JP2004182492A - Spherical microporous silica porous particle and its manufacturing method - Google Patents
Spherical microporous silica porous particle and its manufacturing method Download PDFInfo
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- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 83
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- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 33
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- 238000006243 chemical reaction Methods 0.000 claims description 46
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- 238000000034 method Methods 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、球状マイクロポアシリカ多孔質粒子及びその製造方法に関するものである。より詳細には、アルカリ珪酸塩をシリカ源として使用し、そこから生成するシリカ溶存種を含む酸性溶液相において、非イオン性界面活性剤の秩序形成能に基づいてミクロ構造の規則性と、マクロ形態の規則性を同時に得ることを利用した、球形状の規則形態を持つマイクロポアシリカ多孔質粒子及びその製造法に関するものである。
【０００２】
【従来の技術】
多孔性材料の吸着分離並びに触媒能が、細孔の化学的表面特性並びにその形と大きさおよびその均一性に大きく依存することから、多孔性材料は細孔の大きさによって３つのタイプに分類される。
マイクロポア多孔体 ２ｎｍ以下
メソポア多孔体 ２〜５０ｎｍ
マクロポア多孔体 ５０ｎｍ以上
シリカを主成分とするマイクロポア多孔体の中で、ゼオライトは分子の大きさを識別できる分子ふるい作用を示すことからモレキュラーシーブと呼ばれ、現在最も広く使用されている物質群である。ゼオライトの特異な吸着性や高いイオン交換性は古くから注目され、天然産のものはイオン交換剤、土壌改良剤などに用いられていた。１９５６年ユニオンカーバイド社が商品名ＬＭＳ（Ｌｉｎｄｅ Ｍｏｌｅｃｕｌａｒ Ｓｉｅｖｅ）を開発した。また、１９６０年に固体酸ゼオライト触媒を開発したモービル石油社は、その後もこの方面の研究開発に主導的役割を演じ、１９７０年には高シリカゼオライトＺＳＭ−５を開発した。ゼオライトが工業生産されて以来、分子ふるい特性や触媒特性に関する研究が著しく発展し、幾多の工業プロセスの開発、および新種のゼオライトの合成技術も進展した。
一方、ゼオライトは分子篩い能だけでなく、多くの優れた特性を持つが、細孔径以上の大きな分子に対しては触媒活性を示さない。これは、ゼオライトが１分子の有機テンプレートを鋳型として水熱合成法によって得られる結晶質物質であり、細孔径がゼオライトの結晶構造によって決定されるためである。Ｓｉ、Ａｌを主成分として１ｎｍ以上の細孔径の粒子を合成することは極めて難しいことが知られている。テンプレートとして大きな分子を使用して合成できるのは、Ａｌ（Ｆｅ、Ｓｉ）やＧａのリン酸塩である。これまでに３ｎｍの細孔径を持つ ｃｌｏｖｅｒｉｔｅ、ＪＦＤ−２０等２０員環を持つものも報告されているが、水熱安定性が弱く実用的な耐久性に課題がある。１９９６年には骨格がＳｉ、Ａｌから成り１４員環（細孔径１ｘ０．７５ｎｍ）を持つＵＴＤ−１が合成され、１０００℃まで耐熱性があること、強いブレンステッド酸点の存在等が明らかになった。
【０００３】
さらに、多孔性材料開発の歴史の中で、１９９０年代初頭報告された均一メソ孔がハニカム状に規則配列したメソポア多孔体ＦＳＭ−１６とＭＣＭ−４１の合成法は、エキサイティングな発見として特筆される。メソポーラス材料は界面活性剤の分子集合体をテンプレートとして合成され、その発見以来メソポア材料研究は一気に加速され、分子篩い性に基づいた触媒としてばかりでなく、メソ孔内における機能性分子の規則配列を利用した光、磁気、電気機能を有する包接化合物への応用も考えられている。しかし、吸着材料としての観点からは、細孔容積は大きいものの、吸着物質を取り込む能力においてはゼオライトに劣る場合が多く見られ、現在でもメソポーラス材料に特異な吸着現象を利用した実用化段階に到達した例はほとんどない。また、前述の通り、ゼオライトは結晶構造によって細孔径、さらには細孔容積も一義的に決まり、より大きな細孔空間を有するマイクロポア多孔体を作製することも多孔体開発においては大きな研究課題である。
【０００４】
最近、メソポーラス材料の合成手法である界面活性剤の分子集合体をテンプレートとするマイクロポア多孔体の合成に関する報告がなされている（シリカ系では、Ｃｈｅｍ． Ｃｏｍｍｕｎ． ２０００， ５３３； Ｃｈｅｍ． Ｃｏｍｍｕｎ． ２０００， ２０５７；さらにシリカ・アルミナ系ではＣｈｅｍ． Ｃｏｍｍｕｎ． ２０００， ２０４１； Ｃｈｅｍ． Ｃｏｍｍｕｎ． ２００１， １０１６等が報告されている）。さらに、ゼオライト合成用のシリカ原料にはアルカリ珪酸塩が使用されるが、分子集合体をテンプレートとする上記のマイクロポア多孔体及びメソポーラス材料合成用のシリカ源は、アルコキシシラン等の有機シリコンがほとんどである。最近、メソポーラス材料の実際的な利用の観点から、原料の低コスト化を図るため、アルカリ珪酸塩等の安価なシリカ源を出発原料とした研究が報告され始めた。また、界面活性剤に関しても、無毒性、生分解性、除去が容易等の特徴を有する非イオン系界面活性剤をテンプレートとする合成法が注目されている。
【０００５】
【発明が解決しようとする課題】
上記のとおり、分子集合体をテンプレートとする高細孔容積マイクロポアの合成において、安価なアルカリ珪酸塩をシリカ源とすることは、多孔質材料の利用分野を拡大するという着想において非常に優れたものであるが、その報告例は高価なアルコキシシラン等の有機シリカを原料としたものに比べ極めて少ない。
一方最近では、細孔構造のみならず、ミクロンサイズのマクロ形態まで制御した、定形メソ多孔性材料の開発の重要性が指摘されているが、分子集合体をテンプレートとして利用し、アルカリ珪酸塩をシリカ源とした定形マイクロポア多孔性材料の報告はほとんど知られていない。
【０００６】
本発明の目的は、細孔構造、マクロ形態を制御するために、無毒性で、生分解性の非イオン性界面活性剤を使用し、更にシリカ源として安価なアルカリ珪酸塩を用いた反応系において、反応物質の種類、混合割合、酸性度、反応温度、攪拌速度を変化させることにより、球状マイクロポアシリカ多孔質粒子の前駆体となる界面活性剤を含んだ有機無機ナノ複合体を比較的温和な条件下、短時間で作製し、最終的に有機成分を取除くことによる、球形マイクロポアシリカ多孔質粒子及びその製造方法を提供することにある。
本製造法で得られる球状マイクロポアシリカ多孔質粒子は、ミクロンオーダーの大きさを有すると同時に、マイクロポアがある程度の規則配列をしており、２つの異なるスケールで規則構造を有している。
【０００７】
【課題を解決するための手段】
本発明によれば、細孔径２ｎｍ以下のマイクロポアを０．２５ｍｌ／ｇ以上の細孔容積で有し、ＢＥＴ比表面積が６００ｍ２／ｇ以上、ＢＥＴ解析法によるＣ定数が４５０以上、且つ粒径が２０乃至５００μｍの球状粒子からなることを特徴とする球状マイクロポアシリカ多孔質粒子が提供される。
【０００８】
本発明の球状マイクロポアシリカ多孔質粒子は、小角Ｘ線回折において回折角０．３乃至２．０度（ＣｕＫα）に低強度であるが細孔の規則配列構造を示す回折ピークを有していることより、球状というマクロ形態とミクロの規則配列という２つの異なるスケールで秩序構造を有していることが大きな特徴である。
かかる本発明の球状多孔質粒子においては、
１．走査型顕微鏡観察による短軸（ＤＳ）と長軸（ＤＬ）との長さの比（ＤＳ／ＤＬ）で表される真球度が０．９５以上の球状粒子を９０％以上存在し、且つ単分散していること、
が好ましい。
【０００９】
更に、本発明によれば、非イオン性界面活性剤の存在下でアルカリ珪酸塩水溶液と鉱酸とを混合攪拌し、５℃乃至３５℃の温度で反応を行ない、生成した球状粒子中から非イオン性界面活性剤を除去することにより球状マイクロポアシリカ多孔質粒子を製造する方法であって、
前記鉱酸を、ＳｉＯ２換算で、前記アルカリ珪酸塩１モル当たり３．５乃至１０モルに相当する量で使用し、
前記非イオン界面活性剤として、ポリエチレンオキシドーポリプロピレンオキシド−ポリエチレンオキシド（ＰＥＯ−ＰＰＯ−ＰＥＯ）またはポリエチレンオキシドーポリブチレンオキシド−ポリエチレンオキシド（ＰＥＯ−ＰＢＯ−ＰＥＯ）のトリブロック共重合体であって、分子量が４，５００乃至１６，０００で、全分子量に占める親水部（ＰＥＯ）の割合が７５％以上のものを使用することを特徴とする球状マイクロポアシリカ多孔質粒子の製造方法が提供される。
【００１０】
本発明の球状マイクロポアシリカ多孔質粒子の製造方法においては、
１．前記非イオン性界面活性剤を、ＳｉＯ２換算で、アルカリ珪酸塩１モル当たり０．００３０乃至０．０１２の量で用いること、
２．水を、ＳｉＯ２換算で、アルカリ珪酸塩１モル当たり１４０乃至２０５モルの量で添加すること
が好ましい。
【００１１】
本発明による球状マイクロポアシリカ多孔質粒子は、揮発性有機化合物（ＶＯＣ）用吸着剤、触媒または触媒担体等の用途に利用される。
更に、本発明の球状マイクロポアシリカ多孔質粒子は、サイズが比較的揃った２０〜５００μｍの高単分散性の真球形状を有し、更に規則的に配列したマイクロ孔を同時に有することで、種々の分子の選択的な触媒坦体、吸着剤、乾燥剤、またガスクロマトグラフ並びにイオンクロマトグラフ用の充填剤等として使用することができる。特に、現在環境汚染物質として社会問題化している揮発性有機化合物（ＶＯＣ）等の吸着剤あるいは濃縮剤として使用可能で、汚染分子に対するマイクロポアの高吸着能を活かし、従来の多孔性材料と比較して格段の機能向上が期待できる。さらに、多孔性材料の機能発現に関連する要因としては内部に形成された細孔が最も重要である。また、工学的観点からは多孔体の外部性状が複合化特性、速度挙動などを決める重要な因子となっていることを考慮して、ミクロ細孔の規則性並びに均一性と同時に流通系反応に直接利用できるマクロ形態を併せ持つことが大きな特徴であり、ガスクロマト並びにイオンクロマト用の充填剤、流動層反応媒体等として使用可能である。更に、金属種による多機能性を付与することで、イオン・分子の吸着・分離・貯蔵剤への利用、金属種添加による触媒或は触媒担体としての材料に適している。また、各種塗料、顔料、接着剤等に配合して種々の用途に利用することができる。
【００１２】
【発明の実施形態】
本発明では、ミクロンオーダーの球状マイクロポアシリカ多孔質粒子の製造法において、シリカ源としてアルカリ珪酸塩を用い、金属アルコキシド等の高価な有機シリカを使用する必要がないこと、テンプレートとして無毒性、生分解性、安価な非イオン性界面活性剤を使用できること、更に温和な温度条件下、短時間で球状粒子を高収率で得られること、温度、酸濃度、反応濃度、攪拌速度を変化させることにより細孔径をコントロールできること等、用いる製造手段及びその組合せに格段の進歩性を有する。
【００１３】
即ち、本発明の球状マイクロポアシリカ多孔質粒子は、細孔径２ｎｍ以下に０．２５ｍｌ／ｇ以上、好ましくは０．２７ｍｌ／ｇ以上の細孔容積を有し、ＢＥＴ比表面積が６００ｍ２／ｇ以上、好ましくは６５０ｍ２／ｇ以上であり、下記式（１）で表されるＢＥＴ式におけるＣ定数が４５０以上、好ましくは５００以上で、且つ粒径が２０乃至５００μｍの球状粒子からなる。
多孔質材料の吸着能力に係わる因子としては、細孔容積と吸着ポテンシャルがあり、前者はｔプロット法により求められる細孔容積、後者はＢＥＴ解析により求められるＣ定数によって評価できる。ここでＢＥＴ式（１）は、
ν＝νｍ ＣＰ／（Ｐ０−Ｐ）｛１＋（Ｃ−１）（Ｐ０／Ｐ） ‥（１）
式中、νは吸着量、νｍは単分子吸着量、Ｐ０は飽和蒸気圧、Ｐは平衡圧を表す、
で表され、上記式中のＣ定数は吸着熱を反映するパラメータで、その値が大きいほど吸着相互作用が大きく、低圧部での立ち上がりが顕著となり吸着力が強いことを表している。例えばゼオライト１３Ｘを例にとるとＣ定数は極めて大きく、容量法による市販の吸着分析装置でＣ定数を評価することは難しい程であるが、細孔容積の面では０．２２８ｍｌ／ｇと小さく、後述の通り（図９）ベンゼン等の飽和吸着量は、本発明の多孔質粒子と比較すると顕著に低いことが認められる。尚、本発明の多孔質粒子の窒素吸着等温線の解析は６００℃加熱処理後の試料を用い、ＢＥＴ解析は相対圧０．０５〜０．２５の範囲において相関係数０．９９９９５以上の範囲の直線部分に適用している。 本多孔質粒子の窒素吸着・脱着等温線においてヒステリシスが認められないことが大きな特徴であり、吸着力の指標となるＣ定数は４５０以上、好ましくは５００以上を有する球状マイクロポアシリカ多孔質粒子である。
【００１４】
また、走査型顕微鏡観察による短軸（ＤＳ）と長軸（ＤＬ）との長さの比（ＤＳ／ＤＬ）で表される真球度が０．９５以上、好ましくは、ほぼ１．０で、その球状粒子を９０％以上存在し、且つ単分散している球状マイクロポアシリカ多孔質粒子である。
【００１５】
本発明による球状マイクロポアシリカ多孔質粒子は、既に指摘したとおり、ミクロンオーダーの真球状を有すると同時に、マイクロポアがある程度の規則配列をしており、２つの異なるスケールで秩序構造を有しているが、このような２つの秩序構造の生成機構は以下のように推定される。
強酸に溶解した非イオン性界面活性剤［Ｎ０］は、界面活性剤表面の親水基部分がプロトン［Ｈ＋］に覆われることでプラスの電荷を帯びている。アルカリ珪酸塩をこの強酸性に添加すると、シリカ溶存種はプラスに帯電し［Ｉ＋］、陰イオン［Ｘ−］が介在することで、電気的に安定なメソ構造体前駆体 ［Ｎ０Ｈ＋］［Ｘ−Ｉ＋］が形成される。シリカマトリックス中に非イオン性界面活性剤を包含したメソ構造体前駆体 ［Ｎ０Ｈ＋］［Ｘ−Ｉ＋］を核として、攪拌下において核成長すなわちゲル化が徐々に進行すると考えられる。
非イオン性界面活性剤は数十から数百の分子が会合してミセルを形成する特徴を有し、疎水性ブロックをコアとし、その周りを緩く取り囲んだコロナ様の親水性ブロックから構成されている。この時、特に界面活性剤分子量全体に占める親水部の割合が７５％以上と長鎖の親水性ブロックを有する非イオン性界面活性剤はミセルを形成する会合分子数が少なく、親水性ブロックが長いため、疎水性ブロックの集合体と親水性ブロックの大きさに明確な差異が認められないことが考えられる。
一方、長鎖の親水性ブロックは球状に成長し易く、最終的にミクロンオーダーの規則的なマクロ形態を有する球状粒子に成長すると推定される。さらに、親水部と疎水部の大きさを明確に識別できない場合にも、疎水性ブロックがコアとなって有機無機メソ規則構造体が形成されることから、シリカ溶存種と界面活性剤との協奏的な秩序形成能に基づいてナノ細孔の規則配列を有することになる。有機成分を焼成或は溶媒抽出等の処理により除去することで得られる最終生成物は、ミクロンオーダーの球状を呈すると同時に規則配列したマイクロ孔を併せ持ち、２つの異なるスケールで秩序構造を有していることになる。
【００１６】
添付図面の図１は、本発明における反応系の構成要素を模式的に示したもので、強酸性条件下では界面活性剤の親水基部分はＨ＋に覆われ ［Ｎ０Ｈ＋］、またＳｉ溶存種もプラス電荷を帯び ［Ｉ＋］ 、メソ構造体を形成することになる構成単位はいずれもプラスに帯電している。
添付図面の図２は、本発明のマイクロポア多孔体の基本単位となる有機無機ナノ複合体の模式図であり、非イオン性界面活性剤の疎水性ブロックをシリカ成分が取囲み、そのシリカ壁には親水性ブロックが侵入していることを示している。有機無機ナノ複合体は上記両プラス溶存種間に塩素イオンや硝酸イオン等の陰イオン（Ｘ−）が介在することで電荷が相殺され、複数の界面活性剤分子で形成されるミセルと、シリカ溶存種との間に作用する協奏的秩序形成能によって生成するメソ構造体前駆体［Ｎ０Ｈ＋］［Ｘ−Ｉ＋］を経由して生成する。
添付図面の図３は、本発明のマイクロポアを有するミクロンサイズの球状多孔体のイメージ図であり、図２に示した有機無機ナノ複合体から成る１次粒子が任意に集合し球状粒子に成長し、生成物から界面活性剤を除去することにより、２種類のマイクロポアを持った球状マイクロポアシリカ多孔質粒子が得られることを示している。１つは疎水性ブロックに起因するマイクロポアＢ、他方は親水性ブロックの存在に基づいてＢを連結するマイクロポアＡである。疎水性ブロックと親水性ブロックに基づく細孔径に顕著な差異は認められず、その結果として、３次元的に絡み合った均一細孔径の微細孔がある程度の規則的配列を有して存在することになる。
【００１７】
本反応系において球状粒子を製造するためにはゲル化速度を厳密に制御しなければならない。例えば、界面活性剤の種類、出発原料組成、反応温度、非イオン性界面活性剤の混合比等がゲル化時間に敏感に反映し、マクロ形態に著しい影響を与える。
尚、界面活性剤が存在しない場合は、大過剰の陰イオン（Ｘ−）が系内に存在し、シリカのゲル化が妨げられるが、本発明では界面活性剤の量と陰イオンの量のバランスによりゲル化に要する時間をコントロールできる為、最終的にマクロ形態を制御できると推察される。
【００１８】
前述したように本発明の製造法において、規則的に配列したマイクロ孔を有し、ミクロンオーダーの球状マイクロポアシリカ多孔質粒子の前駆体を、室温付近常圧下において短時間で製造できる。また、界面活性剤量、反応温度、酸濃度、シリカ濃度、攪拌速度をコントロールすることで、マクロ形態及び、細孔構造、更に細孔構造を形成するシリカ骨格から成るシリカ壁厚の制御が可能である。
【００１９】
特に、攪拌速度は、界面活性剤に起因する反応液の粘性に留意し、塊状粒子が認められないように決定する必要がある。
【００２０】
添付図面の図４は、本発明の球状マイクロポアシリカ多孔質粒子の数例の小角Ｘ線回折パターンである。小角Ｘ線回折において回折角１度（ＣｕＫα）付近にマイクロ孔の規則配列構造を示すＸＲＤ回折ピークを有する。Ｘ線強度の点からはマイクロ孔の配列の規則性はそれ程高くはないと推定されるが、本発明の球状マイクロポアシリカ多孔質粒子がある程度の規則的に配列した微細孔を有することは明瞭である。
【００２１】
図５は、本発明の球状マイクロポアシリカ多孔質粒子の数例の粒子形態を示す走査型電子顕微鏡写真である。これらの走査型電子顕微鏡写真から、本発明の球状マイクロポアシリカ多孔質粒子は、真球状で単分散のマクロ形態を有することが分かる。
【００２２】
図６は、本発明の球状マイクロポアシリカ多孔質粒子の数例の体積基準における粒度分布曲線である。
【００２３】
図７は、本発明の球状マイクロポアシリカ多孔質粒子の数例の窒素吸着等温線であり、図８は図７のシリカ粒子のｔプロット図である。図７の窒素吸着等温線がＩ型を示し、図８のｔプロットの形状と２本の外挿直線の交点から、本発明の球状マイクロポアシリカ多孔質粒子がマイクロポア多孔体であり、その細孔径のピークが〜１ｎｍに存在することが推定される。なお、図中には外挿直線は２つのサンプルについて明示した。
既に指摘したとおり、本発明の球状マイクロポアシリカ多孔質粒子は、ミクロンオーダーの真球状を呈すると同時に、１ｎｍ以下の細孔径を有するマイクロポアが規則配列しており、２つの異なるスケールで秩序構造を有していることが顕著な特徴である。
【００２４】
図９は、本発明の球状マイクロポアシリカ多孔質粒子の一例のベンゼンに対する２５℃における吸着等温線であり、市販のゼオライト１３Ｘと比較して示す。本発明の球状マイクロポアシリカ多孔質粒子はマイクロポアを有することから、低相対圧における吸着挙動の立ち上がりがゼオライトに匹敵し、ベンゼン等の揮発性有機化合物（ＶＯＣ）に対する吸着ポテンシャルに優れていることが分かる。さらに、飽和吸着量はゼオライトと比較するとより大きいことが明瞭であり、本発明の球状マイクロポアシリカ多孔質粒子は揮発性有機化合物に対する吸着剤あるいは濃縮剤として優れた特徴を有している。
【００２５】
本発明の製造法において、反応時間により生成物のマクロ形態にも影響が現れる。ゲル化時間が短いと、メソ孔の配列等の規則性及び球形度の程度が低く、更に未反応のアルカリ珪酸塩が残存するため、反応は２０分以上行うことが好ましい。しかし、反応を長時間行ってもマクロ形態、細孔構造に大きな変化は見られず、生成物に与える影響は小さいが、生産効率の問題から経済的に不利になる。
【００２６】
アルカリ珪酸塩と酸との反応温度は、５℃乃至３５℃の範囲が望ましい。反応温度は、シリカのゲル化速度を左右するが、上記温度範囲よりも高い温度で反応を行うと、マクロ形態の規則性が悪化する傾向がある。これは、温度の上昇により非イオン性系面活性剤中の親水基部分の脱水和が起こりやすくなる為、結果的に非イオン性界面活性剤の形成するミセルが大きくなり、マクロ形態に影響を与えると推定される。一方、反応温度が低くなると反応速度が遅くなり生産効率の問題から経済的に不利になる。
【００２７】
本製造法において、界面活性剤量の減少、酸濃度の増加、シリカ濃度の増加によってもシリカのゲル化に要する時間が短縮され、マクロ形態に影響が現れる。一方、界面活性剤量の増加、酸濃度の減少ではゲル化時間が遅くなり、この場合にもマクロ形態に影響が現れる。これは、ゲル化速度が適切でないと、均一反応系からの結晶核の生成と成長が抑制されるためと推定される。
【００２８】
本発明の球状マイクロポアシリカ多孔質粒子は、所定の濃度の酸に溶解した非イオン性界面活性剤溶液と、水で希釈したアルカリ珪酸塩水溶液とを攪拌しながら反応させることにより、非イオン性界面活性剤とシリカ溶存種との協調的秩序形成能に基づいて生成する非イオン性界面活性剤を包含したシリカ複合前駆体から、最終的に非イオン性界面活性剤を焼成或は溶媒抽出等の手段により除去することで得られる。
【００２９】
本発明において、上記原料の添加順序には制限がなく、例えば水で希釈したアルカリ珪酸塩水溶液に酸に溶解した非イオン性界面活性剤溶液を添加してもよく、また逆に、酸に溶解した非イオン性界面活性剤溶液に水で希釈したアルカリ珪酸塩水溶液を添加しても良い。
【００３０】
［原料］
本発明で使用される、シリカ原料、非イオン性界面活性剤、酸について更に説明する。
【００３１】
本発明においてシリカ原料として使用するアルカリ珪酸塩は、比較的廉価であるナトリウム珪酸塩が好ましい。具体的には式（２）、
Ｎａ２Ｏ・ｍＳｉＯ２‥‥（２）
式中、ｍは１乃至４の数、特に２．５乃至３．５の数である、
で表される組成を有するナトリウム珪酸塩の水溶液を使用することが好ましい。
【００３２】
非イオン性界面活性剤としては、ポリエチレンオキシドーポリプロピレンオキシド−ポリエチレンオキシド（ＰＥＯ−ＰＰＯ−ＰＥＯ）またはポリエチレンオキシドーポリブチレンオキシド−ポリエチレンオキシド（ＰＥＯ−ＰＢＯ−ＰＥＯ）から成るトリブロック共重合体が使用される。このトリブロック共重合体の分子量４，５００乃至１６，０００の範囲にあることが必要であり、さらに全分子量に占める親水部（ＰＥＯ）の割合は７５％以上、特に８０％以上である。
【００３３】
本発明において、反応温度は、５℃乃至３５℃が好ましく、３５℃以上では単分散球状粒子を作製することは難しい。一方、反応温度が低くなると反応速度が遅くなり生産効率の問題から経済的に不利になる。
また、用いる非イオン性界面活性剤の使用量は、一般にＳｉＯ２に対するモル比０．００３０乃至０．０１２の範囲でその分子量に応じて適宜調整するのがよい。
【００３４】
酸としては、塩酸、硫酸、硝酸、燐酸、炭酸、酢酸等の無機酸や有機酸が使用されるが、経済的な見地から塩酸、硫酸、硝酸、燐酸等の鉱酸を用いるのがよく、中でも、マクロ形態の一様さの点で塩酸と硝酸が好ましい。
【００３５】
本発明の球状マイクロポアシリカ多孔質粒子の合成において、出発原料の混合モル比は、ＳｉＯ２：非イオン性界面活性剤：Ｎａ２Ｏ：酸：水 ＝ １：０．００３０〜０．０１２：０．２０〜０．８：３．５〜１０：１４０〜２０５であるのが好ましい。
更に、出発原料の混合方式を詳細に記述すると、所定の濃度の酸に溶解した非イオン性界面活性剤溶液（Ａ）と、水に希釈したアルカリ珪酸塩水溶液（Ｂ）とを攪拌下に混合し、そのまま攪拌を継続して所定温度の下で２０分以上好ましくは３０分以上２時間程度、攪拌反応を行う。ここで、原料溶液（Ａ）及び（Ｂ）は予め同じ所定温度に調整して混合する。
【００３６】
反応後懸濁液から固体生成物を分離し、室温〜１００℃で充分乾燥させる。最後に有機成分を除去して球状マイクロポアシリカ多孔質粒子を作製するために、２００℃以上で２時間以上、好ましくは３００℃以上で１時間加熱処理する。
【００３７】
また、本発明の球状シリカ多孔質粒子は、シリカ純成分の球状粒子ばかりでなく、金属種として、Ｓｉの他に、Ｔｉ、Ｚｒ、Ａｌ、Ｆｅ、Ｚｎ、Ｃｒ、Ｍｎ、Ｃｏ、Ｃｕ、Ｎｉ、Ｖ、Ｓｎ、Ｒｕ、Ｃｅ、Ｍｏ、Ｗ、Ｒｈ、Ａｇ等の一種類あるいは複数を含有していてもよい。例えば、上記金属の塩化物、硫酸塩、硝酸塩やその水和物等、酸に可溶な金属塩を出発原料中に含有させることができる。またＡｌ等の両性酸化物の場合には、アルカリに可溶な金属塩、金属酸化物及び金属水酸化物等を使用することができる。
更に、出発原料の混合方式を詳細に記述すると、所定の濃度の酸に溶解した非イオン性界面活性剤（Ａ）と、水に希釈したアルカリ珪酸塩水溶液（Ｂ）と、酸或はアルカリに溶解した金属塩（Ｃ）を攪拌下に混合し後、所定温度の下で２０分以上好ましくは３０分以上２時間程度、攪拌反応を行う。ここで、原料溶液Ａ、Ｂ及びＣは予め同じ所定温度に調整して混合する。
【００３８】
［用途］
本発明の球状マイクロポアシリカ多孔質粒子は、粒径が２０乃至５００μｍで高単分散性の真球形状を有し、更に規則的に配列したマイクロ孔を有することで、種々の分子の選択的な触媒坦体、吸着剤、乾燥剤、またガスクロ並びにイオンクロマト用の充填剤等として使用することができる。特に、現在環境汚染物質として社会問題化している揮発性有機化合物（ＶＯＣ）等の吸着剤あるいは濃縮剤として使用可能で、汚染分子に対するマイクロ孔の高吸着ポテンシャルを活かして、従来のナノ空間材料と比較して格段の機能向上が期待できる。さらに、多孔性材料の機能発現に関連する要因としては内部に形成された細孔が最も重要であるが、工学的観点からは多孔体の外部性状が複合化特性、速度挙動などを決める重要な因子となっていることを考慮して、ミクロ細孔の規則性並びに均一性と同時に流通系反応に直接利用できるマクロ形態を併せ持つことが大きな特徴であり、ガスクロ並びにイオンクロマト用の充填剤、流動床反応媒体等として使用可能である。更に、金属種による多機能性を付与することで、イオン・分子の吸着・分離・貯蔵剤への利用、金属種添加による触媒或は触媒担体としての材料に適している。また、各種塗料、インク用体質顔料、接着剤等に配合して種々の用途に利用することができる。
【００３９】
【実施例】
次に、本発明を実施例によって更に具体的に説明するが、本発明はこの実施例によって限定されない。
尚、実施例で行った各試験方法は次の方法により行った。
【００４０】
（測定法）
（１）走査型電子顕微鏡：日本電子製ＪＳＭ５３００を使用し、加速電圧１０ｋＶ、ＷＤ１０ｍｍで観察した。
（２）比表面積・細孔容積：日本ベル製ＢＥＬＳＯＲＰ２８を使用し、液体窒素温度で測定した窒素吸着等温線からＢＥＴ比表面積を求め、さらに、ｔプロット法により細孔径並びに全細孔容積（マイクロポア容積）を算出した。
（３）形状：走査型電子顕微鏡写真から観察した。
（４）粒度分布：走査型電子顕微鏡写真並びにベックマン・コールター社製Ｍｕｌｔｉｓｉｚｅｒ３で測定した。
（５）小角Ｘ線回折：リガク製ナノスケールＸ線構造評価装置を使用し、ＣｕＫα線源、加速電圧４５ｋＶ、６０ｍＡで測定した。
（６）ベンゼンの吸着等温線：日本ベル製ＢＥＬＳＯＲＰ１８を使用し、２５℃で吸着等温線を測定した。
【００４１】
（実施例１）
１２％の硝酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８ （ＰＥＯ３９ＰＰＯ１０３ＰＥＯ３９） （平均分子量１１４００、親水部ＰＥＯ割合８０％）（ＢＡＳＦ）溶液に、市販のＪＩＳ３号珪酸ナトリウム（ＳｉＯ２：２３．６％、Ｎａ２Ｏ：７．５９％）に水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４２】
（実施例２）
２Ｎの塩酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８の溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４３】
（実施例３）
２Ｎの塩酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８の溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４４】
（実施例４）
１２％の硝酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ６８ （ＰＥＯ７６ＰＰＯ３０ＰＥＯ７６） （平均分子量８４００、親水部ＰＥＯ割合８０％）（ＢＡＳＦ）溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２７℃〜２９℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４５】
（実施例５）
１２％の硝酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ１０８ （ＰＥＯ１３２ＰＰＯ５６ＰＥＯ１３２） （平均分子量１５５００、親水部ＰＥＯ割合８０％）（旭電化工業（株））溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４６】
（実施例６）
２Ｎの塩酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４７】
（実施例７）
３Ｎの塩酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４８】
（実施例８）
２Ｎの塩酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
【００４９】
（実施例９）
１２％の硝酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ８８溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。
混合溶液のモル比は、
反応温度は２５℃〜２７℃で、２時間攪拌反応を行った後、固体生成物を濾別し、６０℃の温水で洗浄後、５０℃で十分乾燥させた。最終的に６００℃の電気炉中で１時間焼成を行うことで有機成分を除去し、真球状定形多孔質シリカ粒子を得た。
以下の表１に、上記実施例１〜９での合成条件を示した。
【００５０】
【表１】
（比較例１）
１２％の硝酸に溶解したトリブロック共重合体Ｐｌｕｒｏｎｉｃ Ｆ１２７ （ＰＥＯ１０６ＰＰＯ７０ＰＥＯ１０６） （平均分子量１２６００、親水部ＰＥＯ割合７０％）（ＢＡＳＦ）溶液に、市販のＪＩＳ３号珪酸ナトリウムに水を加え希釈した珪酸ナトリウム水溶液を６００ｒｐｍで攪拌しながら添加した。混合溶液のモル比は、
【００５２】
以上の実施例及び比較例で得た球状マイクロポアシリカ多孔質粒子の細孔特性を、表２に示した。
【００５３】
【表２】
表２中、比表面積は窒素吸着等温線から求めたＢＥＴ比表面積の値であり、細孔容積はｔプロット法から求めたマイクロ孔のみの細孔容積の値である。２ｔは細孔径に対応するもので、ｔプロット法で描かれる２本の外挿直線の交点に対応している（図８では煩雑さを避けるためａ、ｄに外挿直線を示した）。粒径は電気抵抗法で測定した体積統計値の平均径である。
【００５５】
【発明の効果】
本発明によれば、更にシリカ源として安価なアルカリ珪酸塩を使用し、さらに無毒性で、生分解性の非イオン性界面活性剤を使用することによって、規則的な配列をしたマイクロポアを有し、ミクロンオーダーの粒径を有する球状シリカ多孔質粒子を得ることができる。
この球状マイクロポアシリカ多孔質粒子は、揮発性有機化合物（ＶＯＣ）等の吸着剤あるいは濃縮剤として使用することができ、また、ガスクロマト或いはイオンクロマト用の充填剤、流動層反応媒体等として使用できる。更に、金属種による多機能性を付与することで、イオン・分子の吸着・分離・貯蔵剤への利用、金属種添加による触媒或は触媒担体としての材料に適している。また、各種塗料、顔料、接着剤等に配合して種々の用途に利用することができる。
【図面の簡単な説明】
【図１】本発明の製造方法に用いる反応系のゲル化前の溶液状態を模式的に示す説明図。
【図２】本発明の球状マイクロポアシリカ多孔質粒子製造過程において、非イオン性界面活性剤の分子集合体ミセルとシリカ溶存種との間の協奏的秩序形成によって生成する前駆体を経由して生成する有機無機ナノ複合体の模式図。
【図３】本発明のマイクロポアを有するミクロンサイズの球状マイクロポアシリカ多孔質粒子のイメージ図。
【図４】本発明の球状マイクロポアシリカ多孔質粒子数例の小角Ｘ線回折パターンを示す図。
【図５】本発明の球状マイクロポアシリカ多孔質粒子数例の粒子形態を示す走査型電子顕微鏡写真。
【図６】本発明の球状マイクロポアシリカ多孔質粒子数例の粒度分布を示す図。
【図７】本発明の球状マイクロポアシリカ多孔質粒子の数例の窒素吸着等温線を示す図。
【図８】本発明の球状マイクロポアシリカ多孔質粒子の窒素吸着等温線から得られる数例のｔプロットを示す図。
【図９】本発明の球状マイクロポアシリカ多孔質粒子の一例並びに市販ゼオライト１３Ｘのベンゼン吸着等温線を示す図。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to spherical microporous silica porous particles and a method for producing the same. More specifically, using an alkali silicate as a silica source, in an acidic solution phase containing silica-dissolved species formed therefrom, based on the order-forming ability of the nonionic surfactant, the microstructure regularity and the macrostructure The present invention relates to microporous silica porous particles having a regular spherical shape and utilizing a method of simultaneously obtaining regularity of the shape, and a method for producing the same.
[0002]
[Prior art]
Porous materials are classified into three types according to the size of the pores, since the adsorptive separation and catalytic activity of the porous materials greatly depend on the chemical surface properties of the pores, their shape and size, and their uniformity. Is done.
Porous micropore 2nm or less
Mesopore porous body 2-50nm
Macropore
Among porous micropores mainly composed of silica, zeolite is called a molecular sieve because it exhibits a molecular sieve action capable of discriminating the size of a molecule, and is a substance group most widely used at present. The peculiar adsorptive properties and high ion-exchange properties of zeolites have been attracting attention for a long time, and those of natural origin have been used as ion-exchange agents and soil conditioners. In 1956, Union Carbide Co., Ltd. developed the trade name LMS (Linde Molecular Sieve). Mobil Oil, which developed the solid acid zeolite catalyst in 1960, continued to play a leading role in research and development in this area, and in 1970, developed the high silica zeolite ZSM-5. Since the industrial production of zeolites, research on molecular sieving and catalytic properties has been remarkably advanced, and many industrial processes have been developed, and techniques for synthesizing new types of zeolites have also been developed.
On the other hand, zeolite has not only molecular sieving ability but also many excellent properties, but does not show catalytic activity on large molecules having a pore size or more. This is because zeolite is a crystalline substance obtained by a hydrothermal synthesis method using one molecule of an organic template as a template, and the pore size is determined by the crystal structure of the zeolite. It is known that it is extremely difficult to synthesize particles having a pore diameter of 1 nm or more, mainly containing Si and Al. Al (Fe, Si) and Ga phosphates can be synthesized using a large molecule as a template. So far, those having a 20-membered ring such as cloverite and JFD-20 having a pore diameter of 3 nm have been reported, but have a problem in practical durability due to poor hydrothermal stability. In 1996, UTD-1 having a 14-membered ring (pore diameter 1 x 0.75 nm) composed of Si and Al was synthesized, and it was found that it has heat resistance up to 1000 ° C and the presence of strong Bronsted acid sites. became.
[0003]
Furthermore, in the history of the development of porous materials, the method of synthesizing the porous mesopores FSM-16 and MCM-41 in which uniform mesopores are regularly arranged in a honeycomb shape, reported in the early 1990s, is an exciting discovery. . Mesoporous materials were synthesized using molecular assemblies of surfactants as templates.Since their discovery, research on mesoporous materials has been accelerated at a stretch, not only as a catalyst based on molecular sieving properties, but also as an ordering of functional molecules in mesopores. Application to clathrate compounds having optical, magnetic, and electrical functions is also considered. However, from the viewpoint of the adsorbent material, although the pore volume is large, the ability to take in the adsorbed substance is often inferior to that of zeolite, and even now it has reached the stage of practical application utilizing the adsorption phenomenon unique to mesoporous materials There have been few examples. In addition, as described above, the pore size and the pore volume of zeolite are uniquely determined by the crystal structure, and producing a micropore porous body having a larger pore space is also a major research issue in the development of porous bodies. is there.
[0004]
Recently, there has been a report on the synthesis of a microporous material using a molecular assembly of a surfactant as a template, which is a technique for synthesizing a mesoporous material (for silica, Chem. Commun. 2000, 533; Chem. Commun. 2000; Chem. Commun. 2000, 2041; Chem. Commun. 2001, 1016, etc. are reported for silica-alumina systems). Further, an alkali silicate is used as a silica raw material for synthesizing zeolite. However, the above-mentioned porous silica and a silica source for synthesizing a mesoporous material using a molecular assembly as a template are mostly organic silicon such as alkoxysilane. It is. Recently, from the viewpoint of practical use of mesoporous materials, studies have been started on a study using a low-cost silica source such as an alkali silicate as a starting material in order to reduce the cost of the raw material. As for surfactants, a synthesis method using a nonionic surfactant as a template, which has characteristics such as non-toxicity, biodegradability, and easy removal, has attracted attention.
[0005]
[Problems to be solved by the invention]
As described above, in the synthesis of a high pore volume micropore using a molecular assembly as a template, using an inexpensive alkali silicate as a silica source is extremely excellent in the idea of expanding the field of application of porous materials. However, the number of reported examples is extremely small as compared with those using expensive organic silica such as alkoxysilane as a raw material.
On the other hand, recently, it has been pointed out the importance of developing a regular mesoporous material that controls not only the pore structure but also the microscopic macroscopic form.However, using a molecular assembly as a template, Few reports have been made on a regular microporous material used as a silica source.
[0006]
An object of the present invention is to use a non-toxic, biodegradable nonionic surfactant to control the pore structure and macro morphology, and furthermore to use a reaction system using an inexpensive alkali silicate as a silica source. By changing the type of reactants, the mixing ratio, the acidity, the reaction temperature, and the stirring speed, the organic-inorganic nanocomposite containing a surfactant that is a precursor of the spherical microporous silica porous particles can be relatively formed. It is an object of the present invention to provide spherical microporous silica porous particles produced under a mild condition in a short time and finally removing an organic component, and a method for producing the same.
The spherical microporous silica porous particles obtained by the present production method have a micron-order size, and at the same time, the micropores have a certain degree of ordered arrangement, and have an ordered structure at two different scales.
[0007]
[Means for Solving the Problems]
According to the present invention, a micropore having a pore diameter of 2 nm or less has a pore volume of 0.25 ml / g or more and a BET specific surface area of 600 m2/ G or more, spherical microporous silica porous particles comprising spherical particles having a C constant of 450 or more by BET analysis and a particle size of 20 to 500 μm.
[0008]
The spherical microporous silica porous particles of the present invention have low diffraction intensity at a diffraction angle of 0.3 to 2.0 degrees (CuKα) in small-angle X-ray diffraction, but have a diffraction peak showing a regular array structure of pores. Therefore, it is a major feature that it has an ordered structure at two different scales, that is, a macroscopic morphology of a sphere and a micro-ordered arrangement.
In the spherical porous particles of the present invention,
1. The short axis (DS) And major axis (DL) And the length ratio (DS/ DL) Is 90% or more of spherical particles having a sphericity of 0.95 or more and is monodispersed;
Is preferred.
[0009]
Further, according to the present invention, an aqueous alkali silicate solution and a mineral acid are mixed and stirred in the presence of a nonionic surfactant, and a reaction is carried out at a temperature of 5 ° C. to 35 ° C. A method for producing spherical microporous silica porous particles by removing an ionic surfactant,
Converting said mineral acid to SiO2In conversion, used in an amount corresponding to 3.5 to 10 mol per mol of the alkali silicate,
The non-ionic surfactant is a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) or polyethylene oxide-polybutylene oxide-polyethylene oxide (PEO-PBO-PEO), The present invention provides a method for producing spherical microporous silica porous particles, characterized in that those having a molecular weight of 4,500 to 16,000 and a ratio of a hydrophilic portion (PEO) to the total molecular weight of 75% or more are used. .
[0010]
In the method for producing spherical microporous silica porous particles of the present invention,
1. The non-ionic surfactant is
2. Water with SiO2In terms of conversion, it is added in an amount of 140 to 205 mol per mol of alkali silicate.
Is preferred.
[0011]
The spherical microporous silica porous particles according to the present invention are used for applications such as an adsorbent for volatile organic compounds (VOC), a catalyst or a catalyst carrier.
Furthermore, the spherical microporous silica porous particles of the present invention have a highly monodisperse true spherical shape having a relatively uniform size of 20 to 500 μm, and simultaneously have regularly arranged micropores. It can be used as a selective catalyst carrier for various molecules, as an adsorbent, as a desiccant and as a filler for gas chromatography and ion chromatography. In particular, it can be used as an adsorbent or a concentrating agent for volatile organic compounds (VOCs), which are currently a social problem as an environmental pollutant, and makes use of the high adsorbability of micropores for polluting molecules, compared to conventional porous materials. As a result, a significant improvement in function can be expected. Further, as a factor relating to the function expression of the porous material, the pores formed therein are most important. Also, from the engineering point of view, taking into account that the external properties of the porous material are important factors that determine the composite properties, velocity behavior, etc. It is a great feature that it has a macro form that can be directly used, and it can be used as a filler for gas chromatography and ion chromatography, a fluidized bed reaction medium, and the like. Further, by imparting multifunctionality by a metal species, it is suitable for use as an adsorption / separation / storage agent for ions / molecules and as a catalyst or catalyst carrier by adding a metal species. Further, it can be used for various applications by being blended in various paints, pigments, adhesives and the like.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, in the method for producing micron-order spherical microporous silica porous particles, an alkali silicate is used as a silica source, and there is no need to use expensive organic silica such as metal alkoxide. Decomposable, inexpensive nonionic surfactants can be used, moreover, spherical particles can be obtained in a high yield in a short time under mild temperature conditions, and temperature, acid concentration, reaction concentration, and stirring speed must be changed. The present invention has a remarkable step in the production means to be used and the combination thereof, for example, the pore diameter can be controlled by the method.
[0013]
That is, the spherical micropore silica porous particles of the present invention have a pore volume of 0.25 ml / g or more, preferably 0.27 ml / g or more at a pore diameter of 2 nm or less, and a BET specific surface area of 600 m2/ G or more, preferably 650 m2/ G or more and spherical particles having a C constant of 450 or more, preferably 500 or more in the BET formula represented by the following formula (1), and a particle size of 20 to 500 μm.
Factors relating to the adsorption capacity of the porous material include pore volume and adsorption potential. The former can be evaluated by the pore volume determined by the t-plot method, and the latter can be evaluated by the C constant determined by BET analysis. Here, the BET equation (1) is
ν = νm CP / (P0−P) ｛1+ (C−1) (P0/ P) ‥ (1)
Where ν is the adsorption amount, νmIs the amount of single molecule adsorbed, P0Represents a saturated vapor pressure, P represents an equilibrium pressure,
The C constant in the above equation is a parameter that reflects the heat of adsorption, and the larger the value, the greater the adsorption interaction, the more pronounced the rise in the low-pressure portion, and the stronger the adsorption power. For example, taking the zeolite 13X as an example, the C constant is extremely large, and it is difficult to evaluate the C constant with a commercially available adsorption analyzer by the volumetric method. However, the pore volume is as small as 0.228 ml / g. As will be described later (FIG. 9), it is recognized that the amount of saturated adsorption of benzene and the like is significantly lower than that of the porous particles of the present invention. The nitrogen adsorption isotherm of the porous particles of the present invention was analyzed using a sample after heat treatment at 600 ° C., and the BET analysis was performed in a relative pressure range of 0.05 to 0.25 with a correlation coefficient of 0.99995 or more. Is applied to the straight line part. It is a great feature that no hysteresis is observed in the nitrogen adsorption / desorption isotherm of the porous particles, and the C constant as an index of the adsorption force is 450 or more, preferably 500 or more. is there.
[0014]
In addition, the short axis (DS) And major axis (DL) And the length ratio (DS/ DL) Is a spherical microporous silica porous particle having a sphericity of 0.95 or more, preferably about 1.0, containing at least 90% of the spherical particles, and monodispersed.
[0015]
As already pointed out, the spherical microporous silica porous particles according to the present invention have a true spherical shape on the order of microns, and at the same time, the micropores have a certain degree of ordered arrangement, and have an ordered structure at two different scales. However, the generation mechanism of such two ordered structures is presumed as follows.
Nonionic surfactant dissolved in strong acid [N0] Means that the hydrophilic group on the surface of the surfactant has a proton [H+] To have a positive charge. When an alkali silicate is added to this strong acid, the silica-dissolved species becomes positively charged [I+], Anion [X−], The electrically stable mesostructure precursor [N0H+] [X−I+] Is formed. Mesostructure precursor containing nonionic surfactant in silica matrix [N0H+] [X−I+] As nuclei, it is considered that nucleus growth, that is, gelation, gradually proceeds under stirring.
Nonionic surfactants have the characteristic that dozens to hundreds of molecules associate with each other to form micelles, and are composed of a hydrophobic block as a core and a corona-like hydrophilic block loosely surrounding the core. I have. At this time, the nonionic surfactant having a long-chain hydrophilic block has a small number of associated molecules forming micelles, and the hydrophilic block has a long hydrophilic block in which the ratio of the hydrophilic portion to the entire surfactant molecular weight is 75% or more. Therefore, it is considered that no clear difference is recognized between the size of the aggregate of the hydrophobic blocks and the size of the hydrophilic blocks.
On the other hand, the long-chain hydrophilic block tends to grow into a sphere, and it is presumed that the long-chain hydrophilic block eventually grows into a spherical particle having a regular macro morphology on the order of microns. Furthermore, even when the size of the hydrophilic portion and that of the hydrophobic portion cannot be clearly distinguished, the hydrophobic block serves as a core to form an organic-inorganic meso-ordered structure. Will have a regular arrangement of nanopores based on the ability to form an order. The final product obtained by removing the organic component by a treatment such as calcination or solvent extraction has a spherical shape on the order of microns and simultaneously has regularly arranged micropores, and has an ordered structure on two different scales. Will be.
[0016]
FIG. 1 of the accompanying drawings schematically shows the components of the reaction system according to the present invention. Under strongly acidic conditions, the hydrophilic group portion of the surfactant is H.+[N0H+], And the Si-dissolved species also have a positive charge [I+], All the structural units forming the mesostructure are positively charged.
FIG. 2 of the accompanying drawings is a schematic view of an organic-inorganic nanocomposite which is a basic unit of the microporous body of the present invention, in which a silica component surrounds a hydrophobic block of a nonionic surfactant, and a silica wall thereof. Indicates that a hydrophilic block has entered. The organic-inorganic nanocomposite forms an anion (X) such as chloride ion or nitrate ion between the above-mentioned plus dissolved species.−) Intervenes to cancel the charge, and a mesostructure precursor [N] generated by a concerted ordering ability acting between micelles formed by a plurality of surfactant molecules and silica-dissolved species.0H+] [X−I+].
FIG. 3 of the attached drawings is an image diagram of a micron-sized spherical porous body having micropores according to the present invention. The primary particles composed of the organic-inorganic nanocomposite shown in FIG. 2 arbitrarily aggregate and grow into spherical particles. It shows that spherical surfactant microporous silica particles having two types of micropores can be obtained by removing the surfactant from the product. One is micropore B due to the hydrophobic block, and the other is micropore A connecting B based on the presence of the hydrophilic block. No remarkable difference was observed in the pore size based on the hydrophobic block and the hydrophilic block, and as a result, the micropores with a uniform pore size intertwined three-dimensionally existed with some degree of regular arrangement. Become.
[0017]
In order to produce spherical particles in this reaction system, the gelation rate must be strictly controlled. For example, the type of the surfactant, the starting material composition, the reaction temperature, the mixing ratio of the nonionic surfactant, and the like are sensitively reflected in the gelation time and significantly affect the macro morphology.
When no surfactant is present, a large excess of anions (X−) Is present in the system and inhibits the gelation of silica. However, in the present invention, the time required for gelation can be controlled by the balance between the amount of the surfactant and the amount of the anion. It is presumed that it can be done.
[0018]
As described above, in the production method of the present invention, precursors of microporous microporous silica particles having micropores arranged regularly and having a micron order can be produced in a short time at room temperature and under normal pressure. In addition, by controlling the amount of surfactant, reaction temperature, acid concentration, silica concentration, and stirring speed, it is possible to control the macro morphology, the pore structure, and the silica wall thickness composed of the silica skeleton that forms the pore structure. It is.
[0019]
In particular, the stirring speed needs to be determined in consideration of the viscosity of the reaction solution caused by the surfactant, so that no lump particles are observed.
[0020]
FIG. 4 of the accompanying drawings is a small-angle X-ray diffraction pattern of several examples of the spherical microporous silica porous particles of the present invention. In small-angle X-ray diffraction, it has an XRD diffraction peak showing a regular array structure of micropores at a diffraction angle of about 1 degree (CuKα). From the viewpoint of X-ray intensity, it is estimated that the regularity of the arrangement of the micropores is not so high. However, it is clear that the spherical microporous silica porous particles of the present invention have some regularly arranged micropores. It is.
[0021]
FIG. 5 is a scanning electron micrograph showing the particle morphology of several examples of the spherical microporous silica porous particles of the present invention. These scanning electron micrographs show that the spherical microporous silica porous particles of the present invention have a true spherical and monodispersed macromorphology.
[0022]
FIG. 6 is a particle size distribution curve on a volume basis of several examples of the spherical microporous silica porous particles of the present invention.
[0023]
FIG. 7 is a nitrogen adsorption isotherm of several examples of the spherical microporous silica porous particles of the present invention, and FIG. 8 is a t-plot diagram of the silica particles of FIG. The nitrogen adsorption isotherm in FIG. 7 indicates type I, and from the intersection of the t-plot shape in FIG. 8 and the two extrapolated straight lines, the spherical microporous silica porous particles of the present invention are microporous porous bodies. It is estimated that the peak of the pore diameter exists at に 1 nm. In the drawing, extrapolated straight lines are clearly shown for two samples.
As already pointed out, the spherical microporous silica particles of the present invention exhibit a true spherical shape on the order of microns, and micropores having a pore diameter of 1 nm or less are regularly arranged. Is a remarkable feature.
[0024]
FIG. 9 is an adsorption isotherm of benzene as an example of the spherical microporous silica porous particles of the present invention at 25 ° C., which is shown in comparison with commercially available zeolite 13X. Since the spherical microporous silica porous particles of the present invention have micropores, the rising of the adsorption behavior at a low relative pressure is comparable to that of zeolite, and the adsorption potential for volatile organic compounds (VOC) such as benzene is excellent. I understand. Further, it is clear that the saturated adsorption amount is larger than that of zeolite, and the spherical microporous silica porous particles of the present invention have excellent characteristics as an adsorbent or a condensing agent for volatile organic compounds.
[0025]
In the production method of the present invention, the reaction time also affects the macro form of the product. If the gelation time is short, the regularity such as the arrangement of mesopores and the degree of sphericity are low, and unreacted alkali silicate remains. Therefore, the reaction is preferably performed for 20 minutes or more. However, even if the reaction is carried out for a long time, no significant change is observed in the macro form and the pore structure, and the effect on the product is small, but it is economically disadvantageous due to the problem of production efficiency.
[0026]
The reaction temperature between the alkali silicate and the acid is preferably in the range of 5 ° C to 35 ° C. The reaction temperature affects the gelation rate of silica, but if the reaction is performed at a temperature higher than the above temperature range, the regularity of the macro form tends to deteriorate. This is because the dehydration of the hydrophilic group portion in the nonionic surfactant is likely to occur due to the rise in temperature, and as a result, the micelles formed by the nonionic surfactant become large, and the macro morphology is affected. It is estimated to give. On the other hand, when the reaction temperature is low, the reaction rate is low, which is economically disadvantageous from the viewpoint of production efficiency.
[0027]
In the present production method, the time required for gelation of silica is also shortened by reducing the amount of surfactant, increasing the acid concentration, and increasing the silica concentration, and the macro form is affected. On the other hand, when the amount of the surfactant is increased and the acid concentration is decreased, the gelation time is delayed, and also in this case, the macro form is affected. This is presumably because, if the gelation rate is not appropriate, the generation and growth of crystal nuclei from the homogeneous reaction system are suppressed.
[0028]
The spherical microporous silica porous particles of the present invention are prepared by reacting a nonionic surfactant solution dissolved in an acid having a predetermined concentration with an aqueous alkali silicate solution diluted with water while stirring. From the silica composite precursor containing the nonionic surfactant generated based on the ability of the surfactant and the silica-dissolved species to form a coordinated order, the nonionic surfactant is finally calcined or solvent-extracted. It is obtained by removing by means of
[0029]
In the present invention, the order of addition of the above raw materials is not limited. For example, a nonionic surfactant solution dissolved in an acid may be added to an aqueous alkali silicate solution diluted with water, and conversely, a solution dissolved in an acid may be added. An aqueous solution of an alkali silicate diluted with water may be added to the prepared nonionic surfactant solution.
[0030]
[material]
The silica raw material, the nonionic surfactant, and the acid used in the present invention will be further described.
[0031]
The alkali silicate used as the silica raw material in the present invention is preferably a relatively inexpensive sodium silicate. Specifically, equation (2),
Na2OmSiO2‥‥ (2)
Where m is a number from 1 to 4, especially a number from 2.5 to 3.5;
It is preferable to use an aqueous solution of sodium silicate having a composition represented by the following formula.
[0032]
As the nonionic surfactant, a triblock copolymer composed of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) or polyethylene oxide-polybutylene oxide-polyethylene oxide (PEO-PBO-PEO) is used. Is done. The molecular weight of the triblock copolymer must be in the range of 4,500 to 16,000, and the ratio of the hydrophilic portion (PEO) to the total molecular weight is 75% or more, particularly 80% or more.
[0033]
In the present invention, the reaction temperature is preferably 5 ° C. to 35 ° C., and if it is 35 ° C. or higher, it is difficult to produce monodispersed spherical particles. On the other hand, when the reaction temperature is low, the reaction rate is low, which is economically disadvantageous from the viewpoint of production efficiency.
The amount of the nonionic surfactant to be used is generally SiO 22The molar ratio is preferably adjusted in the range of 0.0030 to 0.012 according to the molecular weight.
[0034]
As the acid, an inorganic acid or an organic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, and acetic acid is used.From an economic viewpoint, it is preferable to use a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Among them, hydrochloric acid and nitric acid are preferable in terms of uniformity of the macro form.
[0035]
In the synthesis of the spherical microporous silica porous particles of the present invention, the mixing molar ratio of the starting materials is SiO 22: Nonionic surfactant: Na2It is preferable that O: acid: water = 1: 0.0030 to 0.012: 0.20 to 0.8: 3.5 to 10: 140 to 205.
Further, the method of mixing the starting materials is described in detail. A nonionic surfactant solution (A) dissolved in an acid having a predetermined concentration and an aqueous alkali silicate solution (B) diluted in water are mixed with stirring. Then, the stirring reaction is continued at a predetermined temperature for at least 20 minutes, preferably at least 30 minutes and about 2 hours at a predetermined temperature. Here, the raw material solutions (A) and (B) are previously adjusted to the same predetermined temperature and mixed.
[0036]
After the reaction, the solid product is separated from the suspension and dried sufficiently at room temperature to 100 ° C. Finally, in order to remove organic components and produce spherical microporous silica porous particles, heat treatment is performed at 200 ° C. or more for 2 hours or more, preferably 300 ° C. or more for 1 hour.
[0037]
The spherical silica porous particles of the present invention include not only spherical particles of pure silica but also Ti, Zr, Al, Fe, Zn, Cr, Mn, Co, Cu, Ni , V, Sn, Ru, Ce, Mo, W, Rh, Ag and the like. For example, an acid-soluble metal salt such as a chloride, a sulfate, a nitrate or a hydrate thereof of the above-mentioned metals can be contained in the starting material. In the case of an amphoteric oxide such as Al, a metal salt, metal oxide, metal hydroxide, or the like that is soluble in alkali can be used.
Further, the method of mixing the starting materials is described in detail. A nonionic surfactant (A) dissolved in a predetermined concentration of an acid, an alkali silicate aqueous solution (B) diluted in water, and an acid or alkali are mixed. After mixing the dissolved metal salt (C) with stirring, a stirring reaction is performed at a predetermined temperature for 20 minutes or more, preferably 30 minutes or more for about 2 hours. Here, the raw material solutions A, B and C are previously adjusted to the same predetermined temperature and mixed.
[0038]
[Use]
The spherical microporous silica porous particles of the present invention have a highly monodisperse spherical shape with a particle size of 20 to 500 μm, and further have regularly arranged micropores, thereby enabling selective selection of various molecules. It can be used as a catalyst carrier, an adsorbent, a desiccant and a filler for gas chromatography and ion chromatography. In particular, it can be used as an adsorbent or a concentrating agent for volatile organic compounds (VOCs), which are currently a social problem as an environmental pollutant. It can be expected that the function will be much improved. Furthermore, the pores formed inside are the most important factor related to the function expression of porous materials, but from the engineering point of view, the external properties of the porous material are important factors that determine the composite characteristics, velocity behavior, etc. Considering that it is a factor, it is a great feature that it has both regularity and uniformity of micropores as well as macro form that can be directly used for flow system reaction. It can be used as a bed reaction medium or the like. Further, by imparting multifunctionality by a metal species, it is suitable for use as an adsorption / separation / storage agent for ions / molecules and as a catalyst or catalyst carrier by adding a metal species. Further, it can be used in various applications by being blended in various paints, extenders for inks, adhesives and the like.
[0039]
【Example】
Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In addition, each test method performed in the Example was performed by the following method.
[0040]
(Measurement method)
(1) Scanning electron microscope: JSM5300 manufactured by JEOL was used for observation at an acceleration voltage of 10 kV and a WD of 10 mm.
(2) Specific surface area / pore volume: Using BELSORP28 manufactured by Bell Japan, the BET specific surface area was determined from a nitrogen adsorption isotherm measured at the liquid nitrogen temperature, and the pore diameter and total pore volume (micro (Pore volume) was calculated.
(3) Shape: Observed from a scanning electron micrograph.
(4) Particle size distribution: Measured with a scanning electron microscope photograph and Multisizer 3 manufactured by Beckman Coulter.
(5) Small-angle X-ray diffraction: Measured with a CuKα radiation source, an acceleration voltage of 45 kV and 60 mA using a nanoscale X-ray structure evaluation device manufactured by Rigaku Corporation.
(6) Adsorption isotherm of benzene: The adsorption isotherm was measured at 25 ° C. using BELSORP18 manufactured by Bell Japan.
[0041]
(Example 1)
Triblock copolymer Pluronic F88 (PEO) dissolved in 12% nitric acid39PPO103PEO39(Average molecular weight 11400, hydrophilic part PEO ratio 80%) A commercially available JIS No. 3 sodium silicate (SiO2: 23.6%, Na2(O: 7.59%), water was added thereto, and a diluted aqueous solution of sodium silicate was added thereto with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0042]
(Example 2)
To a solution of the triblock copolymer Pluronic F88 dissolved in 2N hydrochloric acid, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0043]
(Example 3)
To a solution of the triblock copolymer Pluronic F88 dissolved in 2N hydrochloric acid, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0044]
(Example 4)
Triblock copolymer Pluronic F68 (PEO) dissolved in 12% nitric acid76PPO30PEO76(Average molecular weight 8400, hydrophilic part PEO ratio 80%) To a (BASF) solution, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 27 ° C. to 29 ° C., and after stirring for 2 hours, the solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0045]
(Example 5)
Triblock copolymer Pluronic F108 (PEO) dissolved in 12% nitric acid132PPO56PEO132(Average molecular weight 15500, hydrophilic part PEO ratio 80%) (Asahi Denka Kogyo Co., Ltd.) To a solution was added an aqueous solution of sodium silicate prepared by adding water to commercially available JIS No. 3 sodium silicate while stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0046]
(Example 6)
To a solution of the triblock copolymer Pluronic F88 dissolved in 2N hydrochloric acid, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0047]
(Example 7)
To a solution of the triblock copolymer Pluronic F88 dissolved in 3N hydrochloric acid, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0048]
(Example 8)
To a solution of the triblock copolymer Pluronic F88 dissolved in 2N hydrochloric acid, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
[0049]
(Example 9)
To a solution of the triblock copolymer Pluronic F88 dissolved in 12% nitric acid, an aqueous solution of sodium silicate diluted by adding water to commercially available JIS No. 3 sodium silicate was added with stirring at 600 rpm.
The molar ratio of the mixed solution is
The reaction temperature was 25 ° C. to 27 ° C., and after performing a stirring reaction for 2 hours, a solid product was separated by filtration, washed with warm water of 60 ° C., and dried sufficiently at 50 ° C. Finally, the organic components were removed by baking for 1 hour in an electric furnace at 600 ° C., to obtain spherical spherical porous silica particles.
Table 1 below shows the synthesis conditions in Examples 1 to 9 described above.
[0050]
[Table 1]
(Comparative Example 1)
Triblock copolymer Pluronic F127 (PEO) dissolved in 12% nitric acid106PPO70PEO106(Average molecular weight 12600, hydrophilic part PEO ratio 70%) To a (BASF) solution, a sodium silicate aqueous solution prepared by adding water to a commercially available JIS No. 3 sodium silicate and adding thereto was added with stirring at 600 rpm. The molar ratio of the mixed solution is
[0052]
Table 2 shows the pore characteristics of the spherical microporous silica porous particles obtained in the above Examples and Comparative Examples.
[0053]
[Table 2]
In Table 2, the specific surface area is the value of the BET specific surface area determined from the nitrogen adsorption isotherm, and the pore volume is the value of the pore volume of only the micropores determined by the t plot method. 2t corresponds to the pore diameter, and corresponds to the intersection of two extrapolated straight lines drawn by the t-plot method (in FIG. 8, extrapolated straight lines are shown as a and d to avoid complexity). The particle size is the average size of the volume statistics measured by the electric resistance method.
[0055]
【The invention's effect】
According to the present invention, an inexpensive alkali silicate is further used as a silica source, and a non-toxic, biodegradable nonionic surfactant is used to form a regularly arranged micropore. Thus, spherical silica porous particles having a particle size on the order of microns can be obtained.
These spherical microporous silica porous particles can be used as an adsorbent or a concentrating agent for volatile organic compounds (VOC), etc., and also as a filler for gas chromatography or ion chromatography, a fluidized bed reaction medium and the like. it can. Further, by imparting multifunctionality by a metal species, it is suitable for use as an adsorption / separation / storage agent for ions / molecules and as a catalyst or catalyst carrier by adding a metal species. Further, it can be used for various applications by being blended in various paints, pigments, adhesives and the like.
[Brief description of the drawings]
FIG. 1 is an explanatory view schematically showing a solution state before gelation of a reaction system used in a production method of the present invention.
FIG. 2 In the process of the present invention for producing spherical microporous silica porous particles, via a precursor generated by the concerted order formation between a molecular aggregate micelle of a nonionic surfactant and a silica-dissolved species. FIG. 3 is a schematic view of a generated organic-inorganic nanocomposite.
FIG. 3 is an image diagram of micron-sized spherical micropore silica porous particles having micropores of the present invention.
FIG. 4 is a view showing a small-angle X-ray diffraction pattern of several examples of the spherical microporous silica porous particles of the present invention.
FIG. 5 is a scanning electron micrograph showing the particle morphology of several examples of the spherical microporous silica porous particles of the present invention.
FIG. 6 is a diagram showing the particle size distribution of several examples of the spherical microporous silica porous particles of the present invention.
FIG. 7 shows nitrogen adsorption isotherms of several examples of the spherical microporous silica porous particles of the present invention.
FIG. 8 is a diagram showing t plots of several examples obtained from a nitrogen adsorption isotherm of the spherical microporous silica porous particles of the present invention.
FIG. 9 shows an example of the spherical microporous silica porous particles of the present invention and a benzene adsorption isotherm of commercially available zeolite 13X.
Claims (7)
前記鉱酸を、ＳｉＯ２換算で、前記アルカリ珪酸塩１モル当たり３．５乃至１０モルに相当する量で使用し、
前記非イオン界面活性剤として、ポリエチレンオキシドーポリプロピレンオキシド−ポリエチレンオキシド（ＰＥＯ−ＰＰＯ−ＰＥＯ）またはポリエチレンオキシドーポリブチレンオキシド−ポリエチレンオキシド（ＰＥＯ−ＰＢＯ−ＰＥＯ）のトリブロック共重合体であって、分子量が４，５００乃至１６，０００で、全分子量に占める親水部（ＰＥＯ）の割合が７５％以上のものを使用することを特徴とする球状マイクロポアシリカ多孔質粒子の製造方法。The alkali silicate aqueous solution and the mineral acid are mixed and stirred in the presence of the nonionic surfactant, and the reaction is performed at a temperature of 5 ° C. to 35 ° C. to remove the nonionic surfactant from the generated spherical particles. A method for producing spherical microporous silica porous particles by
The mineral acid is used in an amount corresponding to 3.5 to 10 mol per mol of the alkali silicate in terms of SiO 2 ,
The non-ionic surfactant is a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) or polyethylene oxide-polybutylene oxide-polyethylene oxide (PEO-PBO-PEO), A method for producing spherical microporous silica porous particles, characterized by using a polymer having a molecular weight of 4,500 to 16,000 and a ratio of a hydrophilic portion (PEO) to the total molecular weight of 75% or more.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010228986A (en) * | 2009-03-27 | 2010-10-14 | National Institute Of Advanced Industrial Science & Technology | Rod-shaped porous silica particle |
| JP2018149538A (en) * | 2017-03-13 | 2018-09-27 | 株式会社三井Ｅ＆Ｓホールディングス | Molten slag processing method, silica raw material, high specific surface area silica, mesoporous silica and silica manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010228986A (en) * | 2009-03-27 | 2010-10-14 | National Institute Of Advanced Industrial Science & Technology | Rod-shaped porous silica particle |
| JP2018149538A (en) * | 2017-03-13 | 2018-09-27 | 株式会社三井Ｅ＆Ｓホールディングス | Molten slag processing method, silica raw material, high specific surface area silica, mesoporous silica and silica manufacturing method |
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| CN114685077A (en) * | 2020-12-30 | 2022-07-01 | 博特新材料泰州有限公司 | Slow-release type coagulation promoting composite material, preparation method thereof and application thereof in cement-based materials |
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