JP4340058B2 - Method for producing hydrothermal solidified body - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、Ａｌ2Ｏ3分を含む原料からなる水熱固化体の製造方法に関する。
【０００２】
【従来の技術】
従来、ＣａＯ分とＳｉＯ2分とを含む原料から、水熱固化体を製造する方法は知られている（例えば、特許文献１参照。）。この製造方法では、まず調合工程として、ＣａＯ分とＳｉＯ2分とを含む原料により調合物を用意する。そして、成形工程として、調合物を成形して成形体とする。次いで、水熱工程として、その成形体を水熱処理し、ケイ酸カルシウムを生じて固化した水熱固化体を得る。こうして得られる水熱固化体は、タイル等の建材として実用価値がある。
【０００３】
【特許文献１】
特許第３１９６６１１号公報
【０００４】
【発明が解決しようとする課題】
しかし、種々の原料により水熱固化体を製造することができれば、原料の安定供給、製品コスト等の面で好ましいにもかかわらず、従来の技術ではＡｌ2Ｏ3分を含む原料からは水熱固化体を製造することができなかった。
【０００５】
本発明は、上記従来の実情に鑑みてなされたものであって、Ａｌ2Ｏ3分を含む原料から水熱固化体を製造することを特徴とする解決すべき課題としている。
【０００６】
【課題を解決するための手段】
発明者らは、本発明の契機として、各種無機系廃棄物の水熱固化による再資源化を検討した。すなわち、各種無機系廃棄物のうち、排出量が多いものとして、汚泥が知られている。汚泥はその発生プロセスにおいて、ポリ塩化アルミニウム（ＰＡＣ）による凝集沈殿が用いられる場合が多く、ＰＡＣを中和する過程で生成する水酸化アルミニウム（Ａｌ（ＯＨ）3）を多量に含む場合が多い。水酸化アルミニウムは水熱反応性が高いことが知られているものの、汚泥中の水酸化アルミニウムが水熱固化に及ぼす影響は従来から明らかにされていない。このため、発明者らは、Ａｌ成分を多量に含む汚泥の再資源化を図るため、浄水場で発生する汚泥である浄水汚泥の水熱固化について検討し、本発明を完成させるに至った。
【０００７】
本発明の水熱固化体の製造方法は、ＳｉＯ2分、Ａｌ2Ｏ3分及びＣａＯ分を含む原料からなる調合物を用意する調合工程と、該調合物を成形して成形体とする成形工程と、該成形体を水熱処理して固化した水熱固化体を得る水熱工程とを有し、
前記調合工程では、ＳｉＯ 2 分及びＡｌ 2 Ｏ 3 分を含む第１原料と、ＣａＯ分を含む第２原料とを混合した調合物を用意し、該第１原料はポリ塩化アルミニウムを用いて処理され、水酸化アルミニウムを含む汚泥であり、該第２原料は消石灰であり、
前記調合物は、１０質量％以下の前記第２原料と残部の前記第１原料とが混合されたものであり、
前記水熱固化体は、数〜数十ｎｍサイズの微細な細孔を形成するＡｌ／Ｓｉ（モル比）＝０．９〜１．５の組織を有することを特徴とする。
また、本発明の水熱固化体の製造方法は、ＳｉＯ 2 分及びＡｌ 2 Ｏ 3 分を含む原料からなる調合物を用意する調合工程と、
該調合物を成形して成形体とする成形工程と、
該成形体を水熱処理して固化した水熱固化体を得る水熱工程とを有し、
前記調合工程では、ＳｉＯ 2 分及びＡｌ 2 Ｏ 3 分を含む第１原料を用意し、該第１原料はポリ塩化アルミニウムを用いて処理され、水酸化アルミニウムを含む汚泥であり、
前記水熱固化体は、数〜数十ｎｍサイズの微細な細孔を形成するＡｌ／Ｓｉ（モル比）＝０．９〜１．５の組織を有することを特徴とする。
【０００８】
本発明の製造方法では、Ａｌ2Ｏ3分を含む原料から水熱固化体を製造することができる。このため、従来にも増して種々の原料により水熱固化体を製造することができ、原料の安定供給、製品コスト等の面で好ましい。
【０００９】
調合物は、Ａｌ2Ｏ3分の一部又は全てが水酸化アルミニウムであることが好ましい。水酸化アルミニウムは水への溶解度が高く、水熱処理時の反応性が高いためである。また、これにより汚泥の再資源化を実現することができる。
【００１０】
ＳｉＯ2分は、珪砂、ガラス粉、石英粉、シリカフューム、廃鋳物砂、籾殻灰、珪藻土、ホワイトカーボン、コンクリート屑、シラス、白土等により構成することができる。Ａｌ2Ｏ3分は、長石、粘土、キラ、陶磁器屑、石炭灰、下水汚泥焼却灰、アルミサッシ工場等で発生する水酸化アルミニウムスラッジ、赤泥、スラグ、釉汚泥、メタカオリン、アロフェン、ゼオライト等により構成することができる。また、ＳｉＯ2分及びＡｌ2Ｏ3分を含む原料としては、長石、粘土、ガラス粉、廃鋳物砂、コンクリート屑、シラス、白土、キラ、陶磁器屑、石炭灰、下水汚泥焼却灰、赤泥、スラグ、釉汚泥、メタカオリン、アロフェン、ゼオライト等の他、ＰＡＣを用いて処理された汚泥を採用することができる。第１原料として、ＰＡＣを用いて処理された汚泥を採用すれば、再資源化を実現することができる。
【００１１】
調合物はＣａＯ分を含み得る。ＣａＯ分は消石灰（Ｃａ（ＯＨ）2）等により構成することができる。発明者らは、調合工程では、ＳｉＯ2分及びＡｌ2Ｏ3分を含む第１原料と、ＣａＯ分を含む第２原料とを混合した調合物を用意し、第１原料はＰＡＣを用いて処理された汚泥であり、第２原料は消石灰である場合に本発明の効果を確認した。
【００１２】
第１原料は、ＰＡＣを用いて処理された汚泥を加熱処理したものであることが好ましい。加熱処理により水熱固化に不必要な有機分を除去することができる。また、加熱処理により水分量がほとんどないものになるため、成形及び水熱固化に必要な水分を調整し易く、水熱固化体をより製造し易いからである。加熱処理後の汚泥を湿式粉砕すれば、汚泥中のアルミナ分が再水和し、成形及び水熱固化に必要な水分の調整をより行い易くなる。また、粉砕により汚泥の粒径が小さくなり、反応性が向上する。
【００１３】
発明者らは、調合物が１０質量％以下の第２原料と残部の第１原料とが混合されたものである場合に本発明の効果を確認した。
【００１４】
成形工程を乾式プレス法により行なうことが好ましい。これにより、原料の搬送、保管が容易になる。また、水熱固化に必要な水分を調整した成形体を成形することができ、成形体の乾燥を行なうことなく水熱固化体を製造することができる。これらのため、製造コストの低廉化を実現できる。また、乾式プレス法により成形すれば、原料粒子間の距離が小さくなり、水熱処理で生成する組織を数〜数十ｎｍサイズにして強度発現を効率よく行うことができる。
【００１５】
発明者らは、水熱固化体がＡｌ／Ｓｉ（モル比）＝０．９〜１．５の組織を有して固化していることを確認している。この組織は、数〜数十ｎｍサイズの微細なものであり、アモルファスの可能性もある。このため、Ａｌ／Ｓｉ（モル比）＝０．９〜１．５になるように調合工程を行なうことが好ましいこともわかる。
【００１６】
【発明の実施の形態】
以下、本発明を具体化した実施形態を図面を参照しつつ説明する。
【００１７】
この実施形態では、浄水場で発生する汚泥である浄水汚泥の水熱固化について、調合及び水熱処理温度が水熱固化体の強度発現に及ぼす影響を検討する。
【００１８】
まず、図１に示す調合工程Ｓ１０として、ＰＡＣを用いて処理された浄水汚泥と、宇部マテリアル（株）製の消石灰とを用意する。浄水汚泥は、浄水場で発生した汚泥をフィルタープレスにより脱水した後、乾燥したものである。この浄水汚泥の化学組成を表１に示す。また、この浄水汚泥の構成相をＸＲＤチャートにより図２に示す。図２において、Ｑはquartz（ＳｉＯ2）であり、Ｍはmuscovite（ＫＡｌ2（Ｓｉ3Ａｌ）Ｏ10（ＯＦ，Ｆ）2）であり、Ａはalbite（ＮａＡｌＳｉ3Ｏ8）であり、Ｃｌはclinochlore（（Ｍｇ，Ａｌ）6（Ｓｉ，Ａｌ）4Ｏ10（ＯＨ）8）であり、Ｋはkaolinite（Ａｌ2Ｓｉ2Ｏ5（ＯＨ）4）である（以下、同様。）。なお、浄水汚泥はＰＡＣを用いて処理されているため、ＰＡＣを中和する過程で生成する水酸化アルミニウムを含むが、水酸化アルミニウムは非晶質であるため、ＸＲＤチャートでは、１５〜３５°のハロー（ブロードなバックグラウンドの盛り上がり）として認められる。
【００１９】
【表１】
浄水汚泥の有機分除去のための前処理として、浄水汚泥を６００°Ｃで１０時間加熱処理する。加熱処理後の浄水汚泥をポットミルで４時間湿式粉砕し、乾燥する。これにより浄水汚泥中のアルミナ分が再水和し、成形及び水熱固化に必要な水分の調整が容易になる。また、粉砕により浄水汚泥の粒径が小さくなり、反応性が向上する。前処理前の浄水汚泥と、６００°Ｃで１０時間加熱処理後の浄水汚泥と、４時間の湿式粉砕及び乾燥後の浄水汚泥との構成相をＸＲＤチャートにより図３に示す。図２及び図３より、６００°Ｃの加熱処理でkaoliniteが分解したものの、その他の鉱物はほとんど変化しないことがわかる。
【００２１】
湿式粉砕及び乾燥後の浄水汚泥を第１原料とし、この第１原料に第２原料としての消石灰が０〜２０質量％となるように加えるとともに、外割で３０質量％の蒸留水を加えて混合する。こうして各調合物を得る。
【００２２】
図１に示す成形工程Ｓ２０として、各調合物を乾式プレス法により成形圧力３０ＭＰａで１０ｍｍ×１５ｍｍ×４０ｍｍの直方体に一軸加圧成形し、各成形体を得る。成形体の曲げ強度は１ＭＰａ、成形体の嵩密度は１．０７（ｇ／ｃｍ3）であった。
【００２３】
そして、水熱工程Ｓ３０として、各成形体に対し、１６０〜２２０°Ｃで６時間又は２２０°Ｃで１０時間の水熱処理を行なう。こうして、水熱固化体である各試験体を得る。各試験体の嵩密度は１．０８〜１．０９（ｇ／ｃｍ3）であった。
【００２４】
こうして、この製造方法では、Ａｌ2Ｏ3分を含む原料から水熱固化体を製造することができる。このため、従来にも増して種々の原料により水熱固化体を製造することができ、原料の安定供給、製品コスト等の面で好ましいことが明らかである。
【００２５】
各試験体を８０°Ｃで２日間乾燥後、各試験体について、曲げ強度（３点曲げ試験法）、生成相（粉末Ｘ線回折）及び微構造（ＳＥＭ、水銀圧入法による細孔分布測定）を評価した。
【００２６】
２２０°Ｃで１０時間水熱処理した場合における消石灰の添加量（質量％）と曲げ強度（ＭＰａ）との関係を図４に示す。図４より、消石灰の添加量が５質量％の調合物を用いた試験体が最大の曲げ強度である１３．０ＭＰａを示すことがわかる。消石灰をこれより減少させたり、増加させたりした試験体は曲げ強度が低下している。消石灰が１０質量％以下（０質量％を含み、１０質量％以下）であれば、インターロッキングブロックの規格値である５ＭＰａ以上の曲げ強度の水熱固化体が得られている。このため、１０質量％以下の消石灰と残部の浄水汚泥焼却灰とが混合された調合物により、実用的な水熱固化体を製造できることがわかる。なお、用途によっては、１０ＭＰａ程度の高い曲げ強度の水熱固化体を得る必要があり、消石灰を３〜８質量％にすることがより好ましい。
【００２７】
また、消石灰の添加量が５質量％の試験体を各水熱処理温度で６時間水熱処理した場合における水熱処理温度（°Ｃ）と曲げ強度（ＭＰａ）との関係を図５に示す。図５より、水熱処理温度が高くなれば、徐々に大きな曲げ強度が得られることがわかる。
【００２８】
消石灰の添加量に伴う構成相の変化をＸＲＤチャートにより図６に示す。また、消石灰の添加量が５質量％の試験体における水熱処理温度（°Ｃ）に伴う構成相の変化をＸＲＤチャートにより図７に示す。また、消石灰の添加量が２０質量％の試験体における水熱処理前後の構成相の変化をＸＲＤチャートにより図８に示す。図６〜８において、Ｑ、Ｍ、Ａ、Ｃｌ及びＫは図２に示した場合と同様であり、Ｐはportlandite（Ｃａ（ＯＨ）2）、Ｃはcalcite（ＣａＣＯ3）、Ｈはhydrogarnet（Ｃａ3Ａｌ2（ＳｉＯ4）（ＯＨ）8）、Ａｎはanhdrite（ＣａＳＯ4）、●はＣａ4Ａｌ2ＣＯ9・１１Ｈ2Ｏである（以下、同様。）。図６より、消石灰の添加量が２０質量％の試験体では、hydrogarnetが生成したものの、消石灰の添加量が２０質量％未満の試験体では、hydrogarnetの生成が認められないことがわかる。
【００２９】
消石灰の添加量に伴う水熱処理した各試験体の細孔径分布を図９に示す。また、消石灰の添加量が５質量％で水熱処理温度を変化させた試験体における細孔径分布を図１０に示す。図９及び図１０より、消石灰の添加量が１５質量％以下の試験体で強度発現し、消石灰の添加量が２０質量％の試験体で強度発現しなかった原因は、消石灰の添加量が１５質量％以下の試験体では、１０ｎｍ（０．０１μｍ）を中心とする数〜数十ｎｍサイズの微細な細孔が形成されて強度が発現しているのに対し、消石灰の添加量が２０質量％の試験体では水熱処理の前後で細孔径分布にほとんど変化が認められなかったためであると考えられる。
【００３０】
また、消石灰の添加量が０質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真を図１１に示し、消石灰の添加量が２質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真を図１２に示し、消石灰の添加量が５質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真を図１３に示し、消石灰の添加量が１０質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真を図１４に示し、消石灰の添加量が２０質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真を図１５に示す。
【００３１】
最大の曲げ強度を示した消石灰の添加量が５質量％の試験体は、成形体においてはhydrogarnetの生成は認められなかったものの、水熱処理することで約１０ｎｍの細孔が形成されている。図１１〜１５に示すＳＥＭ観察から、消石灰の添加量が１５質量％以下の試験体では、水熱処理により数〜数１０ｎｍサイズの生成物が認められ、強度発現に寄与していると推察される。一方、消石灰の添加量が２０質量％の試験体では、数〜数十ｎｍサイズの微細組織の形成は認められなかった。
【００３２】
また、ＥＤＳ分析から、各試験体の数〜数十ｎｍサイズの微細組織は主にＳｉＯ2とＡｌ2Ｏ3成分から構成され、Ａｌ／Ｓｉ（モル比）＝０．９〜１．５であることが判明した。また、各試験体のＸＲＤ結果より、Ｃａ（ＯＨ）2の添加量が５質量％の試験体のみ、kaolonite（Ａｌ2Ｓｉ2Ｏ5（ＯＨ）4）と疑われるピークが認められた。以上の結果から、数〜数十ｎｍサイズの生成物はkaolonit若しくはその前駆体であると推測している。
【図面の簡単な説明】
【図１】実施形態の製造方法を示す工程図である。
【図２】前処理前の浄水汚泥の構成相を示すＸＲＤチャートである。
【図３】前処理前の浄水汚泥と、６００°Ｃで１０時間加熱処理後の浄水汚泥と、４時間の湿式粉砕及び乾燥後の浄水汚泥との構成相を示すＸＲＤチャートである。
【図４】２２０°Ｃで１０時間水熱処理した場合における消石灰の添加量と曲げ強度との関係を示すグラフである。
【図５】消石灰の添加量が５質量％の試験体を各水熱処理温度で６時間水熱処理した場合における水熱処理温度と曲げ強度との関係を示すグラフである。
【図６】消石灰の添加量に伴う構成相の変化を示すＸＲＤチャートである。
【図７】消石灰の添加量が５質量％の試験体における水熱処理温度に伴う構成相の変化をＸＲＤチャートである。
【図８】消石灰の添加量が２０質量％の試験体における水熱処理前後の構成相の変化を示すＸＲＤチャートである。
【図９】消石灰の添加量に伴う水熱処理した試験体の細孔径分布を示すグラフである。
【図１０】消石灰の添加量が５質量％で水熱処理温度を変化させた試験体における細孔径分布を示すグラフである。
【図１１】消石灰の添加量が０質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真である。
【図１２】消石灰の添加量が２質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真である。
【図１３】消石灰の添加量が５質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真である。
【図１４】消石灰の添加量が１０質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真である。
【図１５】消石灰の添加量が２０質量％の成形体を２２０°Ｃで１０時間水熱処理した試験体のＳＥＭ写真である。
【符号の説明】
Ｓ１０…調合工程
Ｓ２０…成形工程
Ｓ３０…水熱工程[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a hydrothermal solid body comprising a raw material containing Al 2 O 3 .
[0002]
[Prior art]
Conventionally, a method for producing a hydrothermal solid from a raw material containing a CaO component and a SiO 2 component has been known (see, for example, Patent Document 1). In this manufacturing method, first, as a blending step, a blend is prepared from raw materials containing a CaO component and a SiO 2 component . And as a forming process, the preparation is formed into a formed body. Next, as a hydrothermal process, the compact is hydrothermally treated to obtain a hydrothermal solidified body that is solidified by generating calcium silicate. The hydrothermal solidified body thus obtained has practical value as a building material such as a tile.
[0003]
[Patent Document 1]
Japanese Patent No. 3196611 [0004]
[Problems to be solved by the invention]
However, if a hydrothermal solidified body can be produced from various raw materials, it is preferable from the viewpoint of stable supply of raw materials, product costs, etc., but in the conventional technology, hydrothermal heat is generated from raw materials containing Al 2 O 3. A solidified body could not be produced.
[0005]
The present invention was made in view of the above conventional circumstances, and a problem to be solved, characterized in that to produce a hydrothermally solidified body from a raw material containing Al 2 O 3 minutes.
[0006]
[Means for Solving the Problems]
The inventors studied the recycling of various inorganic wastes by hydrothermal solidification as an opportunity of the present invention. That is, among various inorganic wastes, sludge is known as having a large emission amount. In the generation process of sludge, coagulation precipitation by polyaluminum chloride (PAC) is often used, and a large amount of aluminum hydroxide (Al (OH) 3 ) generated in the process of neutralizing PAC is often included. Although aluminum hydroxide is known to have high hydrothermal reactivity, the influence of aluminum hydroxide in sludge on hydrothermal solidification has not been clarified. Therefore, the inventors have studied hydrothermal solidification of purified water sludge, which is sludge generated at a water purification plant, in order to recycle sludge containing a large amount of Al component, and have completed the present invention.
[0007]
The method for producing a hydrothermal solidified body of the present invention comprises a preparation step of preparing a preparation comprising a raw material containing SiO 2 part , Al 2 O 3 part and CaO part , and molding the preparation into a molded body. a molding step, the molded article and a hydrothermal process to obtain a hydrothermal treatment to solidified hydrothermally solidified body possess,
In the preparation step, a preparation is prepared by mixing a first raw material containing SiO 2 and Al 2 O 3 and a second raw material containing CaO, and the first raw material is treated with polyaluminum chloride. Sludge containing aluminum hydroxide, the second raw material is slaked lime,
The preparation is a mixture of 10% by mass or less of the second raw material and the remaining first raw material,
The hydrothermal solidification body, characterized in that have a Al / Si (molar ratio) = 0.9 to 1.5 of the tissue to form fine pores of several to several tens of nm size.
Moreover, the method for producing the hydrothermal solidified body of the present invention comprises a preparation step of preparing a preparation comprising a raw material containing SiO 2 minutes and Al 2 O 3 minutes,
A molding step of molding the preparation to form a molded body;
A hydrothermal step of obtaining a hydrothermal solidified body obtained by hydrothermally treating the molded body,
In the preparation step, a first raw material containing SiO 2 and Al 2 O 3 is prepared, and the first raw material is sludge treated with polyaluminum chloride and containing aluminum hydroxide,
The hydrothermal solidified body has a structure of Al / Si (molar ratio) = 0.9 to 1.5 forming fine pores having a size of several to several tens of nm.
[0008]
In the production method of the present invention, a hydrothermal solidified product can be produced from a raw material containing Al 2 O 3 . For this reason, a hydrothermal solidification body can be manufactured with various raw materials more than before, and it is preferable in terms of stable supply of raw materials, product costs, and the like.
[0009]
Formulation is preferably Al 2 O 3 minutes of part or all is aluminum hydroxide. This is because aluminum hydroxide has high solubility in water and high reactivity during hydrothermal treatment. This also makes it possible to recycle sludge.
[0010]
The SiO 2 component can be composed of silica sand, glass powder, quartz powder, silica fume, waste casting sand, rice husk ash, diatomaceous earth, white carbon, concrete scrap, shirasu, white clay, and the like. Al 2 O 3 component is feldspar, clay, glitter, ceramic scrap, coal ash, sewage sludge incineration ash, aluminum hydroxide sludge generated in aluminum sash factories, red mud, slag, straw sludge, metakaolin, allophane, zeolite, etc. Can be configured. In addition, raw materials containing SiO 2 and Al 2 O 3 include feldspar, clay, glass powder, waste casting sand, concrete scrap, shirasu, white clay, glitter, ceramic scrap, coal ash, sewage sludge incinerated ash, red mud In addition to sludge, soot sludge, metakaolin, allophane, zeolite, etc., sludge treated with PAC can be employed. If sludge treated with PAC is employed as the first raw material, recycling can be realized.
[0011]
The formulation may contain CaO content. The CaO component can be composed of slaked lime (Ca (OH) 2 ) or the like. We, the compounding process, providing a formulation comprising a mixture of a first material containing SiO 2 minutes and Al 2 O 3 minutes, and a second raw material containing CaO content, the first feedstock with a PAC The effect of the present invention was confirmed when the sludge was treated and the second raw material was slaked lime.
[0012]
It is preferable that the 1st raw material is what heat-processed the sludge processed using PAC. Organic components unnecessary for hydrothermal solidification can be removed by heat treatment. Moreover, since there will be almost no moisture content by heat processing, it is easy to adjust the water | moisture content required for shaping | molding and hydrothermal solidification, and it is easier to manufacture a hydrothermal solidified body. If the heat-treated sludge is wet pulverized, the alumina content in the sludge is rehydrated, and it becomes easier to adjust the moisture necessary for molding and hydrothermal solidification. Moreover, the particle size of sludge becomes small by grinding | pulverization, and the reactivity improves.
[0013]
The inventors confirmed the effect of the present invention when the preparation was a mixture of 10% by mass or less of the second raw material and the remaining first raw material.
[0014]
It is preferable to perform the forming step by a dry press method. Thereby, conveyance and storage of a raw material become easy. Moreover, the molded object which adjusted the water | moisture content required for hydrothermal solidification can be shape | molded, and a hydrothermal solidified body can be manufactured, without drying a molded object. For these reasons, the manufacturing cost can be reduced. Moreover, if it shape | molds by a dry press method, the distance between raw material particles will become small, and the structure | tissue produced | generated by a hydrothermal treatment can be made into several to several tens nm size, and intensity | strength expression can be performed efficiently.
[0015]
The inventors have confirmed that the hydrothermal solidified body has a structure of Al / Si (molar ratio) = 0.9 to 1.5 and is solidified. This structure is a fine one having a size of several to several tens of nanometers, and may be amorphous. For this reason, it turns out that it is preferable to perform a preparation process so that Al / Si (molar ratio) = 0.9-1.5.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, embodiments of the invention will be described with reference to the drawings.
[0017]
In this embodiment, about the hydrothermal solidification of the purified water sludge which is the sludge which generate | occur | produces in a water purification plant, the influence which mixing and hydrothermal treatment temperature exert on the strength expression of a hydrothermal solidified body is examined.
[0018]
First, as the blending step S10 shown in FIG. 1, purified water sludge processed using PAC and slaked lime manufactured by Ube Material Co., Ltd. are prepared. The purified water sludge is obtained by dewatering sludge generated at a water purification plant using a filter press and then drying it. Table 1 shows the chemical composition of this purified water sludge. Moreover, the constituent phase of this purified water sludge is shown in FIG. 2 by an XRD chart. In FIG. 2, Q is quartz (SiO 2 ), M is musclecovite (KAl 2 (Si 3 Al) O 10 (OF, F) 2 ), A is albite (NaAlSi 3 O 8 ), and Cl Is clolinochlore ((Mg, Al) 6 (Si, Al) 4 O 10 (OH) 8 ), and K is kaolinite (Al 2 Si 2 O 5 (OH) 4 ) (the same applies hereinafter). In addition, since purified water sludge is processed using PAC, it contains aluminum hydroxide produced in the process of neutralizing PAC. However, since aluminum hydroxide is amorphous, it is 15 to 35 ° in the XRD chart. Halo (broad background climax).
[0019]
[Table 1]
As a pretreatment for removing organic components from the purified water sludge, the purified water sludge is heated at 600 ° C. for 10 hours. The purified water sludge after the heat treatment is wet pulverized in a pot mill for 4 hours and dried. As a result, the alumina content in the purified water sludge is rehydrated, and the adjustment of moisture necessary for molding and hydrothermal solidification becomes easy. In addition, the particle size of the purified water sludge is reduced by pulverization, and the reactivity is improved. The constituent phases of the purified water sludge before pretreatment, the purified water sludge after heat treatment at 600 ° C. for 10 hours, and the purified water sludge after wet grinding and drying for 4 hours are shown in FIG. 3 by XRD chart. 2 and 3, it can be seen that although kaolinite was decomposed by heat treatment at 600 ° C., other minerals hardly changed.
[0021]
The purified water sludge after wet pulverization and drying is used as the first raw material, and the slaked lime as the second raw material is added to the first raw material so that it is 0 to 20% by mass, and 30% by mass of distilled water is added as an external split Mix. Each formulation is thus obtained.
[0022]
As molding process S20 shown in FIG. 1, each formulation is uniaxially press-molded into a 10 mm × 15 mm × 40 mm rectangular parallelepiped at a molding pressure of 30 MPa by a dry press method to obtain each molded body. The bending strength of the molded body was 1 MPa, and the bulk density of the molded body was 1.07 (g / cm 3 ).
[0023]
And as hydrothermal process S30, the hydrothermal treatment of 160 to 220 degreeC for 6 hours or 220 degreeC for 10 hours is performed with respect to each molded object. In this way, each test body which is a hydrothermal solidified body is obtained. The bulk density of each specimen was 1.08 to 1.09 (g / cm 3 ).
[0024]
Thus, in this production method, a hydrothermal solidified body can be produced from the raw material containing Al 2 O 3 . For this reason, it is clear that hydrothermal solidified bodies can be produced from various raw materials as compared with the prior art, which is preferable in terms of stable supply of raw materials and product costs.
[0025]
After each specimen was dried at 80 ° C for 2 days, the bending distribution (three-point bending test method), product phase (powder X-ray diffraction) and microstructure (SEM, measurement of pore distribution by mercury intrusion method) were used for each specimen. ) Was evaluated.
[0026]
FIG. 4 shows the relationship between the amount of slaked lime added (mass%) and the bending strength (MPa) when hydrothermally treated at 220 ° C. for 10 hours. From FIG. 4, it can be seen that the test body using the preparation in which the amount of slaked lime added is 5% by mass shows 13.0 MPa which is the maximum bending strength. The test body in which the amount of slaked lime is reduced or increased is lower in bending strength. If slaked lime is 10 mass% or less (including 0 mass% and 10 mass% or less), the hydrothermal solidified body of the bending strength of 5 MPa or more which is the standard value of an interlocking block is obtained. For this reason, it turns out that a practical hydrothermal solidification body can be manufactured with the formulation with which 10 mass% or less of slaked lime and the remainder purified water sludge incineration ash were mixed. In addition, depending on a use, it is necessary to obtain a hydrothermal solidified body having a high bending strength of about 10 MPa, and it is more preferable to make
[0027]
Further, FIG. 5 shows the relationship between hydrothermal treatment temperature (° C.) and bending strength (MPa) when a test specimen having a slaked lime addition amount of 5 mass% is hydrothermally treated for 6 hours at each hydrothermal treatment temperature. From FIG. 5, it can be seen that as the hydrothermal treatment temperature is increased, a large bending strength can be obtained gradually.
[0028]
FIG. 6 shows the change of the constituent phase with the amount of slaked lime by XRD chart. Moreover, the change of the structural phase accompanying the hydrothermal treatment temperature ((degreeC)) in the test body with the addition amount of slaked
[0029]
FIG. 9 shows the pore size distribution of each test specimen hydrothermally treated with the amount of slaked lime added. Moreover, the pore diameter distribution in the test body which changed the hydrothermal treatment temperature when the addition amount of slaked lime is 5 mass% is shown in FIG. From FIG. 9 and FIG. 10, the amount of slaked lime added is 15% by mass or less, and the strength of the slaked lime added is 20% by mass. In specimens of less than mass%, fine pores with a size of several to several tens of nm centering on 10 nm (0.01 μm) are formed and the strength is expressed, whereas the addition amount of slaked lime is 20 mass. % Of the specimens were considered to show little change in the pore size distribution before and after hydrothermal treatment.
[0030]
Moreover, the SEM photograph of the test body which hydrothermally processed the molded object with the addition amount of slaked
[0031]
In the test body with the addition amount of slaked lime showing the maximum bending strength of 5% by mass, the formation of hydrogarnet was not observed in the molded body, but pores of about 10 nm were formed by hydrothermal treatment. From the SEM observation shown in FIGS. 11 to 15, in the test body in which the addition amount of slaked lime is 15% by mass or less, a product of several to several tens of nanometers in size is recognized by hydrothermal treatment, and it is assumed that it contributes to strength development. . On the other hand, in the test body in which the amount of slaked lime added was 20% by mass, formation of a fine structure having a size of several to several tens of nm was not recognized.
[0032]
Further, from the EDS analysis, the microstructure of several to several tens of nanometers in each specimen is mainly composed of SiO 2 and Al 2 O 3 components, and Al / Si (molar ratio) = 0.9 to 1.5. It turned out to be. Moreover, from the XRD result of each test body, the peak suspected to be kaolonite (Al 2 Si 2 O 5 (OH) 4 ) was recognized only in the test body in which the added amount of Ca (OH) 2 was 5 mass%. From the above results, it is estimated that a product having a size of several to several tens of nm is kaolonit or a precursor thereof.
[Brief description of the drawings]
FIG. 1 is a process diagram showing a production method of an embodiment.
FIG. 2 is an XRD chart showing a constituent phase of purified water sludge before pretreatment.
FIG. 3 is an XRD chart showing constituent phases of purified water sludge before pretreatment, purified water sludge after heat treatment at 600 ° C. for 10 hours, and purified water sludge after wet grinding and drying for 4 hours.
FIG. 4 is a graph showing the relationship between the amount of slaked lime added and the bending strength when hydrothermally treated at 220 ° C. for 10 hours.
FIG. 5 is a graph showing the relationship between hydrothermal treatment temperature and bending strength when a test specimen with 5% by mass of slaked lime is hydrothermally treated for 6 hours at each hydrothermal treatment temperature.
FIG. 6 is an XRD chart showing the change of the constituent phase with the addition amount of slaked lime.
FIG. 7 is an XRD chart showing the change of the constituent phase with the hydrothermal treatment temperature in a test body in which the amount of slaked lime added is 5 mass%.
FIG. 8 is an XRD chart showing changes in constituent phases before and after hydrothermal treatment in a test specimen with a slaked lime addition amount of 20 mass%.
FIG. 9 is a graph showing the pore size distribution of a hydrothermally treated specimen according to the amount of slaked lime added.
FIG. 10 is a graph showing the pore size distribution in a test specimen in which the amount of slaked lime added is 5% by mass and the hydrothermal treatment temperature is changed.
FIG. 11 is an SEM photograph of a test body that was hydrothermally treated for 10 hours at 220 ° C. with a shaped body having an added amount of slaked lime of 0% by mass.
FIG. 12 is an SEM photograph of a test body obtained by hydrothermally treating a molded body having a slaked lime addition amount of 2% by mass at 220 ° C. for 10 hours.
FIG. 13 is an SEM photograph of a test body that was hydrothermally treated for 10 hours at 220 ° C. with a shaped body having an added amount of slaked lime of 5 mass%.
FIG. 14 is an SEM photograph of a test body that was hydrothermally treated for 10 hours at 220 ° C. with a shaped body having an added amount of slaked lime of 10 mass%.
FIG. 15 is an SEM photograph of a test body obtained by hydrothermally treating a molded body having a slaked lime addition amount of 20% by mass at 220 ° C. for 10 hours.
[Explanation of symbols]
S10 ... Preparation step S20 ... Molding step S30 ... Hydrothermal step
Claims (5)
該調合物を成形して成形体とする成形工程と、
該成形体を水熱処理して固化した水熱固化体を得る水熱工程とを有し、
前記調合工程では、ＳｉＯ 2 分及びＡｌ 2 Ｏ 3 分を含む第１原料と、ＣａＯ分を含む第２原料とを混合した調合物を用意し、該第１原料はポリ塩化アルミニウムを用いて処理され、水酸化アルミニウムを含む汚泥であり、該第２原料は消石灰であり、
前記調合物は、１０質量％以下の前記第２原料と残部の前記第１原料とが混合されたものであり、
前記水熱固化体は、数〜数十ｎｍサイズの微細な細孔を形成するＡｌ／Ｓｉ（モル比）＝０．９〜１．５の組織を有することを特徴とする水熱固化体の製造方法。 A preparation step of preparing a preparation comprising raw materials containing SiO 2 minutes , Al 2 O 3 minutes and CaO content ;
A molding step of molding the preparation to form a molded body;
The molded article possess a hydrothermal process to obtain a hydrothermal treatment to solidified hydrothermal solidified body,
In the preparation step, a preparation is prepared by mixing a first raw material containing SiO 2 and Al 2 O 3 and a second raw material containing CaO, and the first raw material is treated with polyaluminum chloride. Sludge containing aluminum hydroxide, the second raw material is slaked lime,
The preparation is a mixture of 10% by mass or less of the second raw material and the remaining first raw material,
The hydrothermal solidification body, several to several tens nm to form a fine pore size Al / Si (molar ratio) = 0.9 to 1.5 hydrothermal solidification body which is characterized in that chromatic tissue Manufacturing method.
該調合物を成形して成形体とする成形工程と、 A molding step of molding the preparation to form a molded body;
該成形体を水熱処理して固化した水熱固化体を得る水熱工程とを有し、 A hydrothermal step of obtaining a hydrothermal solidified body obtained by hydrothermally treating the molded body,
前記調合工程では、ＳｉＯ In the preparation step, SiO 22 分及びＡｌMinute and Al 22 ＯO 3Three 分を含む第１原料を用意し、該第１原料はポリ塩化アルミニウムを用いて処理され、水酸化アルミニウムを含む汚泥であり、A first raw material containing a portion, the first raw material is a sludge treated with polyaluminum chloride and containing aluminum hydroxide;
前記水熱固化体は、数〜数十ｎｍサイズの微細な細孔を形成するＡｌ／Ｓｉ（モル比）＝０．９〜１．５の組織を有することを特徴とする水熱固化体の製造方法。 The hydrothermal solidified body has a structure of Al / Si (molar ratio) = 0.9 to 1.5 forming fine pores having a size of several to several tens of nanometers. Production method.
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