙げられている、重金属類、有機塩素化合物のＰＣＢ、トリクロールエチレン、パークレン、ダイオキシン及び環境ホルモン撹乱物質のビスフェノールＡ、フタル酸エステル類、オキシ安息香酸類、有機スズ酸エステルなどは、人類の生活環境から安全な形で排除することが好ましいが、多量に発生し続ける環境汚染物質を効率よく処理することは極めて困難である。
【０００３】
ゴミ処理焼却に伴う焼却灰、下水道から発生する活性汚泥焼却灰なども、熔融固化により安全性が高まった様に見られたが、酸性域での重金属溶出が見いだされて、必ずしも熔融固化が安定でなく、更にセメント固化を行うことが安全であるとされている。しかし、セメント固化も６価クロム問題と、セメントの高アルカリにより鉛及びカドミウムの両者が共存する状態では同時に溶出を押さえることが困難であるという問題がある。又、一時、有機キレート化合物による安定化処理が行われていたが、長期安定性が悪く、特にセメント併用系では、有機キレートの分解が確認されている。更に、工場跡地などの土壌汚染は重金属類と有機塩素化合物の複合汚染が多く、多元的な処理が可能な方法が求められている。
【０００４】
これらを安定的に処理する方法として、固化剤としてポルトランドセメントに代わる物質を使用する方法が試みられ、アルミナセメント、珪酸ソーダ、石灰、高炉スラグ、高炉セメントなどが用いられているが、それぞれに問題点があり、単独でなく２種類以上の組み合わせにより行われている。また、前記有機キレートとして、有機硫黄化合物及びＥＤＴＡ、グルコン酸、クエン酸、キレート樹脂として、イミノ二酢酸キレート樹脂、ポリアミン樹脂、アミドキシム樹脂、グルカミン樹脂、ジチオカルバミン酸樹脂、チオ尿素樹脂などが検討されているが、長期安定性に欠ける。更に、鉄塩、フェライト、無機キレートも含めて検討されているが結果は必ずしも好ましくない。例えば、リン酸塩のポリリン酸アンモニウム、及びその他のリン酸塩、水酸化アパタイト、ボビーライトなどをセメントと混合する方法では、リンがセメントの遅延剤として働き、セメントの強度発現を阻害する問題がある。
【０００５】
更に、これらの安定化に向けての処理方法は、単一重金属では有効であるが、複合重金属汚染では、重金属類の中で両性重金属類が混在すると処理を困難とする場合が多かった。
【０００６】
【課題を解決するための手段】
以上の問題を解決する方法として、一般的には、重金属類を水酸化化合物の低い溶解度にして、セメントのごとく水和により硬化し、凝結時間が大幅に調整可能で、ｐＨが１１．０以下の耐水性の高い、キレート性の水硬性セメントが要求される。この条件を満足し、更に選択的に有機塩素化合物を取り込む物質は、活性炭の類いで吸着物質の分子の大きさに対応した空孔を有する選択可能な自由度のものが好ましい。
【０００７】
又、固化物の表面硬度が６Ｈ以上と高く耐摩耗性の良好な物性は、焼却灰等を固化した場合に表面に露出することを防止し、酸性雨に耐え得る耐酸性をもたらすため、好ましい。
【０００８】
本発明者は、これらの要求を満足する環境改善セメント組成物について鋭意検討した結果、マグネシヤ質を主成分とし、これに特定の化合物を併用したものが極めて高い性能を有することを見出し、本発明を完成した。
【０００９】
即ち、本発明はマグネシヤ質７０〜１５５重量部、リン酸塩５〜３０重量部（この内リン酸塩キレート剤１〜５重量部を含む）、活性炭５〜３０重量部、有機酸０．２〜２．０重量部を必須成分とする環境改善セメント組成物、並びにマグネシヤ質７０〜１５５重量部、炭酸化合物５〜２５重量部、リン酸塩キレート剤１〜５重量部、活性炭５〜３０重量部、有機酸０．２〜２．０重量部を必須成分とする環境改善セメント組成物、並びにマグネシヤ質７０〜１５５重量部、リン酸塩５〜３０重量部（この内リン酸塩キレート剤１〜５重量部を含む）、炭酸化合物５〜１０重量部、活性炭５〜３０重量部、有機酸０．２〜２．０重量部を必須成分とする環境改善セメント組成物である。
【００１０】
本発明によれば、環境汚染物質に対し、本発明のセメント組成物３〜１００重量％と水４０〜１７０重量％を添加し、固化処理することにより、環境汚染物質を効果的に処理することができる。
【００１１】
【発明の実施の形態】
以下、本発明を詳細に説明する。本発明に用いられるマグネシヤ質とは、若干の鉄を含む炭酸マグネシウム、水酸化マグネシウム、カンラン石、滑石、蛇紋岩を８００℃近くで焼成して得られる、軽焼マグネシヤ及び軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩を２００メッシュ以下に粉砕して必要により２種以上を混合したものである。
【００１２】
一方、マグネシヤ質の硬化剤となり得る物質としては、リン酸塩と炭酸塩（炭酸化合物）が挙げられる。これらは単品又は混合して使用することができ、リン酸塩としては、リン酸肥料等に用いられている、リン酸アンモニウム、ポリリン酸アンモニウム、スーパーリン酸、過リン酸石灰、重過リン酸石灰、過リン酸マグネシウム、重過リン酸マグネシウム、腐食酸、リグニンスルホン酸、クエン酸可溶の重焼リン、熔リン、トーマスリン肥などである。これらは、ＭｇＯ含有量に換算して１００重量部あたりＰ2Ｏ5として３〜２５重量部を０．１〜１．０重量部の腐食酸、リグニンスルホン酸、クエン酸存在下に反応させる方法である。この時、他の水溶性ピロリン酸塩、トリポリリン酸塩、ポリリン酸塩、好ましくは、縮合リン酸塩、ポリリン酸塩を添加しても良く、メタリン酸ポリリン酸ソーダ、酸性ピロリン酸ソーダ、トリポリリン酸ソーダ１〜５重量部をリン酸キレート剤として添加する。更にこれらは２種以上を混合使用することができる。
【００１３】
又一方、炭酸塩もマグネシヤ質の硬化剤となり利用することができ、例えば無機炭酸塩として重曹、重炭酸カリ、炭酸水素アンモニウム、炭酸アンモ、炭酸グアーニジン、正炭酸マグネシウムをＭｇＯ含有量に換算して１００重量部あたりＣＯ3として３〜２５重量部添加する、有機炭酸化合物として炭酸エチレン、炭酸プロピレン、トリアセチン、エチレングリコールジアセテート、γ−ブチルラクトンをＭｇＯ含有量に換算して１００重量部あたりＣＯ3として５〜２５重量部添加する。これらは同時に０．１〜１．０重量部の腐食酸、リグニンスルホン酸、クエン酸存在の下に反応させると凝結時間を調節する。又、２種以上を混合使用することができる。更に上記リン酸塩と混合して２種類以上の硬化剤として複合使用が可能で、重金属類をアルカリサイドで共沈させて、吸着させることができる。
【００１４】
又、更に有機酸（化合物）は、凝結遅延のみならず、上記マグネシヤ質及び水不溶リン酸塩の可溶化剤と炭酸塩の凝結時間を調節する目的で用いることができ、上記腐食酸、リグニンスルホン酸、クエン酸以外にこれらのナトリウム塩、アンモニウム塩を用いることができ、グルコン酸ソーダ、２−ケトグルタール酸ソーダを併用しても良く２種以上を混合使用することができる。
【００１５】
本発明に使用される活性炭は、各種の活性炭中比較的空孔率の大きいものが適しており、空孔の深さが１００Å〜２００Å、空孔φ５Å〜３０Åであるものが好ましい。特に重金属類にはＬ／Ｄが４〜６：１．０の空孔の深さが１００Å〜１５０Å、空孔φ５Å〜２５Åのものであり、ＰＣＢ及びダイオキシン類ではＬ／Ｄが７〜１０：１．０の空孔深さ１５０Å〜２００Å、空孔φ１５Å〜３０Åのものが適している。これらは粉末の形で添加され、重金属類又は有機塩素化合物の含有量により５〜３０重量部を使用する。活性炭の原料由来としては、重金属類及び低分子有機塩素化合物に対しては塩化亜鉛錻活ヤシ殻活性炭が好ましくは、ＰＣＢ及びダイオキシン類に対しては塩化亜鉛錻活ピトモス活性炭が好ましい。これらは、重金属類の水酸化物を吸着させ、更に上記硬化物で固化することにより、より効果の高い安定化処理を可能にすることができる。
【００１６】
以上にあげた、マグネシヤ質の硬化剤として、リン酸塩（リン酸肥料）、各種の炭酸塩及びリン酸塩キレート剤と可溶化剤と凝結遅延剤を含む有機酸類及び活性炭を含む組成物を、重金属及び有機塩素化合物の封止目的に応じて配合する。基本配合は、ＭｇＯ含有量で換算すると軽焼マグネシヤを使用する場合７０〜８０重量部に対し、リン酸塩５〜３０重量部、有機酸０．２〜２．０重量部にリン酸塩キレート剤１〜５重量部、活性炭５〜３０重量部を添加する。軽焼ホルステライトでは１０３〜１１８重量部に対し、リン酸塩５〜３０重量部、有機酸０．２〜２．０重量部にリン酸塩キレート剤１〜５重量部、活性炭５〜３０重量部を添加する。軽焼滑石、軽焼蛇紋岩では、１１４〜１５５重量部に対し、リン酸塩５〜３０重量部、有機酸０．２〜２．０重量部にリン酸塩キレート剤１〜５重量部、活性炭５〜３０重量部を添加する。この組成物の特徴はリン酸塩の選択により凝結時間が設定できることである。ただし、軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩を使用する場合、それらの反応活性が低い場合は、３０重量部〜５０重量部の軽焼マグネシヤをこれらに追加して使用することができる。
【００１７】
又、軽焼マグネシヤ１００重量部に炭酸化合物を使用する場合は５〜２５重量部を、軽焼ホルステライトでは１０３〜１１８重量部に対し炭酸化合物３〜２３量部、軽焼滑石、軽焼蛇紋岩では、１１４〜１５５重量部に対し炭酸化合物３〜２０量部、好ましくは７〜１５重量部を添加する。この組成物の特徴は、凝結時間が始発を瞬結から４時間に腐食酸、リグニンスルホン酸、クエン酸、グルコン酸ソーダ、２−ケトグルタール酸ソーダの添加量で設定できる利点がある。ただし軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩の反応活性が低い場合は、上記と同様に３０重量部〜５０重量部の軽焼マグネシヤをこれらに追加して使用することができる。
【００１８】
更に、リン酸塩と炭酸化合物を併用する場合において、軽焼マグネシヤ１００重量部にリン酸塩５〜３０重量部（この内リン酸塩キレート剤１〜５重量部を含む）、炭酸化合物５〜１０重量部を混合添加して、リン酸塩の長時間凝結と炭酸化合物の初期凝結の利点を活用でき様々な現場条件に対応できる物性を発現できる。ただし軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩の反応活性が低い場合は、上記と同様に３０重量部〜５０重量部の軽焼マグネシヤをこれらに追加して使用することができる。
【００１９】
本発明の組成物は、マグネシヤ質粉末、リン酸塩粉末（この内リン酸塩キレート剤粉末）、炭酸化合物粉末、活性炭粉末、有機酸粉末を任意に混合して、水分により反応させることを特徴とする組成物である、好ましくは、これらの粉末度が２００メッシュ以下であり、特にマグネシヤ質粉末及び水不溶リン酸塩粉末は好ましくは３００メッシュ以下が適している。
【００２０】
この組成物は、マグネシヤ質粉末に対するリン酸塩粉末及び炭酸化合物粉末の添加量が非化学量論的配合で、理論化学当量より、極めて少なく、ボビーライトとは大きく異なる。化学組成で一般式は、Ｍｇ8Ｈ2（ＰＯ4）6・５Ｈ2Ｏであるとされている。又、炭酸化合物における反応では３４％以下の理論量になり、反応生成物は塩基性炭酸マグネシウムで、リン酸塩と炭酸塩の併用系では、非化学量論リン酸マグネシウムと非化学量論塩基性炭酸マグネシウムの混合物である。未反応のマグネシヤ質は水酸化マグネシウムとして存在し、最終的には空気中の炭酸ガスと反応して、塩基性炭酸マグネシウムを与える。
【００２１】
本発明の組成物は、マグネシヤ質粉末、リン酸塩粉末（この内リン酸塩キレート剤粉末）、炭酸化合物粉末、有機酸粉末が水により反応する過程では重金属類がリン酸塩と反応してリン酸塩キレートを形成するが、この状態における錯塩の安定度が低く、ｐＨに左右され易く不安定な外因が多い。金属イオン［Ｍ］とキレート剤［ｍＺ］が反応した場合、［Ｍ］＋［ｍＺ］≦ＭＺmが好ましく、この反応を右に移行させるにはリン酸塩キレート重金属をマグネシウム塩として不溶化させることでキレート効果を高めることができる。一般的に重金属類の溶解度の最も低下するｐＨ領域は１０〜１１で水酸化マグネシウムのｐＨに近く、リン酸塩キレートの生成領域に一致するため重金属類の封止に適している。
【００２２】
本発明のマグネシヤ質粉末、リン酸塩粉末（この内リン酸塩キレート剤粉末）、炭酸化合物粉末、有機酸粉末に活性炭を添加する組成物では重金属類のリン酸キレートを良く吸着し、水不溶の有機塩素溶剤及びＰＣＢ、ダイオキシン類を選択的に吸着できる。重金属類のリン酸塩キレート固化物は、長期間に酸性雨などにより抽出を受ける場合が考えられ、化学的安定性のみならず活性炭吸着により物理的安定性を固化と併用する系でより高い安定性を獲得し、酸性抽出を受けにくくなる。又、有機塩素溶剤及びＰＣＢ、ダイオキシン類は極性が低く親水性が小さいため、これらを水系で除去することが困難で様々な物理的方法が組み合わされているが、活性炭を含む固化が最も効率が良く約２／１００．０００にＰＣＢ、ダイオキシン類を低減することができる。
【００２３】
マグネシヤ質粉末として軽焼マグネシヤを８０重量部に対し、重過リン酸石灰１０重量部、ポリリン酸ソーダ１重量部、無水クエン酸粉末０．２重量部からなる粉体組成物を、関東ローム１００重量部に１０重量部添加して水６５重量部で混練りするとセメント系固化剤に比較して約３倍の３．５Ｎ／ｍｍ2の一軸圧縮強度が得られる。この硬化物のｐＨは１０．０で植生及び魚貝類に悪影響を与えずセメント系の様な白化現象がなく、耐水性が良好である。本組成物は、無水クエン酸を使用して凝結時間を調節し、２０℃のニートセメントの凝結時間を始発１時間４５分〜４時間３５分に調節が可能であり、本発明の市販リン酸塩の種類を水溶性リン酸含有量で比較すると、リン酸アンモニウム７４〜８５％、ポリリン酸アンモニウム５０〜７０％、過リン酸石灰１６〜２０％、重過リン酸石灰３０〜４８％、重過リン酸マグネシウム３０〜４８％、重焼リン３５％、熔リン３０％、メタリン酸マグネシウム７０％でこの数値によりリン酸塩の配合量を調節する。ただし、完全可溶なリン酸アンモニウム、ポリリン酸アンモニウムは非常にマグネシヤ質との反応が早く、重過リン酸石灰の水溶性リン酸量より低い値で使用することが好ましく、遅延剤として酸性リン酸ソーダ等をあらかじめ反応させた物を使用する。熔リンは凝結時間の長い用途に適し、７日間凝結を遅延させることが可能である。
【００２４】
本発明の組成物における炭酸化合物の用法について説明すると、マグネシヤ質粉末として軽焼マグネシヤを８０重量部に対し、重曹１５重量部、ポリリン酸ソーダ１重量部、無水クエン酸粉末０．４重量部からなる粉体組成物のニートセメントの凝結時間は２０℃で１時間１０分であり、無水クエン酸を無添加では、始発３分１５秒終結６分２５秒と急結性で粉末塩化第一鉄を２重量部添加すると瞬結するようになる。これに比較して、軽焼マグネシヤを８０重量部に対し、重炭酸アンモ１５重量部、ポリリン酸ソーダ１重量部、無水クエン酸粉末０．４重量部からなる粉体組成物は、ニートセメントの凝結時間が２０℃で４５分で無水クエン酸無添加では、始発２分１５秒で瞬結する。軽焼マグネシヤを８０重量部に対し、エチレンカーボネート２０重量部、ポリリン酸ソーダ１重量部、無水クエン酸粉末なしの粉体組成物は、ニートセメントの凝結時間は２０℃で１時間４５分であり、粉末塩化第一鉄を２重量部添加すると６分２５秒で硬化する。同一添加量、同一組成、同一条件の各炭酸化合物、炭酸プロピレンで凝結時間が１時間４５分、トリアセチン凝結時間が１５分、エチレングリコールジアセテート凝結時間が１時間３４分、γ−ブチルラクトン凝結時間が１時間５２分と炭酸化合物の反応性により凝結時間に違いが認められる。
【００２５】
本発明の組成物中、リン酸塩硬化と炭酸化合物併用系の用法は、リン酸塩の影響により特に酸性塩では炭酸化合物の遅延剤として作用し凝結時間が長くなる傾向がある。例えば軽焼マグネシヤを８０重量部に対し、重過リン酸石灰１０重量部、重曹５重量部、ポリリン酸ソーダ１重量部、無水クエン酸粉末０．４重量部からなる粉体組成物のニートセメントの凝結時間は２０℃で２時間７分であり、始発のみが遅延し終結は２時間３４分で１日強さは、重過リン酸石灰のみより３５％向上した。以上のようにマグネシヤ質に対する３種類の硬化剤の選択と有機酸の添加量で凝結時間を自由に調節できる利点がある。
【００２６】
本発明の組成物の主成分であるマグネシヤ質は、軽焼マグネシヤ及び軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩粉末であり、前述の通り軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩はＭｇＯとしての含有量が低い嫌いがある。しかし、これらに軽焼マグネシヤを１０〜３０重量部追加混合すると、軽焼マグネシヤの反応活性と同等な配合が行える。軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩粉末を用いると珪酸を含有するため耐酸性を向上させることができるばかりか、軽焼マグネシヤ資源が地域により偏在しているのに対し、軽焼ホルステライト、軽焼滑石、軽焼蛇紋岩資源は、比較的広範囲に分布するため、軽焼マグネシヤより安価に大量供給が可能であるとされている。このため、セメントより焼成温度が低く生産性が良い利点は、軽焼マグネシヤを多少混合する組成物配合では用途により非常にコスト面で有利である。軽焼ホルステライトは、焼成方法により不活性になり易いが、塩焼き又は塩化マグネシウム焼きにより、この問題を解決することができる。原鉱石産地により鉄分５〜１０％を含有するため焼成粉末は茶褐色になる傾向があり、軽焼マグネシヤの白色又は淡黄色と異なるが、用途により使い分けるこど色調は問題がない。
【００２７】
本発明の組成物を使用するにあたり、セメントに使用される減水剤及び流動化剤を使用すると、スラリーの性質を改善することができる、上記に上げた有機酸類の添加は、減水作用もあり、ニトロフミン酸塩、リグニンスルホン酸塩、クエン酸はマグネシヤ質の良好な減水作用を有する。ナフタリン系、メラミン系、ポリカルボン酸系も併用して利用可能であり、起泡剤、増粘剤、消泡剤、各種の高分子エマルジョンを使用することができる。
【００２８】
【作用】
１）本発明の環境改善セメント組成物は、主成分にマグネシヤ質を用いるものでリン酸塩を硬化剤とする場合は、従来のリン酸マグネシヤセメントの反応モルと異なり、リン酸塩量が極めて少ない非化学量論的配合である。一方の炭酸化合物を使用する場合においても炭酸化合物量が極めて少ない非化学量論的配合であり、両者の併用系でも同様な非化学量論的配合である。これらの原料組成は安全性が極めて高い、肥料成分又は食品添加物かこれに準ずる原料を使用するため、万一自然界に拡散しても安全性が高くｐＨも低く、主原料のマグネシヤ質の溶解度は０．０００９で石灰の０．１６に比較して１／１７７であり、凝結時間が自由に調節できる利点とセメント系に匹敵する物理的強度を有する。
２）セメント系固化剤の欠点であるＣｒ 6+ の問題がなく、ローム系土壌では少量で固化が可能であり、有機土壌及びセメント系で固化不能な産業廃棄物、汚泥、廃石灰、海底堆積物、温泉汚泥、硫黄含有物などを固化し、重金属類、有機溶剤、ＰＣＢ、ダイオキシンなどを安定化することができる。特に複合土壌汚染防止や河川汚泥などの複雑な含有物に有効で、アンモニヤ、メルカプタン、硫化水素、などの臭気を固定できる消臭作用がある。
３）有害物質含有がなくｐＨが低いため、生物環境適合し環境負荷がないため、成型物は土に直接循環させることができ、農業用途や魚礁、護岸コンクリートなどの従来のセメントにない広範囲な再資源的用途がある。
【００２９】
【実施例】
以下に、本発明を実施例により更に具体的に説明するが、本発明は、これらの例によって、限定されるものではない。
参考例１
Ｏ市下水道活性汚泥焼却灰の環境省４６号試験による原灰１００重量部と、本発明の環境改善セメント組成物（以下本発明組成物という）である軽焼マグネシヤ（２００メッシュ以下）８５重量部、重焼リン粉末（２００メッシュ以下）１５重量部、無水石膏５重量部、無水クエン酸０．１重量部の粉体混合物３０重量部を混合して、これに水７０重量部を添加して５分間ポバートミキサーで混合し、５０φ×１００の土質試験型枠に充填して硬化させた。２８日間室温気中養生した成型物をＪＩＳ Ａ １２１６に従い、圧縮試験を行った。この結果は、３６．４Ｎ／ｍｍ2であった。この破砕供試体を５ｍｍ以下に粉砕して、篩分し環境省４６号試験を行い重金属類の検出を行った。重金属等の溶出試験の結果を表１に示す。
【００３０】
【表１】
実施例１
Ｋ市焼却炉飛灰を環境省４６号試験により分析し、本発明の組成物として軽焼マグネシヤ（２００メッシュ以下）８５重量部、重焼リン粉末（２００メッシュ以下）１５重量部、無水石膏５重量部、無水クエン酸０．１重量部にポリリン酸ソーダ２．０重量部、ビート活性炭３．０重量部の粉体混合物３５重量部を上記焼却炉飛灰１００重量部と混合して、これに水６０重量部を添加して５分間ポバートミキサーで混合し、５０φ×１００の土質試験型枠に充填して硬化させた。２８日間室温気中養生した成型物をＪＩＳ Ａ １２１６に従い、圧縮試験を行った。この結果は、２３．２Ｎ／ｍｍ2であった。この破砕供試体を５ｍｍ以下に粉砕して、篩分し環境省４６号試験を行い重金属類の検出を行った。結果を表２に示す。
【００３２】
【表２】
＊ダイオキシン含有飛灰固化処理物０．２７ng/ｌは、１８０℃／１０ｋｇのオートクレーブ６時間処理により０．０１ng/ｌ以下にすることができた。
実施例２
関東ロームに環境省４６号試験基準値の１０倍、１００倍量の重金属類（塩化水銀、塩化カドミウム、硝酸鉛、重クロム酸カリ、３塩化ヒ素、塩化銅）を添加した。本発明組成物として軽焼マグネシヤ（２００メッシュ以下）８５重量部、重過リン酸石灰粉末（２００メッシュ以下）１５重量部、無水石膏５重量部、無水クエン酸０．１重量部にポリリン酸ソーダ２．０重量部、ビート活性炭３．０重量部の粉体混合物３５重量部を上記関東ローム１００重量部と混合して、これに水６５重量部を添加して５分間ポバートミキサーで混合して、５０φ×１００の土質試験型枠に充填して硬化させる。２８日間室温気中養生した成型物をＪＩＳ Ａ １２１６に従い、圧縮試験を行った。この結果、１４．３Ｎ／ｍｍ2であった。この破砕供試体を５ｍｍ以下に粉砕して、篩分し環境省４６号試験を行い重金属類の検出を行った。表３に負荷試験の結果を示す。
【００３４】
【表３】
参考例２
軽焼ホルステライト（３６０メッシュ全通）１００重量部に重曹１５重量部、無水クエン酸０．４重量部、キーレト剤兼硬化剤としてポリリン酸アンモニウム２重量部を粉体混合して、本発明のセメント組成物を得た。２０℃の始発時間は１時間１６分、終結時間は１時間４６分であり、無水クエン酸無添加の２０℃の始発時間は４．２分、終結時間は７．４分であった。これを含水率３００％河川汚泥１００重量部に本発明のセメント組成物５０重量部添加して、５分間ポバートミキサーで混合し、５０φ×１００の土質試験型枠に充填したところ、６時間後には硬化した。７日間室温気中養生した成型物をＪＩＳ Ａ １２１６に従い、圧縮試験を行うと、０．４３Ｎ／ｍｍ2の強度を示した。固化物の臭気は完全に消失して無臭であった。
実施例３
本発明の配合代表例を、表４に示す。
【００３６】
【表４】
尚、配合２、配合３及び配合７は参考品である。
＊ 活性炭量は、適宜目的に応じて５〜２０重量部を添加する。
＊ 凝結試験及び強さ試験は、ＪＩＳ Ｒ ５２０１に準じて試験を行った。
＊ 供試体ｐＨは、５ｍｍ以下に粉砕して１０倍量の純水に７日間浸けて試験を行った。
＊ アオコ発生日数は、供試体ｐＨに用いた試験に従い室温野外放置の試験結果である。
＊ ポルトランドセメント供試体を上記と比較すると、この期間内ではアオコ発生がない。
実施例４
採取河川堆積（汚泥含水率２００％）１００重量部に、実施例３−配合４の本発明組成物２０重量部(活性炭５重量部を含む）を混合して固化させた。固化物の７日後のコーン指数は５．０でｐＨは８．７であった。
参考例３
乾燥した関東ローム１００重量部に、トリクロロエタン２重量部及びテトラクロロエチレン２重量部を混合して、実施例３−配合７の組成物３０重量部とビート活性炭１０重量部及びビート活性炭１５重量部を加えて、水７５重量部で混練りして固化させた。この試料を５ｍｍ以下に粉砕して、６時間水で浸透抽出を行い、濾過して抽出液をＪＩＳ Ｋ ０１２５５．２に準じて試験を行った。結果を表５に示す。
【００３８】
【表５】
この負荷試験では、酒精用活性炭でも同様な結果を得た。
実施例５
乾燥した関東ローム１００重量部に、活性炭２００重量部、実施例３−配合１の本発明組成物３０重量部に水７０重量部を加えて、混合し粒径３．５ｍｍ〜５．４ｍｍの造粒品を得た。この造粒品を直径１００ｍｍφ、長さ１０００ｍｍのパイプに充填して、上部より汚泥水を流下させると、精透して臭気のない水が得られた。この水にアンモニヤ水１０ｍｇ／ｌ及び４０％リン酸１０ｍｇ／ｌを添加して下部から流失する水をサンプリングしてアンモニヤ及びリン酸を定量すると、アンモニヤ０．０００１ｍｇ／ｌ、リン酸０．００００６ｍｇ／ｌであった。更に、この造粒品１ｋｇを水１０ｌの水槽に入れ金魚を飼育すると２８日間金魚の死亡率は０であった。
比較例１
アカメダカ１００匹を水１０ｌ中に放流し、１分間２００ｃｃの曝気を行いつつポルトランドセメントスラリー（セメント１００ｇ／水１００ｇ）を少量ずつ添加したところ、ＬＣ50に至る急性毒性は、１６．５ｇ／ｌであった。一方、本発明の環境セメント組成物は、同様の試験の結果、ＬＣ50に至る急性毒性は、６３．５ｇ／ｌであった。
比較例２
ポルトランドセメント固化と本発明の環境セメント組成物固化の重金属類の溶出量を図１に示す。試験方法は環境庁１３号試験及び環境庁４６号試験に準じて行った。
【００４０】
【発明の効果】
本発明は、ポルトランドセメントに代わる固化剤を目指すものであり、リン酸塩のキレート作用により重金属を補捉し、活性炭の併用で有機塩素化合物を安定化できる複合型環境対応セメント組成物である。本発明のセメント組成物は、環境負荷が極めて低く、直接生物環境を犯すことがなく、廃棄する場合でも肥料成分として循環が可能である。
【図面の簡単な説明】
【図１】 ポルトランドセメント固化と本発明の環境セメント組成物固化の重金属類の溶出量を比較するグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a technology for stabilizing incineration ash, contaminated soil, sludge, factory waste, and construction waste soil, and more particularly, to an environment-improving cement composition that solidifies and seals heavy metals and organochlorine compounds. .
[0002]
[Prior art and problems to be solved by the invention]
Heavy metals, PCBs of organic chlorine compounds, trichlorethylene, parkrene, dioxins and environmental hormone disrupting substances bisphenol A, phthalates, oxybenzoates, organostannates, etc., listed as environmental pollutants, Although it is preferable to remove it safely from the living environment of mankind, it is extremely difficult to efficiently treat environmental pollutants that continue to be generated in large quantities.
[0003]
Incineration ash from garbage incineration and activated sludge incineration ash generated from sewers seemed to have improved safety due to melting and solidification, but elution of heavy metals in the acidic range was found, and the melting and solidification was not always stable. It is said that it is safe to further solidify the cement. However, cement solidification has a problem of hexavalent chromium, and it is difficult to suppress elution at the same time in the state where both lead and cadmium coexist due to the high alkali of the cement. Moreover, although the stabilization process with the organic chelate compound was once performed, long-term stability is bad, and especially decomposition | disassembly of an organic chelate has been confirmed in the cement combined use system. Furthermore, soil contamination such as factory ruins is often a complex contamination of heavy metals and organochlorine compounds, and a method capable of multiple treatment is required.
[0004]
As a method for stably treating these, a method using a substance instead of Portland cement as a solidifying agent has been tried, and alumina cement, sodium silicate, lime, blast furnace slag, blast furnace cement, etc. have been used. There is a point, and it is carried out by a combination of two or more, not alone. In addition, as the organic chelate, organic sulfur compounds and EDTA, gluconic acid, citric acid, chelating resins, iminodiacetic acid chelating resin, polyamine resin, amidoxime resin, glucamine resin, dithiocarbamic acid resin, thiourea resin, etc. have been studied. But lacks long-term stability. Furthermore, studies have been made including iron salts, ferrites, and inorganic chelates, but the results are not always preferable. For example, ammonium phosphate polyphosphate, and other phosphates, hydroxideConversionIn the method of mixing apatite, bobby light, etc. with cement, there is a problem that phosphorus acts as a cement retarder and inhibits the development of cement strength.
[0005]
Furthermore, these stabilizationProcessing methodIs valid for single heavy metalsIn effectHowever, in complex heavy metal contamination, if amphoteric heavy metals are mixed among heavy metals, the treatment is often difficult.
[0006]
[Means for Solving the Problems]
As a method for solving the above problems, in general, heavy metals are mixed with hydroxide.ConversionThere is a need for chelating hydraulic cements that have low compound solubility, harden by hydration like cement, have a highly adjustable setting time, and have a high water resistance with a pH of 11.0 or less. A substance that satisfies this condition and that selectively takes in an organic chlorine compound is preferably a substance having selectable degrees of freedom having pores corresponding to the molecular size of the adsorbent, similar to activated carbon.
[0007]
Moreover, since the surface hardness of the solidified product is as high as 6H or more and the wear resistance is good, it is preferable that the incinerated ash and the like are exposed to the surface when solidified, resulting in acid resistance that can withstand acid rain. .
[0008]
As a result of intensive studies on an environment-improving cement composition that satisfies these requirements, the present inventor has found that a material mainly composed of magnesia and having a specific compound in combination has extremely high performance. Was completed.
[0009]
That is, the present invention is composed of 70 to 155 parts by weight of magnesium, 5 to 30 parts by weight of phosphate (including 1 to 5 parts by weight of the phosphate chelating agent), 5 to 30 parts by weight of activated carbon, 0.2 of organic acid. Environment-improving cement composition containing 2.0 parts by weight as essential components, and 70-155 parts by weight of magnesium, 5-25 parts by weight of carbonic acid compound, 1-5 parts by weight of phosphate chelating agent, 5-30 parts by weight of activated carbon Part, an environment-improving cement composition containing 0.2 to 2.0 parts by weight of an organic acid as essential components, as well as 70 to 155 parts by weight of magnesium and 5 to 30 parts by weight of a phosphate (including a phosphate chelating agent 1 And 5 to 10 parts by weight of carbonic acid compound, 5 to 30 parts by weight of activated carbon, and 0.2 to 2.0 parts by weight of organic acid.
[0010]
According to the present invention, 3 to 100% by weight of the cement composition of the present invention and 40 to 170% by weight of water are added to the environmental pollutant and solidified to effectively treat the environmental pollutant. Can do.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. The magnesia used in the present invention is light-burned magnesium, light-burned holsterite, light-burned holsterite, light-burned magnesium obtained by baking magnesium carbonate, magnesium hydroxide, olivine, talc, and serpentine containing some iron. Yarn talc and light-fired serpentine are pulverized to 200 mesh or less and, if necessary, two or more types are mixed.
[0012]
On the other hand, as a substance that can be a magnetic hardener, phosphate and carbonate(Carbonate compound)Is mentioned. These can be used singly or as a mixture. As phosphates, used in phosphate fertilizers, etc., ammonium phosphate, ammonium polyphosphate, superphosphate, superphosphate lime, heavy superphosphate Lime, magnesium perphosphate, magnesium heavy perphosphate, corrosive acid, lithiumGExamples include ninsulfonic acid, citric acid-soluble heavy burnt phosphorus, molten phosphorus, and Thomaslin fertilizer. These are calculated as P per 100 parts by weight in terms of MgO content.2OFive3 to 25 parts by weight of 0.1 to 1.0 parts by weight of corrosive acid,GThis is a method of reacting in the presence of ninsulfonic acid and citric acid. At this time, other water-soluble pyrophosphate, tripolyphosphate, polyphosphate,Preferably, condensed phosphate and polyphosphate may be added, and 1 to 5 parts by weight of sodium metaphosphate, sodium pyrophosphate, and sodium tripolyphosphate are added as phosphate chelating agents..Furthermore, these can be used in combination of two or more.
[0013]
On the other hand, carbonates can also be used as a magnetic curing agent. For example, sodium carbonate, potassium bicarbonate, ammonium bicarbonate, ammonium carbonate, guanidine carbonate, and magnesium carbonate as inorganic carbonates are converted into MgO content. CO per 100 parts by weightThreeAs an organic carbonate compound, ethylene carbonate, propylene carbonate, triacetin, ethylene glycol diacetate, and γ-butyl lactone are converted to MgO content and CO per 100 parts by weight.Three5 to 25 parts by weight are added. These are 0.1 to 1.0 parts by weight of corrosive acid,GAdjusting the setting time when reacted in the presence of ninsulfonic acid and citric acid.Two or more kinds can be mixed and used. Furthermore, it can be used in combination with two or more kinds of curing agents by mixing with the above-mentioned phosphate, and heavy metals can be coprecipitated with an alkali side and adsorbed.
[0014]
Moreover, furtherOrganic acids (compounds)It can be used not only for setting delay but also for the purpose of adjusting the setting time of solubilizing agent and carbonate for the above-mentioned magnesium and water-insoluble phosphates.GThese sodium salts and ammonium salts can be used in addition to ninsulfonic acid and citric acid. Sodium gluconate and sodium 2-ketoglutarate may be used in combination, or two or more kinds may be used in combination.
[0015]
As the activated carbon used in the present invention, those having a relatively large porosity among various activated carbons are suitable, and those having a pore depth of 100 to 200 mm and a hole diameter of 5 to 30 mm are preferable. In particular, heavy metals have an L / D of 4-6: 1.0 and a hole depth of 100 to 150 mm and a hole diameter of 5 to 25 mm, and PCBs and dioxins have an L / D of 7 to 10: A 1.0 hole depth of 150 to 200 mm and a hole diameter of 15 to 30 mm are suitable. These are added in the form of powder, and 5 to 30 parts by weight are used depending on the content of heavy metals or organochlorine compounds. As the raw material of activated carbon, zinc chloride-activated coconut shell activated carbon is preferable for heavy metals and low-molecular organic chlorine compounds, and zinc chloride-activated pitmos activated carbon is preferable for PCBs and dioxins. These can adsorb heavy metal hydroxides and further solidify with the cured product, thereby enabling a more effective stabilization treatment.
[0016]
As a magnetic hardening agent, a composition containing phosphate (phosphate fertilizer), various carbonates and phosphate chelating agents, organic acids including solubilizers and setting retarders, and activated carbon. , Blended according to the purpose of sealing heavy metals and organic chlorine compounds. The basic formulation is 5 to 30 parts by weight of phosphate and 0.2 to 2.0 parts by weight of organic acid with respect to 70 to 80 parts by weight when using light-burned magnesia in terms of MgO content.To1-5 parts by weight of phosphate chelating agent and 5-30 parts by weight of activated carbon are added. In light-burned holsterite, 5 to 30 parts by weight of phosphate and 0.2 to 2.0 parts by weight of organic acid with respect to 103 to 118 parts by weightTo1-5 parts by weight of phosphate chelating agent and 5-30 parts by weight of activated carbon are added. In light-burning talc and light-burning serpentine, 5 to 30 parts by weight of phosphate and 0.2 to 2.0 parts by weight of organic acid with respect to 114 to 155 parts by weightTo1-5 parts by weight of phosphate chelating agent and 5-30 parts by weight of activated carbon are added. The characteristic of this composition is that the setting time can be set by the choice of phosphate.Andis there. However, light-burned holsterite, light-fired talc, light-fired serpentineIf you use themWhen the reaction activity of is low, 30 to 50 parts by weight of light-burning magnesia can be additionally used.
[0017]
In addition, 5 to 25 parts by weight when carbonic acid compound is used for 100 parts by weight of lightly burned magnesium, 3 to 23 parts by weight of carbonated compound with respect to 103 to 118 parts by weight of lightly burned forsterite, lightly burned talc, lightly burned serpentine For rocks, 3 to 20 carbonates for 114 to 155 parts by weightPart,Preferably 7 to 15 parts by weightTheAdded.This composition is characterized by the fact that the setting time starts from the initial setting to 4 hours from the instant setting.GThere is an advantage that it can be set by the addition amount of ninsulfonic acid, citric acid, sodium gluconate and sodium 2-ketoglutarate.TheHowever, if the light activity of horsterite, light calcite talc, and light calcite serpentinite is low,As above30 parts by weight to 50 parts by weight of light-burning magnesia can be additionally used.
[0018]
Furthermore, in the case where a phosphate and a carbonate compound are used in combination, 5 to 30 parts by weight of a phosphate (including 1 to 5 parts by weight of the phosphate chelating agent) is added to 100 parts by weight of light-burned magnesium, Mixing and adding 10 parts by weight, it is possible to take advantage of the long-term setting of phosphate and the initial setting of carbonate compound, and to develop physical properties that can respond to various on-site conditions.. TheHowever, if the light activity of horsterite, light calcite talc, and light calcite serpentinite is low,As above30 parts by weight to 50 parts by weight of light-burning magnesia can be additionally used.
[0019]
The composition of the present invention is characterized in that a magnetic powder, a phosphate powder (in which a phosphate chelating agent powder is included), a carbonate compound powder, an activated carbon powder, and an organic acid powder are arbitrarily mixed and reacted with moisture. Preferably, the fineness of these is 200 mesh or less, and in particular, magnesia powder and water-insoluble phosphate powder are preferably 300 mesh or less.
[0020]
This composition has a non-stoichiometric amount of phosphate powder and carbonic acid compound powder added to the magnesia powder, which is much less than the theoretical chemical equivalent, and is significantly different from bobbylite. The chemical composition and the general formula is Mg8H2(POFour)6・ 5H2O. In addition, the theoretical amount of carbon compound is 34% or less, and the reaction product is basic magnesium carbonate. In the combined system of phosphate and carbonate, non-stoichiometric magnesium phosphate and non-stoichiometric base are used. It is a mixture of basic magnesium carbonate. Unreacted magnesia exists as magnesium hydroxide and finally reacts with carbon dioxide in the air to give basic magnesium carbonate.
[0021]
In the composition of the present invention, in the process in which magnesium powder, phosphate powder (within this phosphate chelating agent powder), carbonate compound powder, and organic acid powder react with water, heavy metals react with phosphate. Form phosphate chelateButIn this state, the stability of the complex salt is low, and there are many unstable external factors that are easily influenced by pH. When the metal ion [M] reacts with the chelating agent [mZ], [M] + [mZ] ≦ MZm is preferable. To shift this reaction to the right, the phosphate chelate heavy metal is insolubilized as a magnesium salt. The chelating effect can be enhanced. Generally, the pH range where the solubility of heavy metals is most lowered is 10 to 11, which is close to the pH of magnesium hydroxide and matches the production region of phosphate chelates, which is suitable for sealing heavy metals.
[0022]
The present inventionThe maIn the composition in which activated carbon is added to gneissy powder, phosphate powder (of which phosphate chelating agent powder is included), carbonate compound powder, and organic acid powder, it absorbs heavy metal phosphate chelate well and is water-insoluble organic chlorine. Can selectively adsorb solvents, PCBs and dioxinsThe HeavyMetal phosphate chelate solidified products may be extracted for a long time due to acid rain, etc., and not only chemical stability but also physical stability combined with solidification by activated carbon adsorption is more stable Gains sex and is less susceptible to acidic extraction. Organic chlorine solvents, PCBs, and dioxins are low in polarity and low in hydrophilicity, so it is difficult to remove them in an aqueous system, and various physical methods are combined, but solidification including activated carbon is most efficient. It is possible to reduce PCB and dioxins to about 2 / 100.000.
[0023]
MaA powder composition comprising 10 parts by weight of lime heavy superphosphate, 1 part by weight of sodium polyphosphate, and 0.2 parts by weight of anhydrous citric acid powder with respect to 80 parts by weight of light-burned magnesium as a gnecia powder,
[0024]
Use of carbonate compounds in the composition of the present inventionTo explainThe setting time of neat cement of a powder composition comprising 15 parts by weight of baking soda, 1 part by weight of sodium polyphosphate, and 0.4 parts by weight of anhydrous citric acid powder with respect to 80 parts by weight of light-burned magnesium as a magnesium powder is 20 At 1 ° C. for 1 hour and 10 minutes, without addition of anhydrous citric acid, the initial setting was 3 minutes and 15 seconds, and the final setting was 6 minutes and 25 seconds. Compared with this, a powder composition comprising 15 parts by weight of ammonium bicarbonate, 1 part by weight of sodium polyphosphate, and 0.4 parts by weight of anhydrous citric acid powder with respect to 80 parts by weight of light-burned magnesium is neat cement. With a setting time of 45 ° C. at 20 ° C. and no addition of anhydrous citric acid, instantaneous setting takes place in 2 minutes and 15 seconds. The powder composition of 20 parts by weight of ethylene carbonate, 1 part by weight of sodium polyphosphate and no anhydrous citric acid powder with respect to 80 parts by weight of light-burned magnesia has a setting time of neat cement of 20 hours at 20 ° C. for 1 hour and 45 minutes. When 2 parts by weight of powdered ferrous chloride is added, curing takes 6 minutes and 25 seconds. Each carbonate compound with the same addition amount, the same composition and the same conditions, and a setting time of 1 hour 45 minutes with propylene carbonate, a triacetin setting time of 15 minutes, an ethylene glycol diacetate setting time of 1 hour 34 minutes, a γ-butyllactone setting time However, there is a difference in the setting time due to the reactivity of the carbonate compound with 1 hour 52 minutes.
[0025]
In the composition of the present invention, the use of the phosphate curing and carbonate compound combination system tends to act as a retarder for the carbonate compound due to the influence of phosphate, and the setting time tends to be long..For example, a neat cement of a powder composition comprising 80 parts by weight of lightly burned magnesium, 10 parts by weight of lime heavy superphosphate, 5 parts by weight of sodium bicarbonate, 1 part by weight of sodium polyphosphate, and 0.4 parts by weight of anhydrous citric acid powder. The setting time was 2 hours and 7 minutes at 20 ° C., only the first start was delayed, and the end time was 2 hours and 34 minutes. The strength of the day was 35% higher than that of heavy superphosphate alone. As described above, there is an advantage that the setting time can be freely adjusted by selecting three kinds of curing agents for the magnetic material and adding the organic acid.
[0026]
The present inventionIs the main component of the compositionMagnesia is light burned magnesium and light burned holsterite, light burned talc, light burned serpentine powder,As mentioned above, lightly burned holsterite, lightly burned talc, and lightly burned serpentineContent as MgOButHave a low dislike.However, when 10 to 30 parts by weight of light-burning magnesia is additionally mixed with these, a composition equivalent to the reaction activity of light-burning magnesia can be performed. Lightly burned holsterite, lightly burned talc, and lightly burnt serpentinite powder not only improve acid resistance due to the inclusion of silicic acid, but lightly burned magnesia resources are unevenly distributed in different regions. Holsterite, light burned talc, and light burned serpentinite resources are distributed over a relatively wide area, and are said to be able to be supplied in large quantities at a lower cost than light burned magnesia. For this reason, the advantage that the firing temperature is lower than cement and the productivity is good is very advantageous in terms of cost depending on the use of the composition blended with lightly burned magnesium. Light-burned holsterite tends to become inactive depending on the baking method, but this problem can be solved by baking with salt or baking with magnesium chloride. Since it contains 5-10% of iron depending on the raw ore production area, the baked powder tends to be brown and differs from white or light yellow of light baked magnesia.
[0027]
In using the composition of the present invention, the use of a water reducing agent and a fluidizing agent used in cement can improve the properties of the slurry. The addition of the organic acids as described above also has a water reducing action, Nitrohumates, lignin sulfonates, and citric acid have a good water-reducing effect on magnesia. Naphthalene-based, melamine-based, and polycarboxylic acid-based materials can be used in combination, and foaming agents, thickeners, antifoaming agents, and various polymer emulsions can be used.
[0028]
[Action]
1) The environment-improving cement composition of the present invention uses magnesium as the main component, and when phosphate is used as a curing agent, the amount of phosphate is different from the reaction mole of conventional magnesium phosphate cement. Very low non-stoichiometric formulation. Even when one carbonic acid compound is used, it is a non-stoichiometric compound with very little carbonic acid compound.,The non-stoichiometric composition is the same in both combined systems. These raw material compositions are extremely safe and use fertilizer ingredients, food additives, or similar raw materials, so even if they diffuse into nature, they are safe and have a low pH, and the solubility of the main ingredient magnesia Is 0.0009, which is 1/177 compared to 0.16 for lime, and has the advantage that the setting time can be freely adjusted and the physical strength comparable to cement systems.
2) Cr, a disadvantage of cement-based solidifying agents 6+ In loam soil, solidification is possible in a small amount, and solidified organic waste and industrial waste that cannot be solidified in cement, sludge, waste lime, seabed sediment, hot spring sludge, sulfur-containing materials, etc. Heavy metals, organic solvents, PCBs, dioxins and the like can be stabilized. It is particularly effective for complex inclusions such as complex soil pollution prevention and river sludge, and has a deodorizing action that can fix odors such as ammonia, mercaptan, and hydrogen sulfide.
3) Because it does not contain harmful substances and has a low pH, it is compatible with the biological environment and has no environmental impact, so the molded product can be circulated directly into the soil, and it is not available in conventional cement such as agricultural applications, fish reefs, and revetment concrete. There are reusable uses.
[0029]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Reference example 1
100 parts by weight of raw ash according to the Ministry of the Environment No. 46 test of O city sewer activated sludge incineration ash, and 85 parts by weight of light-burned magnesia (200 mesh or less) which is the environmental improvement cement composition of the present invention (hereinafter referred to as the present invention composition). , 15 parts by weight of heavy calcined phosphorus powder (200 mesh or less), 5 parts by weight of anhydrous gypsum and 30 parts by weight of powder mixture of 0.1 part by weight of anhydrous citric acid were mixed, and 70 parts by weight of water was added thereto The mixture was mixed with a Pobert mixer for 5 minutes, filled in a soil test mold of 50φ × 100, and cured. The molded product cured in the air at room temperature for 28 days was subjected to a compression test according to JIS A 1216. This result is 36.4 N / mm2Met. The crushed specimen was pulverized to 5 mm or less, sieved, and subjected to the Ministry of the Environment No. 46 test to detect heavy metals. Table 1 shows the results of dissolution tests for heavy metals and the like.
[0030]
[Table 1]
Example1
K city incinerator fly ash was analyzed by the Ministry of the Environment No. 46 test, and as a composition of the present invention, 85 parts by weight of lightly burned magnesia (200 mesh or less), 15 parts by weight of heavy burnt phosphorus powder (200 mesh or less), anhydrous gypsum 5 35 parts by weight of a powder mixture of 2.0 parts by weight of sodium polyphosphate and 3.0 parts by weight of beet activated carbon are mixed with 100 parts by weight of the incinerator fly ash. 60 parts by weight of water was added thereto, mixed for 5 minutes with a Pobart mixer, filled into a 50φ × 100 soil test mold and cured. The molded product cured in the air at room temperature for 28 days was subjected to a compression test according to JIS A 1216. This result is 23.2 N / mm2Met. The crushed specimen was pulverized to 5 mm or less, sieved, and subjected to the Ministry of the Environment No. 46 test to detect heavy metals. The results are shown in Table 2.
[0032]
[Table 2]
* The dioxin-containing fly ash solidified product 0.27 ng / l could be reduced to 0.01 ng / l or less by the autoclave treatment at 180 ° C./10 kg for 6 hours.
Example2
Ten times and 100 times the amount of heavy metals (mercury chloride, cadmium chloride, lead nitrate, potassium dichromate, arsenic trichloride, copper chloride) 10 times and 100 times the standard value of the Ministry of the Environment No. 46 test were added to Kanto Loam. As a composition of the present invention, 85 parts by weight of light-burned magnesium (200 mesh or less), 15 parts by weight of heavy superphosphate powder (200 mesh or less), 5 parts by weight of anhydrous gypsum, 0.1 part by weight of anhydrous citric acid, sodium polyphosphate 35 parts by weight of a powder mixture of 2.0 parts by weight and 3.0 parts by weight of beet charcoal is mixed with 100 parts by weight of the above Kanto Loam, and 65 parts by weight of water is added to this and mixed with a Pobert mixer for 5 minutes. Then, it is filled into a 50φ × 100 soil test mold and cured. The molded product cured in the air at room temperature for 28 days was subjected to a compression test according to JIS A 1216. As a result, 14.3 N / mm2Met. The crushed specimen was pulverized to 5 mm or less, sieved, and subjected to the Ministry of the Environment No. 46 test to detect heavy metals. Table 3 shows the results of the load test.
[0034]
[Table 3]
Reference example 2
A powdered mixture of 15 parts by weight of baking soda, 0.4 parts by weight of anhydrous citric acid and 2 parts by weight of ammonium polyphosphate as a keying agent / curing agent was added to 100 parts by weight of light-burned holsterite (360 mesh). A cement composition was obtained. The initial start time at 20 ° C. was 1 hour 16 minutes, the end time was 1 hour 46 minutes, the initial start time at 20 ° C. without addition of anhydrous citric acid was 4.2 minutes, and the end time was 7.4 minutes. When 50 parts by weight of the cement composition of the present invention was added to 100 parts by weight of water sludge with a water content of 300%, and mixed with a Pobert mixer for 5 minutes and filled into a 50φ × 100 soil test form, after 6 hours. Cured. When a compression test is performed on a molded product cured at room temperature for 7 days in accordance with JIS A 1216, 0.43 N / mm2The strength of was shown. The odor of the solidified product disappeared completely and was odorless.
Example3
Table 4 shows typical blending examples of the present invention.
[0036]
[Table 4]
Formula 2,
* The amount of activated carbon is suitably 5 to 20 parts by weight depending on the purpose.
* The setting test and the strength test were performed according to JIS R 5201.
* The specimen pH was crushed to 5 mm or less and immersed in 10 times the amount of pure water for 7 days for testing.
* Number of days of occurrence of blue sea cucumber is the result of a room temperature field test according to the test used for the specimen pH.
* When the Portland cement specimen is compared with the above, there is no occurrence of blue sea bream within this period.
Example4
Example on 100 parts by weight of collected river sediment (water content of
Reference example 3
Example of mixing 100 parts by weight of dried Kanto loam with 2 parts by weight of trichloroethane and 2 parts by weight of tetrachloroethylene3-Formulation 7Set of30 parts by weight of the composition, 10 parts by weight of beet activated carbon and 15 parts by weight of beet activated carbon were added and kneaded with 75 parts by weight of water to solidify. This sample was pulverized to 5 mm or less, subjected to osmotic extraction with water for 6 hours, filtered, and the extract was tested according to JIS K 01255.2. The results are shown in Table 5.
[0038]
[Table 5]
In this load test, similar results were obtained with activated carbon for alcohol.
Example5
100 parts by weight of dried Kanto loam, 200 parts by weight of activated carbon, Examples3-70 parts by weight of water was added to 30 parts by weight of the composition of the present invention of Formulation 1 and mixed to obtain a granulated product having a particle size of 3.5 mm to 5.4 mm. When this granulated product was filled into a pipe having a diameter of 100 mmφ and a length of 1000 mm, and sludge water was allowed to flow down from the upper part, water with no odor was obtained. Ammonia and phosphoric acid were quantified by adding 10 mg / l of ammonia water and 10 mg / l of 40% phosphoric acid to this water and sampling the water flowing from the bottom to determine ammonia and phosphoric acid 0.00006 mg / l. l. Further, when 1 kg of this granulated product was placed in a 10 l water tank and goldfish were bred, the mortality of goldfish was 0 for 28 days.
Comparative Example 1
When 100 Akamedaka were released into 10 liters of water and Portland cement slurry (100 g of cement / 100 g of water) was added in small portions while aeration for 200 cc for 1 minute, the acute toxicity to LC50 was 16.5 g / l. It was. On the other hand, as a result of the same test, the environmental cement composition of the present invention had an acute toxicity of 63.5 g / l reaching LC50.
Comparative Example 2
The elution amount of heavy metals in Portland cement solidification and environmental cement composition solidification of the present invention is shown in FIG. The test method was performed according to the Environmental Agency No. 13 test and the Environmental Agency No. 46 test.
[0040]
【The invention's effect】
The present invention aims to be a solidifying agent that replaces Portland cement, and is a composite environmentally friendly cement composition that can capture heavy metals by the chelating action of phosphate and stabilize organochlorine compounds in combination with activated carbon. The cement composition of the present invention has an extremely low environmental load, does not directly violate the biological environment, and can be circulated as a fertilizer component even when discarded.
[Brief description of the drawings]
FIG. 1 is a graph comparing the elution amounts of heavy metals in Portland cement solidification and environmental cement composition solidification of the present invention.
Claims (4)
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