JP2004107140A - Zeolite molded product and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost zeolite molded product obtained from a reaction mixture containing zeolite, a plasticizer and a binder, and its manufacturing process. <P>SOLUTION: The zeolite molded product is obtained from the reaction mixture containing zeolite, the plasticizer and the binder. Here, the binder is a silanol group-containing polysiloxane represented by the formula: R<SP>1</SP><SB>m</SB>Si(OH)<SB>p</SB>(OR<SP>2</SP>)<SB>q</SB>O<SB>(4-m-p-q)/2</SB>(wherein R<SP>1</SP>is a 1-20C (un)substituted monovalent hydrocarbon group; R<SP>2</SP>is a 1-6C alkyl group or a 2-6C alkenyl or acyl group; and m, p and q are each a number satisfying 0.5≤m≤1.8, 0<p≤2.0, 0≤q≤0.5, 0<p+q≤2.0 and 0.5≤m+p+q≤3.3). The obtained zeolite molded product shows high compressive strength, even when baked at a low temperature. <P>COPYRIGHT: (C)2004,JPO

Description

（式中、Ｒ^６、Ｒ^７、Ｒ^１０〜Ｒ^１７は水素原子又は炭素数１〜８の一価炭化水素基であり、Ｒ^６とＲ^７、Ｒ^１０とＲ^１１とＲ^１２、Ｒ^１３とＲ^１４、Ｒ^１５とＲ^１６とＲ^１７は互いに同一であっても異なっていてもよい。Ｒはハロゲン原子を示す。Ｒ^８、Ｒ^９は炭素数１〜８の二価炭化水素基で、Ｒ^８とＲ^９は互いに同一であっても異なっていてもよい。ｐは０又は１〜３の整数である。）
【００３６】
なお、炭素数１〜８の一価炭化水素基としては、アルキル基、アリール基等、Ｒ^４で例示したものと同様のものが挙げられる。炭素数１〜８の二価炭化水素基としては、アルキレン基などが挙げられる。
【００３７】
Ｙとして具体的には、下記式で示されるものを挙げることができる。
Ｈ_２ＮＣＨ_２−、Ｈ（ＣＨ_３）ＮＣＨ_２−、Ｈ_２ＮＣＨ_２ＣＨ_２−、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２−、Ｈ_２ＮＣＨ_２ＣＨ_２ＣＨ_２−、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＣＨ_２−、（ＣＨ_３）_２ＮＣＨ_２ＣＨ_２ＣＨ_２−、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２−、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２−、（ＣＨ_３）_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２−、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２−、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２−、Ｃｌ⁻（ＣＨ_３）_３Ｎ^＋ＣＨ_２ＣＨ_２ＣＨ_２−、Ｃｌ⁻（ＣＨ_３）_２（Ｃ_６Ｈ_５ＣＨ_２）Ｎ^＋ＣＨ_２ＣＨ_２ＣＨ_２−、
【化２】

【００３８】
これらの中で以下のものが好ましい。
Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２−、
【化３】

【００３９】
なお、式（３）において、ａは０又は１である。
【００４０】
上記式（３）の窒素原子含有有機基を含有する加水分解性シラン（Ａ）としては、下記のものを例示することができる。
Ｈ_２ＮＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２ＮＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ（ＣＨ_３）ＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、（ＣＨ_３）_２ＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、（ＣＨ_３）_２ＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｃｌ⁻（ＣＨ_３）_３Ｎ^＋ＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｃｌ⁻（ＣＨ_３）_３Ｎ^＋ＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｃｌ⁻（ＣＨ_３）_２（Ｃ_６Ｈ_５ＣＨ_２）Ｎ^＋ＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｃｌ⁻（ＣＨ_３）_２（Ｃ_６Ｈ_５ＣＨ_２）Ｎ^＋ＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、
【００４１】
【化４】

【００４２】
【化５】

【００４３】
これらの中で特に好ましくは、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３であり、これらの部分加水分解物を用いてもよい。
【００４４】
一方、上記加水分解性シラン（Ａ）又はその部分加水分解物と混合して用いられる加水分解性シラン（Ｂ）は、下記一般式（４）で表され、その１種を単独で又は２種以上を組み合わせて用いることができ、その部分加水分解物を使用してもよい。
Ｒ^４ _ｂＳｉ（ＯＲ^３）_４−ｂ　　　　　　　　　　　　　　　　（４）
ここで、Ｒ^３、Ｒ^４は上記と同様である。ｂは０、１又は２である。
【００４５】
この式（４）の加水分解性シラン（Ｂ）としては、下記のものを例示することができる。
Ｓｉ（ＯＣＨ_３）_４、Ｓｉ（ＯＣＨ_２ＣＨ_３）_４、Ｓｉ（ＯＣＨ_２ＣＨ_２ＣＨ_３）_４、Ｓｉ（ＯＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_３）_４、ＣＨ_３Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、ＣＨ_３Ｓｉ（ＯＣＨ_２ＣＨ_２ＣＨ_３）_３、ＣＨ_３Ｓｉ（ＯＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_３）_３、（ＣＨ_３）_２Ｓｉ（ＯＣＨ_３）_２、（ＣＨ_３）_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_２、（ＣＨ_３）_２Ｓｉ（ＯＣＨ_２ＣＨ_２ＣＨ_３）_２、（ＣＨ_３）_２Ｓｉ（ＯＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_３）_２、
【化６】

【００４６】
これらの中で特に好ましくは、Ｓｉ（ＯＣＨ_３）_４、Ｓｉ（ＯＣＨ_２ＣＨ_３）_４、ＣＨ_３Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３及びこれらの部分加水分解物である。
【００４７】
上記窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物に式（４）の加水分解性シラン（Ｂ）又はその部分加水分解物を混合して用いる場合、その混合比は、窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物１００重量部に対し加水分解性シラン（Ｂ）又はその部分加水分解物５〜２００重量部の割合であり、より好ましくは加水分解性シラン（Ｂ）又はその部分加水分解物の量が１０〜１５０重量部である。この量が２００重量部を超えると液の安定性が悪化する場合がある。
【００４８】
上記加水分解性シラン（Ａ）、（Ｂ）又はそれらの部分加水分解物を用いて加水分解し、本発明のポリシロキサンを得る場合、溶媒は主として水を使用するが、必要に応じて、水と溶解する有機溶媒であるアルコール、エステル、ケトン、グリコール類を水に添加する形で用いることができる。有機溶媒としては、メチルアルコール、エチルアルコール、１−プロピルアルコール、２−プロピルアルコール等のアルコール類、酢酸メチル、酢酸エチル、アセト酢酸エチル等のエステル類、アセトン、メチルエチルケトン等のケトン類、グリセリン、ジエチレングリコール等のグリコール類などを挙げることができる。
【００４９】
溶媒の量は原料シラン１００重量部に対して４００〜５０００重量部が好ましい。更に好ましくは１０００〜３０００重量部である。溶媒の量が４００重量部より少ないと反応が進行しすぎ、系が均一にならない場合がある。また液の保存安定性も悪くなる場合がある。一方、５０００重量部より多いと経済的に不利な場合が生じるおそれがある。
【００５０】
また、溶媒中の水の量は、水／原料シランのモル比率で５〜５０が好ましい。このモル比率が５より少ないと加水分解が完全に進行しにくく、液の安定性が悪化する場合がある。一方、５０を超えると経済的に不利な場合が生じる。
【００５１】
反応方法としては、（１）混合シランを水中あるいは加水分解に必要である以上の量の水を含む有機溶剤中に滴下する方法、（２）混合シランあるいは有機溶剤含有混合シラン中に水を滴下する方法、（３）加水分解性シラン（Ｂ）又はその部分加水分解物を水中あるいは加水分解に必要である以上の量の水を含む有機溶剤中に滴下し、その後、窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物を滴下する方法、（４）窒素原子含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物を水中あるいは加水分解に必要である以上の量の水を含む有機溶剤中に滴下し、その後、加水分解性シラン（Ｂ）又はその部分加水分解物を滴下する方法などが挙げられるが、得られるポリシロキサンの安定性の点から、特に（１）の反応方法が好ましい。
【００５２】
なお、ポリシロキサンは水溶液の形で得られるが、必要に応じて更に水を加えたり除去したりして、ポリシロキサン１００重量部に対して水１０〜２，０００重量部、好ましくは１０〜１，０００重量部の比率に調整することにより、ポリシロキサン水溶液を形成することが好ましい。この場合、水の量が１０重量部より少ないとポリシロキサン自体の保存安定性が悪化する場合がある。また、２，０００重量部より多いとポリシロキサンを加える量が多くなってしまい、コスト的に好ましくない。
【００５３】
なお、この水溶性ポリシロキサンの数平均分子量は、２００〜３，０００、特に５００〜２，０００であることが好ましい。
【００５４】
また、バインダー［ＩＶ］として、下記平均組成式（５）
Ｒ^５ _ｃ（ＯＲ^３）_ｄＳｉＯ_{（４−ｃ−ｄ）／２}　　　　　　　　　　　（５）
（式中、Ｒ^５は炭素数１〜６のアルキル基、Ｒ^３は前記の通りである。ｃは０．７５〜１．５、ｄは０．２〜３で、かつ０．９＜ｃ＋ｄ＜４を満足する正数である。）
で表される有機ケイ素化合物（Ｃ）１００重量部と、下記一般式（３）
ＹＲ^４ _ａＳｉ（ＯＲ^３）_３−ａ　　　　　　　　　　　　　　　（３）
（式中、Ｙ、Ｒ^３、Ｒ^４、ａは前記の通りである。）
で表される窒素原子含有有機基を含有する加水分解性シラン又はその部分加水分解物（Ａ）０．５〜４９重量部とを有機酸又は無機酸の存在下で共加水分解縮合して得られるポリシロキサン自体も水溶性が付与されたものであり水に容易に溶解するため、ゼオライト成形体のバインダーとして使用するとより均質に処理が可能であり、副生するアルコール類も限りなく少ないため収縮等の変形もなく良好な成形体を得ることができる。
【００５５】
ここで、式（５）において、Ｒ^３は上述したものと同様である。Ｒ^５は炭素数１〜６、好ましくは１〜３のアルキル基である。具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等が挙げられ、特にメチル基が好ましい。
【００５６】
上記式（５）のオルガノオキシ基含有シロキサンは、例えば具体例として、
ＣＨ_３Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３Ｓｉ（ＯＣ_２Ｈ_５）_３、ＣＨ_３Ｓｉ（ＯＣＨ（ＣＨ_３）_２）_３、ＣＨ_３ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３ＣＨ_２Ｓｉ（ＯＣ_２Ｈ_５）_３、ＣＨ_３ＣＨ_２Ｓｉ（ＯＣＨ（ＣＨ_３）_２）_３、Ｃ_３Ｈ_６Ｓｉ（ＯＣＨ_３）_３、Ｃ_３Ｈ_６Ｓｉ（ＯＣ_２Ｈ_５）_３、Ｃ_３Ｈ_６Ｓｉ（ＯＣＨ（ＣＨ_３）_２）_３、Ｃ_４Ｈ_９Ｓｉ（ＯＣＨ_３）_３、Ｃ_４Ｈ_９Ｓｉ（ＯＣ_２Ｈ_５）_３、Ｃ_４Ｈ_９Ｓｉ（ＯＣＨ（ＣＨ_３）_２）_３、Ｃ_５Ｈ_１１Ｓｉ（ＯＣＨ_３）_３、Ｃ_５Ｈ_１１Ｓｉ（ＯＣ_２Ｈ_５）_３、Ｃ_５Ｈ_１１Ｓｉ（ＯＣＨ（ＣＨ_３）_２）_３、Ｃ_６Ｈ_１３Ｓｉ（ＯＣＨ_３）_３、Ｃ_６Ｈ_１３Ｓｉ（ＯＣ_２Ｈ_５）_３、Ｃ_６Ｈ_１３Ｓｉ（ＯＣＨ（ＣＨ_３）_２）_３等のアルコキシ基含有シロキサンを部分加水分解縮合することにより得ることができる。
これらは単独で加水分解縮合させても２種類以上の混合物を加水分解縮合させてもよいし、混合シランの部分加水分解物を使用してもよい。
【００５７】
この場合の部分加水分解物のケイ素原子の数は２〜１０、特に２〜４であることが好ましい。更に（Ｃ）成分としては、水中で炭素原子数１〜６のアルキルトリクロロシランとメタノール又はエタノールとの反応により得られるものでもよい。この場合もケイ素原子数が２〜６、特に２〜４であることが好ましく、また、２５℃で３００ｍｍ^２／ｓ以下の粘度を有しているものが好ましく、特に１〜１００ｍｍ^２／ｓの粘度を有するものが好適である。
【００５８】
また、式（３）の窒素原子含有有機基を含有する加水分解性シラン（Ａ）は、前記した通りである。
【００５９】
このような上記式（３）の窒素原子含有有機基を含有する加水分解性シランの具体例としては、Ｈ_２Ｎ（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）_３、Ｈ_２Ｎ（ＣＨ_２）_２Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２Ｎ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、Ｈ_２Ｎ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、ＣＨ_３ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、ＣＨ_３ＮＨ（ＣＨ_２）_５Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３ＮＨ（ＣＨ_２）_５Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２Ｎ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、Ｈ_２Ｎ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、ＣＨ_３ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、ＣＨ_３ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｃ_４Ｈ_９ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、Ｃ_４Ｈ_９ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_２ＣＨ_３）_３、Ｈ_２Ｎ（ＣＨ_２）_２ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２Ｎ（ＣＨ_２）_２ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｈ_２Ｎ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２Ｎ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、ＣＨ_３ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_３）_２、ＣＨ_３ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、ＣＨ_３ＮＨ（ＣＨ_２）_５ＳｉＣＨ_３（ＯＣＨ_３）_２、ＣＨ_３ＮＨ（ＣＨ_２）_５ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｈ_２Ｎ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｈ_２Ｎ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、ＣＨ_３ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_３）_２、ＣＨ_３ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２、Ｃ_４Ｈ_９ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_３）_２、Ｃ_４Ｈ_９ＮＨ（ＣＨ_２）_２ＮＨ（ＣＨ_２）_３ＳｉＣＨ_３（ＯＣＨ_２ＣＨ_３）_２等が挙げられる。
【００６０】
これらの中で、特に、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン等が好適に用いられる。
【００６１】
上記（Ｃ）及び（Ａ）成分の使用割合は、（Ｃ）成分１００重量部に対して（Ａ）成分０．５〜４９重量部、好ましくは５〜２０重量部である。（Ａ）成分が０．５重量部未満であると水溶性が弱くなり、水溶液にした時の安定性が悪くなる場合がある。また、（Ａ）成分が４９重量部を超えるとコスト的に不利になるおそれがある。
【００６２】
モル換算としては、（Ｃ）成分のＳｉ原子１モルに対し（Ａ）成分のＳｉ原子が０．０１〜０．３モル、特に０．０５〜０．２モルとなるように用いることが好ましい。
【００６３】
これら（Ｃ）及び（Ａ）成分を用いて水溶性ポリシロキサンを製造するには、有機酸又は無機酸の存在下で共加水分解させればよい。この場合、最初に（Ｃ）成分を有機酸あるいは無機酸の存在下で加水分解し、この（Ｃ）成分の加水分解物と（Ａ）成分を混合し、有機酸あるいは無機酸の存在下、更に加水分解させることが好ましい。
【００６４】
まず、（Ｃ）成分を加水分解する際に使用される有機酸及び無機酸としては、例えば塩酸、硫酸、メタンスルホン酸、ギ酸、酢酸、プロピオン酸、クエン酸、シュウ酸及びマレイン酸などから選ばれる少なくとも１種の酸が用いられるが、特に酢酸、プロピオン酸が好適である。この酸の使用量は、（Ｃ）成分１００重量部に対して２〜４０重量部、特に３〜１５重量部が好適である。この酸の使用量が少なすぎると加水分解の進行が遅く、また、組成物の水溶液の安定性が悪化することがある。
【００６５】
加水分解の際は適度に溶剤で希釈した状態で行うのが好ましい。溶剤としては、アルコール系溶剤が好適であり、特にメタノール、エタノール、イソプロピルアルコール、第三ブチルアルコールが好適である。この溶剤の使用量は、（Ｃ）成分１００重量部に対して５０〜３００重量部、特に７０〜２００重量部が好ましい。溶剤の使用量が５０重量部より少ないと、縮合が進行しすぎる場合があり、また、３００重量部を超えると、加水分解に時間がかかることがある。
【００６６】
また、（Ｃ）成分を加水分解させるために加える水量は、（Ｃ）成分１モルに対し０．５〜４モル量、特に１〜３モル量が好適である。加える水量が０．５モル量より少ないとアルコキシ基が多く残存してしまう場合があり、４モル量を超えると縮合が進行しすぎる場合がある。（Ｃ）成分を加水分解させる際の反応条件は、反応温度１０〜４０℃、特に２０〜３０℃が好ましく、反応時間は１〜３時間で加水分解反応させるのがよい。
【００６７】
このようにして得られた（Ｃ）成分の加水分解物と（Ａ）成分とを反応させる。なお、反応条件は、反応温度６０〜１００℃、反応時間１〜３時間が好ましい。反応終了後は、溶剤の沸点以上まで温度を上げ、アルコール溶剤を留去させる。この場合、系内の全アルコール（反応溶剤としてのアルコール、副生成物としてのアルコール）の含有量を３０重量％以下、特に１０重量％以下となるように留去させることが好ましい。アルコールが多く含まれていると、水で希釈した場合、白濁したりゲル化したりすることがあり、保存安定性も低下することがある。上記方法で製造できるポリシロキサンは、２５℃における粘度が５〜２，０００ｍｍ^２／ｓ、特に５０〜５００ｍｍ^２／ｓであることが好ましい。粘度が高すぎると作業性や保存安定性が低下したり、水への溶解性が低下することがある。
【００６８】
このようにして得られた水溶性ポリシロキサンを有効成分として好ましくは０．１〜２０重量％、特に好ましくは１〜１０重量％を水に均一混合した水溶性ポリシロキサン溶液をバインダーとして用いることが望ましい。この時、水溶性ポリシロキサンの濃度が０．１重量％より少ないと処理効率が悪くなる場合がある。また２０重量％より多いとコスト的に不利であり、水溶液安定性も悪くなる場合がある。
【００６９】
なお、この水溶性ポリシロキサンの数平均分子量は、２００〜５，０００、特に５００〜２，０００であることが好ましい。
【００７０】
本発明のゼオライト成形体は、上述したように、上記バインダー［Ｉ］、［ＩＩ］、［ＩＩＩ］又は［ＩＶ］と、ゼオライトと、可塑剤とを含む反応混合物から得られるものであるが、この場合、本発明に使用されるゼオライトは、ゼオライト３Ａ、ゼオライト４Ａ、ゼオライト５Ａ及びゼオライトＸ並びにこれらの任意の混合物から選ばれるものを使用することが好ましい。
【００７１】
本発明で用いられる可塑剤は水に可溶なものであり、可塑剤としては、メチルセルロース等のセルロースエーテル、ポリサッカライド、ポリビニルアルコール、澱粉、又はこれらを任意に混合したものを用いることができる。
【００７２】
更に、必要により、滑剤としてワックスエマルジョン及び／又は脂肪酸混合物を反応混合物に添加して、レオロジー調節を行うこともできる。
【００７３】
本発明の成形体を製造するための反応混合物は、全反応混合物に対して１〜３５重量％の含量のバインダー、４０〜９０重量％の含量のゼオライト及び５〜４０重量％の含量の可塑剤を含むことが好ましい。これにより吸着、触媒及び機械的性質に優れた成形体を得ることができる。
【００７４】
この場合、上記バインダー［Ｉ］、［ＩＩ］を用いる際は、２〜２５重量％、特に５〜２０重量％とすることが好ましく、これにより成形中に最適の変形特性を得ることができ、また最大の圧縮強度値を達成した成形体を得ることができる。また、バインダー［ＩＩＩ］、［ＩＶ］を用いる場合は、１０〜３５重量％、特に１５〜３０重量％が好ましい。少なすぎると処理効率が悪くなり、多すぎると水溶液の安定性が悪くなるおそれがある。
【００７５】
また、ゼオライトのより好ましい使用量は、４０〜６０重量％であり、可塑剤のより好ましい使用量は５〜１５重量％である。
【００７６】
ここで、本発明の成形体を製造するための反応混合物は、例えば、水及び可塑剤としてメチルセルロースを含む場合、可塑剤の含有量が少ないと押出機により成形される押出物は寸法安定性に劣るおそれがある。４００セル／インチ^２（約６２セル／ｃｍ^２）を備えた本発明による四方形のハニカム状成形体の押出成形の場合、水の添加量に対して約１０重量％以上、更に好ましくは約１５重量％以上のメチルセルロースを含有する。これにより、流量限度が増大し、押出物の吸入圧力損失が著しく低減され、寸法安定性に優れた押出物が得られる。その結果、ダイスに沿った圧力低下が小さくなり、押出機における背圧長が減少する。そのため、押出機スクリュウの圧力蓄積帯域への剪断力がより少なくなり、熱の放散が少なく、反応混合物の加熱が回避される。
【００７７】
なお、水の配合量は、０〜５４重量％、好ましくは５〜４０重量％、特に１０〜３５重量％である。
【００７８】
また、上述したように、ワックスエマルジョン及び／又は脂肪酸混合物を滑剤として配合し得るが、その配合量は０〜２０重量％、特に０〜１０重量％である。この場合、上記バインダー［Ｉ］、［ＩＩ］は、同時に滑剤としても作用し、これらバインダー［Ｉ］、［ＩＩ］を用いた反応混合物は、製造プロセス中の流動限度及び吸気圧力損失が低く、反応混合物の成形性が著しく改善され、更に滑剤を添加する必要がない。
【００７９】
本発明の、ゼオライト、可塑剤及びバインダーを含む反応混合物のゼオライト成形体は下記の工程により製造される。
第１工程：ゼオライト、可塑剤及びバインダーの反応混合物の調製
第２工程：反応混合物の押出成形
第３工程：１８０〜２８０℃の温度における押出物の焼成
【００８０】
本発明の製造方法の実質的利点は、焼成が約１８０〜２８０℃の温度範囲内で実施されることである。市販のバルク形態のゼオライトの固定床及び先行文献に記載された成形体はいずれも、少なくとも４００℃以上、一般的には５００〜７００℃の温度で焼成される。これらは焼成温度が高温なため、バルク品や成形体を製造する時に非常に大きなエネルギーを消費する。一方、本発明の製造方法では、このような高温度下で焼成する必要がないため、成形体の製造コストを著しく低減し得る。また、バインダーであるポリシロキサン中のアルコキシ基も少ないことから、反応により副生する引火性のアルコールが実質的にないため、防爆性の装置などの使用する必要がなく、更にコストの低減が可能となったものである。上記温度範囲で焼成された本発明の成形体は、優れた機械的及び吸着特性をも有する。
【００８１】
本発明の製造方法の第１工程及び第２工程は連続的に行うのが好ましい。即ち、各成分の配合及び成形用組成物の成形を連続的に一工程で行う。押出成形は、単軸又は２軸スクリュー押出機を採用できるが、例えば、同方向に回転するスクリューを備えた２軸スクリュー押出機を用いた場合、同方向に回転するスクリューを備えた高密配合２軸スクリュー押出機は、混合装置及びハニカム状押出物の押出用圧力発生機として機能する。反応混合物の各成分のうち、可塑剤及びゼオライトの粉末状成分は、それぞれ重力落下計量装置を介して供給され、水及びバインダーの液体状成分は膜を介して又はピストンポンプで供給される。本発明方法の成形体の連続製造においては、プロセス全体にわたる利益性を著しく高めることができる。また、これにより混練済みの反応混合物を押出機へ移動する操作を省くことができる。
【００８２】
本発明方法の第３工程は、１８０〜２８０℃、好ましくは２００〜２５０℃、更に好ましくは２１０〜２３５℃の温度で焼成を行う。この温度範囲内で焼成を行った場合、これ以外の温度範囲で焼成した場合に比べて、極めて高い圧縮強度を有する成形体を得ることができる。また、吸着及び触媒特性にも優れた成形体を得ることができる。なお、押出物の追加乾燥は、本発明方法の第２及び第３工程の間で実施できる。
【００８３】
シリコーンマトリックスの完全な架橋結合は、これらの温度範囲で達成される。ゼオライトも共有結合される最大数の共有架橋結合が焼成工程中に形成する。焼成温度が２８０℃を超えると、バインダーからのメチル基や窒素原子含有有機基の断絶脱離が開始し、その結果として形成マトリックスが弱化され、本発明による成形体の圧縮強度が低下する場合がある。一方、１８０℃より低い温度では、バインダーの架橋及び共有結合の形成が僅かに起こるだけであり、好ましくない。
【００８４】
本発明による成形体の圧縮強度は、約２０Ｎ／ｍｍ^２以上、好ましくは約３０Ｎ／ｍｍ^２以上、更に好ましくは約５０Ｎ／ｍｍ^２以上である。本発明による成形体は、１８０〜２８０℃の温度範囲で焼成することにより最大圧縮強度を備えることができる。
【００８５】
本発明の成形体の圧縮強度は、アタパルジャイトのような粘度材料あるいはバインダーとしてオルトケイ酸メチルを用いて製造されるゼオライトペレットと比較して数倍高い。本発明による成形体について達成され得る高い圧縮強度は、成形体を更に熱処理する際に生じる収縮や、押出物中にこの収縮によって誘起される内在ストレスが補償されるため有利である。それにより本発明の成形体における亀裂等が回避され、表面品質及び機械的性質に優れた成形体を得ることができる。
【００８６】
また、バルク形態のゼオライトの固定床と比較して、特にハニカム状押出物とした場合、表面積が大きいため吸着性が著しく改善される。例えば、温度２３℃及び相対湿度１０％の気象キャビネット（ｃｌｉｍａｔｅ　ｃａｂｉｎｅｔ）中での吸着容量の水の増加の測定値は、タイプ４Ａのゼオライトを使用して３時間後、成形体に対して１３重量％から１７重量％以上である。
【００８７】
更には、本発明による成形体は、９９％よりも大きな磨耗抵抗を有する。磨耗抵抗は、アメリカン・ペニィ・アトリション・テスト（Ａｍｅｒｉｃａｎ　Ｐｅｎｎｙ　Ａｔｔｒｉｔｉｏｎ　Ｔｅｓｔ：Ｗ．Ｊ．ミッチェル等の１９５６年の米国特許第２，９７３，３２７号）に準拠して以下のように測定した値である。完全円筒形ゼオライト系ペレット（Ｄ＝５ｍｍ、Ｌ／Ｄ＝１．５）３ｇを、プラスチック容器へ導入して閉鎖する。この容器をレッツシュ（Ｒｅｔｓｃｈ）のモデル３Ｄ振動篩機で２０分間６０スケール単位の振動数で振動させる。増大した磨耗及び真の荷重を模擬するために、そのプラスチック容器は更にペニッヒ硬貨片を１枚含む。次いで、得られる磨耗した材料をメッシュ幅５００μｍの篩で２０スケール単位の振動数において２分間にわたり分離する。
【００８８】
本発明の成形体は、管、円筒、ビーズ、タブレット、環、シート等の形状で製造することができるが、ハニカム体の形状を有するのが好ましい。ハニカム状成形体はセル密度が高く、他の成形体、例えばシートの形態のものと比較して、極めて大きな表面積を有し、本発明の成形体の触媒及び吸収特性、特に吸収性が著しく改善される。
【００８９】
本発明によるゼオライト成形体は、極めて安価に製造でき、機械的応力に対して安定性が高く、従って種々の用途に利用することができる。
【００９０】
また、特にゼオライトのバルク状の固定床で生じるような、磨耗による成形体の装置又は機械下流側の閉塞又は破損が起こらないため、工業装置で長期間使用するのに好適である。更に、バルク状の固定床でゼオライト材料の変化が生じなく、装置の運転費用が低減され、本発明の成形体を使用することにより、圧力損失を極めて低くできる。
【００９１】
本発明のゼオライト成形体は、気体及び液体の乾燥、調質、精製及び分離等広い用途に使用することができる。使用した成形体は、交番加圧プロセス、熱処理、又は溶媒による洗浄と乾燥のいずれかによって再生することができる。
【００９２】
また、本発明のゼオライト成形体は、残留水分の除去のため、例えば、回転吸収器（Ｒｏｔｏｒ　Ａｂｓｏｒｂｅｒ）で使用できる。更に、本発明のゼオライト成形体は、圧縮空気の乾燥のために使用できる。新鮮空気と共に圧縮空気系に入る水分は、圧縮／圧力開放中に凝縮され、装置等を腐食し、系の機能に損害を与え得る。この場合、本発明によるゼオライト成形体を吸収剤として組み込むことにより、エアーブレーキ系統、空気圧駆動及び制御装置から水を除去することができ、それにより腐食を抑制することができる。
【００９３】
また、本発明の成形体は、ＣＦＣ不使用冷凍装置において冷媒乾燥のためにも使用できる。この場合、本発明の成形体の容量は１０〜１５年であるため、成形体の再生は必要でない。冷凍装置が組み立て中に閉じられると、水分は規則的に導入され、本発明による成形体を冷媒の乾燥に使用することによって、生じる欠点は回避される。
【００９４】
使用済みの冷媒の乾燥及びリサイクルは、本発明の成形体を吸収剤として使用することにより行うことができる。吸収剤の再生は、熱処理によって行うことができる。
【００９５】
本発明による成形体は、スプレー缶高圧ガス（例えば、ブタン）としての液体炭化水素の脱硫（臭気抑制）のためにも使用できる。
【００９６】
更に、本発明による成形体は、空気分離装置に使用でき、窒素を吸収し、そして例えば吸入用空気の酸素強化が結果としてなされる。再生は、熱処理によって実施できる。
【００９７】
本発明による成形体は、更にエア・コンディショニング装置においても使用できる。この場合、吸収及び気化エンタルピーは熱発生又は冷却のために利用される。
【００９８】
本発明による成形体は、水軟化装置においてイオン交換剤として使用できる。この場合、カルシウム−ナトリウム交換により所望の効果が達成される。
【００９９】
【発明の効果】
本発明によるシラノール基含有ポリシロキサンあるいは水溶性ポリシロキサンをバインダーとして使用することにより、低温度で焼成しても高圧縮強度を有するゼオライトの成形体を得ることができる。また、副生するアルコールもないか、あるいは非常に少量のため、安全性も高く、防爆性の装置も必要としないため、コスト削減になり、更に副生アルコールによる成形体の収縮や寸法変化もない。
【０１００】
【実施例】
以下、合成例、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、％は重量％、部は重量部を示す。
【０１０１】
〔合成例１〕シラノール基含有ポリシロキサン１の製造
２Ｌのフラスコにメチルトリメトキシシラン４０８ｇ（３．０モル）及びトルエン３００ｇを仕込み、４０℃で撹拌しながら２％の塩酸水溶液９７ｇを１時間かけて滴下混合し、加水分解させた。更に、４０℃で１時間撹拌しながら熟成した。次いで、１０％の硫酸ナトリウム水溶液１００ｇを加えて１０分間撹拌した後、静置して水層を分離除去するという水洗操作を３回繰り返した。得られたシラノール基含有ポリシロキサンから５０℃、６．７ｋＰａの条件下でメタノールを減圧留去し、その後、濾過してシラノール基含有ポリシロキサンを得た。ＧＰＣ測定の結果、このシラノール基含有ポリシロキサンの数平均分子量は２，０００であった。また、シラノール基量を定量したところ、その含有量は４．２％（対シラノール基含有ポリシロキサン）であり、クラッキング法によりメトキシ基量を定量したところ、１．４％（対シラノール基含有ポリシロキサン）であった。以上から、得られたシラノール基含有ポリシロキサン１は、以下の組成で表すことができると認められた。
（ＣＨ_３）_１．０Ｓｉ（ＯＨ）_０．１７（ＯＣＨ_３）_０．０３Ｏ_１．４０
【０１０２】
〔合成例２〕シラノール基含有ポリシロキサン２の製造
２Ｌのフラスコにメチルトリメトキシシラン４０８ｇ（３．０モル）を仕込み、窒素雰囲気下、０℃で水７８６ｇを加えてよく混合した後、氷冷下０．０５Ｎの塩酸水溶液２１６ｇを４０分かけて滴下して加水分解反応を行い、滴下終了後、１０℃以下で１時間、更に室温で２時間撹拌して加水分解反応を完結させた。次いで、生成したメタノール及び水を７０℃、８．０ｋＰａの条件で減圧留去し、留去液中にメタノールが検出されなくなるまで継続した。初期の８８％まで濃縮した時点でメタノールは検出されなくなり、同時に液は白濁し始めた。この溶液を１昼夜静置したところ、２層に分離し、シラノール基含有ポリシロキサンは沈降した。このシラノール基含有ポリシロキサンから水を分離し、シラノール基量と数平均分子量を測定したところ、その含有量は８．２％（対シラノール基含有ポリシロキサン）、数平均分子量は１，８００であった。赤外吸収スペクトル分析の結果、メトキシ基が残存していないので、得られたシラノール基含有ポリシロキサン２は、以下の組成で表すことができると認められた。
（ＣＨ_３）_１．０Ｓｉ（ＯＨ）_０．３４Ｏ_１．３３
【０１０３】
〔合成例３〕水溶性ポリシロキサン１の製造
水２４６ｇ（１３．７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた５００ｍｌの反応器に入れ、撹拌した。ここに、Ｈ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３４４．４ｇ（０．２ｍｏｌ）及びＳｉ（ＯＣＨ_２ＣＨ_３）_４２０．８ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５６℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノール、エタノールを除去することにより、水溶性ポリシロキサン１を２５０ｇ得た。このものの不揮発分（１０５℃／３時間）は１４．９％であった。また、数平均分子量は１，８００であった。
【０１０４】
〔合成例４〕水溶性ポリシロキサン２の製造
水２７８ｇ（１５．４ｍｏｌ）を撹拌機、温度計及び冷却器を備えた５００ｍｌの反応器に入れ、撹拌した。ここにＨ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３５５．６ｇ（０．２５ｍｏｌ）及びＳｉ（ＯＣＨ_２ＣＨ_３）_４１０．４ｇ（０．０５ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２７℃から４９℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９８℃まで上げ、副生したメタノール、エタノールを除去することにより、水溶性ポリシロキサン２を２７４ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．１％であった。また、数平均分子量は１，６００であった。
【０１０５】
〔合成例５〕水溶性ポリシロキサン３の製造
水２０２ｇ（１１．２ｍｏｌ）を撹拌機、温度計及び冷却器を備えた５００ｍｌの反応器に入れ、撹拌混合した。ここにＨ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３３３．３ｇ（０．１５ｍｏｌ）及びＳｉ（ＯＣＨ_２ＣＨ_３）_４３１．２ｇ（０．１５ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から５１℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノール、エタノールを除去することにより、水溶性ポリシロキサン３を２１０ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．３％であった。また、数平均分子量は１，１００であった。
【０１０６】
〔合成例６〕水溶性ポリシロキサン４の製造
水３０８ｇ（１７．１ｍｏｌ）を撹拌機、温度計及び冷却器を備えた５００ｍｌの反応器に入れ、撹拌混合した。ここにＨ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３５３．１ｇ（０．２ｍｏｌ）及びＳｉ（ＯＣＨ_３）_４１５．２ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２８℃から５３℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、水溶性ポリシロキサン４を３００ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．４％であった。また、数平均分子量は２，０００であった。
【０１０７】
〔合成例７〕水溶性ポリシロキサン５の製造
水２５３ｇ（１４．１ｍｏｌ）を撹拌機、温度計及び冷却器を備えた５００ｍｌの反応器に入れ、撹拌混合した。ここにＨ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３４４．４ｇ（０．２ｍｏｌ）及びＣＨ_３Ｓｉ（ＯＣＨ_３）_３１３．６ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２６℃から４２℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノールを除去することにより、水溶性ポリシロキサン５を２４４ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．６％であった。また、数平均分子量は１，６００であった。
【０１０８】
〔合成例８〕水溶性ポリシロキサン６の製造
水２４１ｇ（１３．４ｍｏｌ）を撹拌機、温度計及び冷却器を備えた５００ｍｌの反応器に入れ、撹拌混合した。ここにＨ_２ＮＣＨ_２ＣＨ_２ＨＮＣＨ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３４４．４ｇ（０．２ｍｏｌ）、Ｓｉ（ＯＣＨ_２ＣＨ_３）_４１８．７ｇ（０．０９ｍｏｌ）及びＣＨ_３Ｓｉ（ＯＣＨ_３）_３１．４ｇ（０．０１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２６℃から４９℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９９℃まで上げ、副生したメタノール、エタノールを除去することにより、水溶性ポリシロキサン６を２４１ｇ得た。このものの不揮発分（１０５℃／３時間）は１５．７％であった。また、数平均分子量は１，５００であった。
【０１０９】
〔合成例９〕水溶性ポリシロキサン７の製造
冷却管、温度計及び滴下漏斗を備えた５００ｍｌの四つ口フラスコにメチルトリメトキシシランのオリゴマー８５ｇ（ダイマー換算で０．３７モル）、メタノール１５４ｇ及び酢酸５．１ｇを入れ、撹拌しているところに水６．８ｇ（０．３７モル）を投入し、２５℃で２時間撹拌した。そこに、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン８．９ｇ（０．０４モル）を滴下した。その後、メタノールの還流温度まで加熱して１時間反応後、エステルアダプターにて、内温が１１０℃になるまでメタノールを留去し、粘度７１ｍｍ^２／ｓの薄黄色透明溶液８１ｇを得た（数平均分子量１，１００）。これを水で１５重量％となるように希釈し、淡黄色透明の水溶性ポリシロキサン７を得た。
【０１１０】
〔合成例１０〕水溶性ポリシロキサン８の製造
Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシランを３−アミノプロピルトリエトキシシラン１７．７ｇ（０．０８モル）とした以外は、合成例９と同様に反応を行い、粘度２２０ｍｍ^２／ｓの薄黄色透明溶液９０ｇを得た（数平均分子量１，３００）。これを水で１５重量％となるように希釈し、透明の水溶性ポリシロキサン８を得た。
【０１１１】
〔実施例、比較例〕
圧縮強度
Ｚｗｉｃｋ社の引張り／加圧試験機モデルＵＰ１４５５を使用し測定した。
５ｍｍの試験材直径を有する完全に円筒形の押出物を７ｍｍの試験材長さに切断した。正確かつ再現性ある測定のために、押出物の両前面が面平行であることが確保されなければならない。測定は室温にて、試験圧力１Ｎ、試験速度１ｍｍ／分で実施された。試験力は両前面に作用する。
【０１１２】
〔実施例１〕
２００ｇの合成ゼオライトＡ−３粉末（和光純薬社製）、可塑剤として２５ｇのメチルセルロースＭＣ　１２０００（Ａｑｕａｌｏｎ社製）、６３ｇのシラノール含有ポロシロキサン１及び１６０ｇの水を含む反応混合物を２軸スクリュー押出機ＺＳＫ（ウエルナー＆フライデルエル（Ｗｅｒｎｅｒ　＆　Ｐｆｌｅｉｄｅｒｅｒ）社製）を用い、５０ｒｐｍの回転速度にて配合及びハニカム状形体への成形を行った。押出機のバレル部分の温度は１５度であった。メチルセルロースは４０℃より高い温度において熱によりゲル化し、その水保持性を失うため、加工中はバレル部分の適切な冷却を確保しなければならない。次いで、予備乾燥することなく２２５℃の温度で６０分間焼成した。得られた成形体の圧縮強度は５０．１Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１３】
〔実施例２〕
合成ゼオライトＡ−４粉末（和光純薬社製）２００ｇ、２５ｇのメチルセルロースＭＣ　１２０００、３５ｇのシラノール基含有ポロシロキサン２及び１００ｇの水を用いてハニカム状及びペレット状の成形体を製造した。この反応混合物は、１４℃の温度において、実施例１で使用した２軸スクリュー押出機で押出した。次いで、６０分間２００℃でハニカム状成形体を製造した。得られた成形体の圧縮強度は、５７Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１４】
〔実施例３〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン１を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４３．７Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１５】
〔実施例４〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン２を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４１．７Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１６】
〔実施例５〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン３を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４５．９Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１７】
〔実施例６〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン４を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４２．５Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１８】
〔実施例７〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン５を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４４．３Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１１９】
〔実施例８〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン６を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４７．７Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１２０】
〔実施例９〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン７を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４８．１Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１２１】
〔実施例１０〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００及び水溶性ポリシロキサン８を２５０ｇ含む反応混合物を実施例１と同様に処理し、成形体を製造した。得られた成形体の圧縮強度は４７．９Ｎ／ｍｍ^２であった。成型時及びその後も寸法の変化・収縮などは見られなかった。
【０１２２】
〔比較例１〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００、バインダーとして６３ｇのメチルシロキサンエーテル　ＭＳＥ　１００及び１６０ｇの水を含む反応混合物を実施例１と同様に処理し、成形体を製造した。ここで、メチルシロキサンエーテル　ＭＳＥ　１００は、ケイ酸メチルの種々のオリゴマー体の混合物であり、加水分解及び縮合によって反応して硬質ケイ素樹脂を与えるものである。得られた成形体の圧縮強度は４６．７Ｎ／ｍｍ^２であったが、成型時収縮が見られた。
【０１２３】
〔比較例２〕
２００ｇの合成ゼオライトＡ−３粉末、２５ｇのメチルセルロースＭＣ　１２０００、１００ｇの量の正珪酸エチル及び１６０ｇの水を含む反応混合物を実施例１と同様に処理し成形体を製造したが、焼成温度が低いためか、得られた成形体の圧縮強度は１８．１Ｎ／ｍｍ^２しかなかった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a zeolite molded article obtained from a reaction mixture containing a zeolite, a plasticizer and a binder, and a method for producing the same.
[0002]
[Prior art]
Zeolites are crystalline, microporous materials having a specific pore structure. This zeolite is used industrially in the form of a fixed bed in bulk form and has various applications, for example, in gas drying, removal of volatile hydrocarbons from waste air streams and separation of hydrocarbon fractions.
[0003]
The use of zeolites in the form of fixed beds in bulk form has the disadvantage that, during operation, abrasion occurs, in particular. This dust-like erosion substance damages equipment and devices arranged on the downstream side, and when gas flows through, the fixed bed in a bulk form has a pressure fluctuation compared to a zeolite-based honeycomb body. Occurs, and the pressure loss is extremely large.
[0004]
On the other hand, when the zeolite powder is formed into a molded body, it is necessary to add certain additives to the composition in the compounding step in order to impart plasticity to the molding composition. Next, after obtaining a molded product by extrusion molding or the like, the plasticizer in the molded product is removed so that no residue is generated as much as possible. This is because if the molded article contains a residue, even if the amount is small, the adsorptivity and the catalytic properties of the molded article deteriorate.
[0005]
Further, in order to obtain a molded article having excellent dimensional stability, it is necessary to further add a binder to the molding composition. The binder decomposes upon firing to form solid crosslinks.
[0006]
As a specific method for producing a zeolite molded body, for example, there is a method for producing a hard, destruction-resistant catalyst from a pentasil-based zeolite (for example, see Patent Document 1). Here, 5% by weight of tetramethyl orthosilicate is used as a binder, and 2% by weight of hydroxyethyl cellulose is used as a plasticizer. After kneading this mixture, it is transferred to an extruder and formed into a strand. After drying the thus obtained molded body, it is fired at a temperature of 400 to 800 ° C. for 2 hours.
[0007]
However, when a zeolite molded body is produced by this method, there is a disadvantage that it is very cost-intensive because it is calcined at a high temperature for a long time. Another factor is that the mixing and extrusion of the molding composition are performed in separate steps. Furthermore, since tetramethyl orthosilicate as a binder has a small molecule, it deposits and blocks inside a pentasil-based zeolite, and thus has a problem of impairing the adsorptive properties and catalytic properties of a zeolite molded body.
[0008]
Also, there is a method for producing a molecular sieve molded product of zeolite mainly using silica sol as a binder (for example, see Patent Document 2). SiO contained in this silica sol₂The specific surface area of the particles is 150 to 400 m as measured by the BET method.²/ G. Further, in a molding composition in which silica sol and ethyl silicate are mixed, a small amount of ethyl silicate is added to the silica sol. By adding a lubricant to the molding composition, the rheology can be precisely adjusted. Such a molecular sieve compact includes a Y-type or mordenite-type zeolite. This molecular sieve compact is first mixed and kneaded with the molding composition, then transferred to the extruder in the second step, and calcined at 500 to 800 ° C.
[0009]
However, since the molecular sieve molding is manufactured discontinuously at a very high temperature, there is a disadvantage that the manufacturing cost of the molding is significantly increased. In addition, in a mixture of silica sol and ethyl silicate, there was a problem that a continuous matrix could not be formed because the silica sol was present in a colloidal state. Further, such a solid binder such as silica sol is inferior in dispersibility as compared with a liquid binder, and has a problem that the cost is increased since a lubricant must be added.
[0010]
Further, there is a zeolite molded article using an alkylalkoxysilane oligomer as a binder (for example, see Patent Document 3). Since a liquid alkoxysilane oligomer is used, a continuous method can be adopted, and the firing temperature during molding can be lowered. However, basically, since water is added to and mixed with the reaction mixture, a flammable substance such as an alcohol is generated by hydrolysis of the alkoxysilane oligomer, and the explosion-proof specification line must be provided to prevent ignition or the like due to the flammable substance. This results in increased manufacturing costs. In addition, in the step of drying and removing alcohol by-produced, bubbles and cracks may be generated on the surface of the zeolite molded body due to rapid evaporation of the alcohol, which may cause deformation and shrinkage of the molded body. No binder was desired.
[0011]
[Patent Document 1]
German Patent Application No. 32 31 498
[Patent Document 2]
DE 37 38 916 A1
[Patent Document 3]
JP-T-2002-509788
[0012]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and provides a low-cost zeolite molded article that avoids the conventional problems and a method for producing the same.
[0013]
Means for Solving the Problems and Embodiments of the Invention
The present inventors have conducted intensive studies to achieve the above object, and as a result, by using a silanol group-containing siloxane oligomer as a binder for a zeolite molded body, the moldability of the reaction mixture was improved, and the stability against mechanical stress was improved. It was found that a molded article excellent in the above was obtained.
[0014]
In addition, by using various water-based siloxane oligomers as binders, more uniform treatment can be performed, and by-produced alcohols are extremely small, so that a good molded product with high safety and no shrinkage or deformation can be obtained. Was found.
[0015]
Even more surprisingly, it has been found that the shaped bodies according to the invention can be produced by firing at a temperature of 300 ° C. or lower, in particular at a temperature of 180 to 280 ° C. This is because, despite the fact that the temperature is much lower than before, the molded article of the present invention has high compressive strength, and furthermore, it has been found that the manufacturing cost can be significantly reduced. The present invention has been made.
[0016]
Accordingly, the present invention provides the following zeolite molded article and a method for producing the same.
[I] A zeolite molded article obtained from a reaction mixture containing a zeolite, a plasticizer and a binder, wherein the binder has the following average composition formula (1)
R¹ _mSi (OH)_p(OR²)_qO_{(4-mpq) / 2}(1)
(Where R¹Are the same or different, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R²Represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group or acyl group having 2 to 6 carbon atoms. m, p, and q are 0.5 ≦ m ≦ 1.8, 0 <p ≦ 2.0, 0 ≦ q ≦ 0.5, 0 <p + q ≦ 2.0, and 0.5 ≦ m + p + q ≦ 3.3. It is the number to satisfy. )
A zeolite molded article, characterized by being a silanol group-containing polysiloxane represented by the formula:
[0017]
[II] The binder has the following general formula (2)
R¹ _nSi (OR³)_4-n(2)
(Where R¹Is as described above, and R³Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group or an acyl group having 2 to 6 carbon atoms. n is 0, 1 or 2. )
The zeolite molded product according to [I], which is a silanol group-containing polysiloxane obtained by hydrolyzing at least one kind of hydrolyzable silane represented by the following formula or a partial hydrolyzate thereof.
[0018]
[III] The binder has the following general formula (3)
YR⁴ _aSi (OR³)_3-a(3)
Wherein Y is a nitrogen atom-containing organic group;⁴Is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R³Is as described above. a is 0 or 1. )
And 100 parts by weight of a hydrolyzable silane (A) or a partial hydrolyzate thereof containing a nitrogen atom-containing organic group represented by the following general formula (4):
R⁴ _bSi (OR³)_4-b(4)
(Where R³, R⁴Is as described above. b is 0, 1 or 2. )
Or a polysiloxane obtained by hydrolyzing 5 to 200 parts by weight of a hydrolyzable silane (B) or a partial hydrolyzate thereof.
[0019]
[IV] The binder has the following average composition formula (5)
R⁵ _c(OR³)_dSiO_{(4-cd) / 2}(5)
(Where R⁵Is an alkyl group having 1 to 6 carbon atoms, R³Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group or an acyl group having 2 to 6 carbon atoms, c is 0.75 to 1.5, d is 0.2 to 3, and 0. It is a positive number that satisfies 9 <c + d <4. )
100 parts by weight of an organosilicon compound (C) represented by the following general formula (3)
YR⁴ _aSi (OR³)_3-a(3)
Wherein Y is a nitrogen atom-containing organic group;⁴Is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R³Is as described above. a is 0 or 1. )
Is obtained by co-hydrolyzing and condensing a hydrolyzable silane containing a nitrogen atom-containing organic group or a partial hydrolyzate thereof (A) in an amount of 0.5 to 49 parts by weight in the presence of an organic acid or an inorganic acid. The molded article of zeolite according to [I], wherein
[0020]
[V] A method for producing a molded zeolite, comprising extruding the reaction mixture and then firing the extrudate at a temperature of 180 to 280 ° C.
[0021]
Hereinafter, the present invention will be described in more detail.
The present invention is a molded zeolite obtained from a reaction mixture containing a zeolite, a plasticizer and a binder.
The binder used in the zeolite molded article according to the present invention has the following average composition formula (1) R¹ _mSi (OH)_p(OR²)_qO_{(4-mpq) / 2}(1)
(Where R¹Are the same or different, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R²Represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group or acyl group having 2 to 6 carbon atoms. m, p, and q are 0.5 ≦ m ≦ 1.8, 0 <p ≦ 2.0, 0 ≦ q ≦ 0.5, 0 <p + q ≦ 2.0, and 0.5 ≦ m + p + q ≦ 3.3. It is the number to satisfy. )
(Hereinafter referred to as a binder [I]).
[0022]
Where R¹Is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms.
[0023]
R above¹As the substituted or unsubstituted monovalent hydrocarbon group represented by, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and a decyl group, and an aryl group such as a phenyl group And, those in which part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine and chlorine, for example, trifluoropropyl group, perfluorobutylethyl group, perfluorooctylethyl group, 3-chloropropyl group, 2- (chloromethylphenyl) ethyl group and the like; those substituted with an epoxy functional group such as a glycidyloxy group and an epoxycyclohexyl group, for example,
3-glycidyloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group; (meth) acryl functional groups such as methacryl group and acrylic group Such as 3- (meth) acryloxypropyl group, (meth) acryloxymethyl group, 11- (meth) acryloxyundecyl group; amino group, aminoethylamino group, phenylamino group, dibutylamino Substituted with an amino functional group such as, for example, 3-aminopropyl group, N- (2-aminoethyl) aminopropyl group, 3- (N-phenylamino) propyl group, 3-dibutylaminopropyl group, etc .; mercapto Substituted with a sulfur-containing functional group such as a group or a tetrasulfide group, for example, a 3-mercaptopropyl group or a 2- (4-mercaptopropyl group). A group substituted with an alkyl ether functional group such as a polyoxyalkylene alkyl ether group; for example, a polyoxyethyleneoxypropyl group; a group substituted with an anionic group such as a carboxyl group or a sulfonyl group; -Hydroxycarbonylpropyl group and the like; those substituted with a quaternary ammonium salt structure-containing group and the like, for example, 3-tributylammoniumpropyl group and the like.
[0024]
R²Represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group or acyl group having 2 to 6 carbon atoms. Hydrolyzable group OR²Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a t-butoxy group, an isopropenoxy group, and an acetoxy group. Among these, it is preferable to use a methoxy group, an ethoxy group, and an isopropoxy group from the viewpoint of hydrolysis and condensation reactivity. m, p, and q represent numbers satisfying 0.5 ≦ m ≦ 1.8, 0 <p ≦ 2.0, 0 ≦ q ≦ 0.5, and 0 <p + q ≦ 2.0, respectively. When m is less than 0.5, R¹, The curing reaction is too fast, and cracks are generated in the formed zeolite molded body. If m exceeds 1.8, the number of chain units increases, and the hardness of the molded body decreases. For the same reason, more preferably 0.6 ≦ m ≦ 1.5.
[0025]
Further, in the above formula (1), the silanol group is an essential component, but when p representing the content of the silanol group exceeds 2.0, the polysiloxane itself becomes unstable. Preferably, 0.05 ≦ p ≦ 1.5, especially 0.2 ≦ p ≦ 0.8.
[0026]
Crosslinkable hydrolyzable group OR other than silanol group²May be present, but its abundance q must be 0.5 or less. When q exceeds 0.5, it is easily hydrolyzed in water, and a large amount of alcohol as an organic solvent is by-produced in the system. Preferably, 0 ≦ q ≦ 0.2. Further, p + q representing the total number of crosslinkable substituents must satisfy 0 <p + q ≦ 2.0. If p + q is 0, it will not cure, and if it exceeds 2.0, the molecules will be too small. Preferably, 0.05 ≦ p + q ≦ 1.5, particularly 0.2 ≦ p + q ≦ 1.0.
Note that m + p + q satisfies 0.5 ≦ m + p + q ≦ 3.3, particularly 0.6 ≦ m + p + q ≦ 2.8.
[0027]
The number average molecular weight of this polysiloxane is preferably from 200 to 5,000, particularly preferably from 500 to 2,000.
[0028]
In this case, as the binder, the following general formula (2)
R¹ _nSi (OR³)_4-n(2)
(Where R¹Is as described above, and R³Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group or an acyl group having 2 to 6 carbon atoms. n is 0, 1 or 2. )
And a silanol group-containing polysiloxane (hereinafter, referred to as a binder [II]) obtained by hydrolyzing at least one kind of hydrolyzable silane represented by the following formula or a partial hydrolyzate thereof.
[0029]
In particular, the following general formula (3)
YR⁴ _aSi (OR³)_3-a(3)
Wherein Y is a nitrogen atom-containing organic group;⁴Is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R³Is as described above. a is 0 or 1. )
And 100 parts by weight of a hydrolyzable silane (A) or a partial hydrolyzate thereof containing a nitrogen atom-containing organic group represented by the following general formula (4):
R⁴ _bSi (OR³)_4-b(4)
(Where R³, R⁴Is as described above. b is 0, 1 or 2. )
It is preferable to use a water-soluble polysiloxane (hereinafter, referred to as a binder [III]) obtained by hydrolyzing the hydrolyzable silane (B) represented by the following formula or a partial hydrolyzate thereof in an amount of 5 to 200 parts by weight. .
[0030]
That is, such an organopolysiloxane has water solubility imparted to itself, and is easily dissolved in water. Therefore, when used as a binder for a zeolite molded article, it can be treated more uniformly, and can be a by-product. Since there is no alcohol to be formed, a good molded body can be obtained without deformation such as shrinkage.
[0031]
More specifically, the hydrolyzable silane (A) containing a nitrogen atom-containing organic group used for obtaining the water-soluble polysiloxane is a component used to make the system water-soluble, and has the following general formula (3) ), And one or more of them are appropriately selected and used. Moreover, the partial hydrolyzate can also be used.
[0032]
YR⁴ _aSi (OR³)_3-a(3)
Wherein Y is a nitrogen atom-containing organic group;⁴Is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R³Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group or an acyl group having 2 to 6 carbon atoms. a is 0 or 1. )
[0033]
Where R³As the alkyl group, alkenyl group and acyl group of²This is the same as that exemplified above. R⁴Unsubstituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, etc. Examples thereof include an alkenyl group such as an alkyl group, an allyl group, a 5-hexenyl group, and a 9-decenyl group, and an aryl group such as a phenyl group. Of these, a methyl group, a propyl group, a hexyl group, and a phenyl group are preferable.
[0034]
Y is a nitrogen atom-containing organic group, for example, those represented by the following formulas (6) to (10).
[0035]
Embedded image

(Where R⁶, R⁷, R¹⁰~ R¹⁷Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms;⁶And R⁷, R¹⁰And R¹¹And R¹², R^ThirteenAnd R¹⁴, R^FifteenAnd R¹⁶And R¹⁷May be the same or different from each other. R represents a halogen atom. R⁸, R⁹Is a divalent hydrocarbon group having 1 to 8 carbon atoms;⁸And R⁹May be the same or different from each other. p is 0 or an integer of 1-3. )
[0036]
The monovalent hydrocarbon group having 1 to 8 carbon atoms includes, for example, an alkyl group, an aryl group, and the like.⁴And the same as those exemplified above. Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms include an alkylene group.
[0037]
Specific examples of Y include those represented by the following formula.
H₂NCH₂-, H (CH₃) NCH₂-, H₂NCH₂CH₂-, H (CH₃) NCH₂CH₂-, H₂NCH₂CH₂CH₂-, H (CH₃) NCH₂CH₂CH₂−, (CH₃)₂NCH₂CH₂CH₂-, H₂NCH₂CH₂HNCH₂CH₂CH₂-, H (CH₃) NCH₂CH₂HNCH₂CH₂CH₂−, (CH₃)₂NCH₂CH₂HNCH₂CH₂CH₂-, H₂NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂-, H (CH₃) NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂-, Cl⁻(CH₃)₃N⁺CH₂CH₂CH₂-, Cl⁻(CH₃)₂(C₆H₅CH₂) N⁺CH₂CH₂CH₂−,
Embedded image

[0038]
Of these, the following are preferred.
H₂NCH₂CH₂HNCH₂CH₂CH₂−,
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[0039]
In the formula (3), a is 0 or 1.
[0040]
Examples of the hydrolyzable silane (A) containing a nitrogen atom-containing organic group of the above formula (3) include the following.
H₂NCH₂Si (OCH₃)₃, H₂NCH₂Si (OCH₂CH₃)₃, H₂NCH₂SiCH₃(OCH₃)₂, H₂NCH₂SiCH₃(OCH₂CH₃)₂, H₂NCH₂CH₂Si (OCH₃)₃, H₂NCH₂CH₂Si (OCH₂CH₃)₃, H₂NCH₂CH₂SiCH₃(OCH₃)₂, H₂NCH₂CH₂SiCH₃(OCH₂CH₃)₂, H₂NCH₂CH₂CH₂Si (OCH₃)₃, H₂NCH₂CH₂CH₂Si (OCH₂CH₃)₃, H₂NCH₂CH₂CH₂SiCH₃(OCH₃)₂, H₂NCH₂CH₂CH₂SiCH₃(OCH₂CH₃)₂, H (CH₃) NCH₂CH₂CH₂Si (OCH₃)₃, H (CH₃) NCH₂CH₂CH₂Si (OCH₂CH₃)₃, H (CH₃) NCH₂CH₂CH₂SiCH₃(OCH₃)₂, H (CH₃) NCH₂CH₂CH₂SiCH₃(OCH₂CH₃)₂, (CH₃)₂NCH₂CH₂CH₂Si (OCH₃)₃, (CH₃)₂NCH₂CH₂CH₂Si (OCH₂CH₃)₃, Cl⁻(CH₃)₃N⁺CH₂CH₂CH₂Si (OCH₃)₃, Cl⁻(CH₃)₃N⁺CH₂CH₂CH₂Si (OCH₂CH₃)₃, Cl⁻(CH₃)₂(C₆H₅CH₂) N⁺CH₂CH₂CH₂Si (OCH₃)₃, Cl⁻(CH₃)₂(C₆H₅CH₂) N⁺CH₂CH₂CH₂Si (OCH₂CH₃)₃, H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃, H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₂CH₃)₃, H₂NCH₂CH₂HNCH₂CH₂CH₂SiCH₃(OCH₃)₂, H₂NCH₂CH₂HNCH₂CH₂CH₂SiCH₃(OCH₂CH₃)₂, H₂NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃, H₂NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂Si (OCH₂CH₃)₃, H₂NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂SiCH₃(OCH₃)₂, H₂NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂SiCH₃(OCH₂CH₃)₂,
[0041]
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[0042]
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[0043]
Of these, particularly preferred is H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃, H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₂CH₃)₃And these partial hydrolysates may be used.
[0044]
On the other hand, the hydrolyzable silane (B) used by being mixed with the hydrolyzable silane (A) or a partial hydrolyzate thereof is represented by the following general formula (4). The above can be used in combination, and a partial hydrolyzate thereof may be used.
R⁴ _bSi (OR³)_4-b(4)
Where R³, R⁴Is the same as above. b is 0, 1 or 2.
[0045]
The following can be exemplified as the hydrolyzable silane (B) of the formula (4).
Si (OCH₃)₄, Si (OCH₂CH₃)₄, Si (OCH₂CH₂CH₃)₄, Si (OCH₂CH₂CH₂CH₃)₄, CH₃Si (OCH₃)₃, CH₃Si (OCH₂CH₃)₃, CH₃Si (OCH₂CH₂CH₃)₃, CH₃Si (OCH₂CH₂CH₂CH₃)₃, (CH₃)₂Si (OCH₃)₂, (CH₃)₂Si (OCH₂CH₃)₂, (CH₃)₂Si (OCH₂CH₂CH₃)₂, (CH₃)₂Si (OCH₂CH₂CH₂CH₃)₂,
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[0046]
Of these, Si (OCH₃)₄, Si (OCH₂CH₃)₄, CH₃Si (OCH₃)₃, CH₃Si (OCH₂CH₃)₃And their partial hydrolysates.
[0047]
When the hydrolyzable silane (B) of the formula (4) or the partial hydrolyzate thereof is used in combination with the hydrolyzable silane (A) or the partial hydrolyzate thereof containing the nitrogen-containing organic group, the mixture is used. The ratio is a ratio of 5 to 200 parts by weight of the hydrolyzable silane (B) or its partial hydrolyzate to 100 parts by weight of the hydrolyzable silane (A) or its partial hydrolyzate containing a nitrogen atom-containing organic group. The amount of the hydrolyzable silane (B) or a partial hydrolyzate thereof is more preferably 10 to 150 parts by weight. If this amount exceeds 200 parts by weight, the stability of the liquid may be deteriorated.
[0048]
When the polysiloxane of the present invention is obtained by hydrolysis using the hydrolyzable silane (A), (B) or a partial hydrolyzate thereof, water is mainly used as a solvent. And alcohols, esters, ketones, and glycols, which are organic solvents that dissolve in water, can be used in the form of being added to water. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol and 2-propyl alcohol; esters such as methyl acetate, ethyl acetate and ethyl acetoacetate; ketones such as acetone and methyl ethyl ketone; glycerin and diethylene glycol. And the like.
[0049]
The amount of the solvent is preferably 400 to 5000 parts by weight based on 100 parts by weight of the raw material silane. More preferably, it is 1000 to 3000 parts by weight. If the amount of the solvent is less than 400 parts by weight, the reaction may proceed too much and the system may not be uniform. In addition, the storage stability of the solution may be deteriorated. On the other hand, if it is more than 5000 parts by weight, there may be a case where it is economically disadvantageous.
[0050]
Further, the amount of water in the solvent is preferably 5 to 50 in a molar ratio of water / raw material silane. When the molar ratio is less than 5, hydrolysis does not easily proceed completely, and the stability of the solution may be deteriorated. On the other hand, if it exceeds 50, economically disadvantageous cases may occur.
[0051]
As the reaction method, (1) a method in which the mixed silane is dropped into water or an organic solvent containing water in an amount larger than necessary for hydrolysis, and (2) water is dropped into the mixed silane or the mixed silane containing the organic solvent. (3) The hydrolyzable silane (B) or a partial hydrolyzate thereof is dropped into water or an organic solvent containing water in an amount larger than necessary for hydrolysis, and then the nitrogen-containing organic group is removed. A method of dropping the contained hydrolyzable silane (A) or a partial hydrolyzate thereof, and (4) converting the hydrolyzable silane (A) or a partial hydrolyzate thereof containing a nitrogen atom-containing organic group into water or hydrolyzed. Dropping into an organic solvent containing water in an amount larger than necessary, followed by dropping a hydrolyzable silane (B) or a partial hydrolyzate thereof, may be mentioned. From, in particular, the reaction method (1) preferred.
[0052]
The polysiloxane is obtained in the form of an aqueous solution, and water is added or removed as needed to obtain 10 to 2,000 parts by weight of water, preferably 10 to 1 part by weight of water, based on 100 parts by weight of the polysiloxane. It is preferable to form a polysiloxane aqueous solution by adjusting the ratio to 2,000 parts by weight. In this case, if the amount of water is less than 10 parts by weight, the storage stability of the polysiloxane itself may deteriorate. On the other hand, if the amount is more than 2,000 parts by weight, the amount of the polysiloxane to be added increases, which is not preferable in terms of cost.
[0053]
The number average molecular weight of the water-soluble polysiloxane is preferably from 200 to 3,000, particularly preferably from 500 to 2,000.
[0054]
Further, as the binder [IV], the following average composition formula (5)
R⁵ _c(OR³)_dSiO_{(4-cd) / 2}(5)
(Where R⁵Is an alkyl group having 1 to 6 carbon atoms, R³Is as described above. c is 0.75 to 1.5, d is 0.2 to 3, and is a positive number satisfying 0.9 <c + d <4. )
100 parts by weight of an organosilicon compound (C) represented by the following general formula (3)
YR⁴ _aSi (OR³)_3-a(3)
(Where Y, R³, R⁴, A are as described above. )
Is obtained by co-hydrolyzing and condensing a hydrolyzable silane containing a nitrogen atom-containing organic group or a partial hydrolyzate thereof (A) in an amount of 0.5 to 49 parts by weight in the presence of an organic acid or an inorganic acid. The polysiloxane itself is also given water solubility and easily dissolves in water, so it can be treated more uniformly when used as a binder for zeolite moldings, and shrinks because it produces as little by-product alcohols as possible. A good molded body can be obtained without deformation such as
[0055]
Here, in equation (5), R³Is the same as described above. R⁵Is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, and a methyl group is particularly preferable.
[0056]
The organooxy group-containing siloxane of the formula (5) is, for example, as a specific example,
CH₃Si (OCH₃)₃, CH₃Si (OC₂H₅)₃, CH₃Si (OCH (CH₃)₂)₃, CH₃CH₂Si (OCH₃)₃, CH₃CH₂Si (OC₂H₅)₃, CH₃CH₂Si (OCH (CH₃)₂)₃, C₃H₆Si (OCH₃)₃, C₃H₆Si (OC₂H₅)₃, C₃H₆Si (OCH (CH₃)₂)₃, C₄H₉Si (OCH₃)₃, C₄H₉Si (OC₂H₅)₃, C₄H₉Si (OCH (CH₃)₂)₃, C₅H₁₁Si (OCH₃)₃, C₅H₁₁Si (OC₂H₅)₃, C₅H₁₁Si (OCH (CH₃)₂)₃, C₆H_ThirteenSi (OCH₃)₃, C₆H_ThirteenSi (OC₂H₅)₃, C₆H_ThirteenSi (OCH (CH₃)₂)₃Can be obtained by partially hydrolyzing and condensing an alkoxy-containing siloxane such as
These may be hydrolyzed and condensed singly, or may be hydrolyzed and condensed with a mixture of two or more types, or a partially hydrolyzed product of a mixed silane may be used.
[0057]
In this case, the number of silicon atoms in the partial hydrolyzate is preferably 2 to 10, particularly preferably 2 to 4. Further, the component (C) may be obtained by reacting an alkyltrichlorosilane having 1 to 6 carbon atoms with methanol or ethanol in water. Also in this case, the number of silicon atoms is preferably 2 to 6, particularly 2 to 4, and at 25 ° C., 300 mm²/ S having a viscosity of not more than 1 / s, especially 1 to 100 mm²/ S is preferred.
[0058]
The hydrolyzable silane (A) containing a nitrogen atom-containing organic group of the formula (3) is as described above.
[0059]
Specific examples of such a hydrolyzable silane containing a nitrogen atom-containing organic group of the above formula (3) include H₂N (CH₂)₂Si (OCH₃)₃, H₂N (CH₂)₂Si (OCH₂CH₃)₃, H₂N (CH₂)₃Si (OCH₃)₃, H₂N (CH₂)₃Si (OCH₂CH₃)₃, CH₃NH (CH₂)₃Si (OCH₃)₃, CH₃NH (CH₂)₃Si (OCH₂CH₃)₃, CH₃NH (CH₂)₅Si (OCH₃)₃, CH₃NH (CH₂)₅Si (OCH₂CH₃)₃, H₂N (CH₂)₂NH (CH₂)₃Si (OCH₃)₃, H₂N (CH₂)₂NH (CH₂)₃Si (OCH₂CH₃)₃, CH₃NH (CH₂)₂NH (CH₂)₃Si (OCH₃)₃, CH₃NH (CH₂)₂NH (CH₂)₃Si (OCH₂CH₃)₃, C₄H₉NH (CH₂)₂NH (CH₂)₃Si (OCH₃)₃, C₄H₉NH (CH₂)₂NH (CH₂)₃Si (OCH₂CH₃)₃, H₂N (CH₂)₂SiCH₃(OCH₃)₂, H₂N (CH₂)₂SiCH₃(OCH₂CH₃)₂, H₂N (CH₂)₃SiCH₃(OCH₃)₂, H₂N (CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH (CH₂)₃SiCH₃(OCH₃)₂, CH₃NH (CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH (CH₂)₅SiCH₃(OCH₃)₂, CH₃NH (CH₂)₅SiCH₃(OCH₂CH₃)₂, H₂N (CH₂)₂NH (CH₂)₃SiCH₃(OCH₃)₂, H₂N (CH₂)₂NH (CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH (CH₂)₂NH (CH₂)₃SiCH₃(OCH₃)₂, CH₃NH (CH₂)₂NH (CH₂)₃SiCH₃(OCH₂CH₃)₂, C₄H₉NH (CH₂)₂NH (CH₂)₃SiCH₃(OCH₃)₂, C₄H₉NH (CH₂)₂NH (CH₂)₃SiCH₃(OCH₂CH₃)₂And the like.
[0060]
Among them, particularly, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-Aminopropylmethyldiethoxysilane and the like are preferably used.
[0061]
The proportion of the components (C) and (A) used is 0.5 to 49 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the component (C). If the amount of the component (A) is less than 0.5 parts by weight, the water solubility may be weakened, and the stability of the aqueous solution may be poor. If the amount of the component (A) exceeds 49 parts by weight, the cost may be disadvantageous.
[0062]
In terms of molar conversion, it is preferable to use the Si atom of the component (A) in an amount of 0.01 to 0.3 mol, particularly 0.05 to 0.2 mol, per 1 mol of the Si atom of the component (C). .
[0063]
In order to produce a water-soluble polysiloxane using these components (C) and (A), co-hydrolysis may be performed in the presence of an organic acid or an inorganic acid. In this case, first, the component (C) is hydrolyzed in the presence of an organic acid or an inorganic acid, and the hydrolyzate of the component (C) is mixed with the component (A). Further hydrolysis is preferred.
[0064]
First, the organic acid and the inorganic acid used in hydrolyzing the component (C) are selected from, for example, hydrochloric acid, sulfuric acid, methanesulfonic acid, formic acid, acetic acid, propionic acid, citric acid, oxalic acid and maleic acid. At least one acid is used, and acetic acid and propionic acid are particularly preferred. The amount of the acid is preferably 2 to 40 parts by weight, particularly preferably 3 to 15 parts by weight, per 100 parts by weight of the component (C). If the amount of the acid used is too small, the progress of hydrolysis is slow, and the stability of the aqueous solution of the composition may be deteriorated.
[0065]
The hydrolysis is preferably performed in a state of being appropriately diluted with a solvent. As the solvent, an alcohol-based solvent is preferable, and particularly, methanol, ethanol, isopropyl alcohol, and tert-butyl alcohol are preferable. The amount of the solvent to be used is preferably 50 to 300 parts by weight, particularly preferably 70 to 200 parts by weight, per 100 parts by weight of the component (C). If the amount of the solvent is less than 50 parts by weight, the condensation may proceed too much, and if it exceeds 300 parts by weight, the hydrolysis may take a long time.
[0066]
The amount of water added to hydrolyze the component (C) is preferably 0.5 to 4 mol, and more preferably 1 to 3 mol, per 1 mol of the component (C). If the amount of water added is less than 0.5 mol, a large amount of alkoxy groups may remain, and if it exceeds 4 mol, condensation may proceed too much. The reaction conditions for hydrolyzing the component (C) are preferably a reaction temperature of 10 to 40 ° C, particularly preferably 20 to 30 ° C, and the hydrolysis time is preferably 1 to 3 hours.
[0067]
The hydrolyzate of the component (C) thus obtained is reacted with the component (A). The reaction conditions are preferably a reaction temperature of 60 to 100 ° C. and a reaction time of 1 to 3 hours. After the completion of the reaction, the temperature is raised to the boiling point of the solvent or higher, and the alcohol solvent is distilled off. In this case, it is preferable to distill off the content of the entire alcohol (alcohol as a reaction solvent and alcohol as a by-product) in the system to 30% by weight or less, particularly 10% by weight or less. When a large amount of alcohol is contained, when diluted with water, it may become cloudy or gel, and storage stability may be reduced. The polysiloxane that can be produced by the above method has a viscosity at 25 ° C. of 5 to 2,000 mm.²/ S, especially 50 to 500 mm²/ S. If the viscosity is too high, workability and storage stability may decrease, or solubility in water may decrease.
[0068]
The thus obtained water-soluble polysiloxane is preferably used as a binder, and a water-soluble polysiloxane solution obtained by uniformly mixing 0.1 to 20% by weight, particularly preferably 1 to 10% by weight, with water is used as a binder. desirable. At this time, if the concentration of the water-soluble polysiloxane is less than 0.1% by weight, the processing efficiency may be deteriorated. On the other hand, if it is more than 20% by weight, it is disadvantageous in terms of cost and the stability of the aqueous solution may be deteriorated.
[0069]
The number average molecular weight of the water-soluble polysiloxane is preferably from 200 to 5,000, particularly preferably from 500 to 2,000.
[0070]
As described above, the zeolite molded article of the present invention is obtained from a reaction mixture containing the binder [I], [II], [III] or [IV], zeolite, and a plasticizer, In this case, the zeolite used in the present invention is preferably selected from zeolite 3A, zeolite 4A, zeolite 5A, zeolite X, and an arbitrary mixture thereof.
[0071]
The plasticizer used in the present invention is soluble in water. As the plasticizer, cellulose ether such as methylcellulose, polysaccharide, polyvinyl alcohol, starch, or a mixture thereof arbitrarily can be used.
[0072]
Further, if necessary, a rheology control can be carried out by adding a wax emulsion and / or a fatty acid mixture as a lubricant to the reaction mixture.
[0073]
The reaction mixture for producing the shaped bodies according to the invention comprises a binder having a content of 1 to 35% by weight, a zeolite having a content of 40 to 90% by weight and a plasticizer having a content of 5 to 40% by weight, based on the total reaction mixture. It is preferable to include As a result, a molded article having excellent adsorption, catalyst and mechanical properties can be obtained.
[0074]
In this case, when the binders [I] and [II] are used, the content is preferably 2 to 25% by weight, particularly 5 to 20% by weight, so that optimal deformation characteristics can be obtained during molding. In addition, it is possible to obtain a molded body having achieved the maximum compressive strength value. When the binders [III] and [IV] are used, the amount is preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight. If the amount is too small, the processing efficiency will be poor, and if it is too large, the stability of the aqueous solution may be poor.
[0075]
The more preferred amount of the zeolite is 40 to 60% by weight, and the more preferred amount of the plasticizer is 5 to 15% by weight.
[0076]
Here, the reaction mixture for producing the molded article of the present invention is, for example, when methyl cellulose is contained as water and a plasticizer, if the content of the plasticizer is small, the extrudate molded by the extruder has dimensional stability. May be inferior. 400 cells / inch²(About 62 cells / cm²In the case of extrusion molding of a square honeycomb formed article according to the present invention having the above-mentioned (1), the content of methylcellulose is about 10% by weight or more, more preferably about 15% by weight or more based on the amount of water added. As a result, the flow rate limit is increased, the suction pressure loss of the extrudate is significantly reduced, and an extrudate having excellent dimensional stability is obtained. As a result, the pressure drop along the die is reduced and the back pressure length in the extruder is reduced. As a result, less shear is exerted on the pressure accumulation zone of the extruder screw, less heat is dissipated and heating of the reaction mixture is avoided.
[0077]
The amount of water is 0 to 54% by weight, preferably 5 to 40% by weight, particularly 10 to 35% by weight.
[0078]
As described above, the wax emulsion and / or the fatty acid mixture can be blended as a lubricant, but the blending amount is 0 to 20% by weight, particularly 0 to 10% by weight. In this case, the binders [I] and [II] simultaneously act as lubricants, and the reaction mixture using these binders [I] and [II] has low flow limit and suction pressure loss during the production process, The moldability of the reaction mixture is significantly improved and no additional lubricant is required.
[0079]
The zeolite molded product of the reaction mixture of the present invention containing a zeolite, a plasticizer and a binder is produced by the following steps.
First step: Preparation of reaction mixture of zeolite, plasticizer and binder
Step 2: Extrusion of the reaction mixture
Third step: firing of the extrudate at a temperature of 180 to 280 ° C
[0080]
A substantial advantage of the manufacturing method of the present invention is that the calcination is performed in a temperature range of about 180-280 ° C. Both commercially available fixed beds of zeolite in bulk form and shaped bodies described in the prior art are calcined at a temperature of at least 400 ° C. or higher, generally 500-700 ° C. Since these materials have a high sintering temperature, they consume a very large amount of energy when manufacturing bulk products and molded products. On the other hand, in the production method of the present invention, since it is not necessary to perform firing at such a high temperature, the production cost of the molded body can be significantly reduced. In addition, since there are few alkoxy groups in the polysiloxane as a binder, there is virtually no flammable alcohol by-produced by the reaction, so there is no need to use explosion-proof equipment, etc., further reducing costs. It has become. The molded article of the present invention fired in the above temperature range also has excellent mechanical and adsorption characteristics.
[0081]
The first and second steps of the production method of the present invention are preferably performed continuously. That is, the blending of each component and the molding of the molding composition are continuously performed in one step. For extrusion molding, a single screw or twin screw extruder can be employed. For example, when a twin screw extruder having a screw rotating in the same direction is used, a high-density compound 2 having a screw rotating in the same direction is used. The screw extruder functions as a mixing device and a pressure generator for extruding the honeycomb-shaped extrudate. Among the components of the reaction mixture, the pulverulent components of the plasticizer and the zeolite are respectively supplied via a gravity drop meter, and the liquid components of water and the binder are supplied via a membrane or by a piston pump. In the continuous production of shaped bodies according to the method of the invention, the profitability over the whole process can be significantly increased. In addition, the operation of moving the kneaded reaction mixture to the extruder can be omitted.
[0082]
In the third step of the method of the present invention, calcination is performed at a temperature of 180 to 280C, preferably 200 to 250C, more preferably 210 to 235C. When sintering is performed in this temperature range, a molded body having extremely high compressive strength can be obtained as compared with the case where sintering is performed in other temperature ranges. In addition, a molded article having excellent adsorption and catalytic properties can be obtained. The additional drying of the extrudate can be performed between the second and third steps of the method of the present invention.
[0083]
Complete cross-linking of the silicone matrix is achieved in these temperature ranges. A maximum number of covalent crosslinks, which are also covalently bound to zeolites, form during the firing step. When the firing temperature exceeds 280 ° C., the break-off of methyl groups and nitrogen-containing organic groups from the binder starts, and as a result, the formed matrix is weakened and the compressive strength of the molded article according to the present invention may be reduced. is there. On the other hand, at a temperature lower than 180 ° C., crosslinking of the binder and formation of a covalent bond only slightly occur, which is not preferable.
[0084]
The compression strength of the molded article according to the present invention is about 20 N / mm.²Above, preferably about 30 N / mm²Above, more preferably about 50 N / mm²That is all. The molded article according to the present invention can have the maximum compressive strength by firing in a temperature range of 180 to 280 ° C.
[0085]
The compact of the present invention has several times higher compressive strength than viscous materials such as attapulgite or zeolite pellets produced using methyl orthosilicate as a binder. The high compressive strength that can be achieved with the shaped bodies according to the invention is advantageous because the shrinkage that occurs during further heat treatment of the shaped bodies and the intrinsic stresses induced by this shrinkage in the extrudate are compensated for. Thereby, cracks and the like in the molded article of the present invention are avoided, and a molded article having excellent surface quality and mechanical properties can be obtained.
[0086]
Further, as compared with a fixed bed of zeolite in a bulk form, especially in the case of a honeycomb-shaped extrudate, the adsorptivity is remarkably improved due to a large surface area. For example, a measurement of the increase in water of adsorption capacity in a climate cabinet (climate @ cabinet) at a temperature of 23 ° C. and a relative humidity of 10% shows that after 3 hours using a type 4A zeolite, the weight of the molded body is 13% by weight. % To 17% by weight or more.
[0087]
Furthermore, the shaped bodies according to the invention have an abrasion resistance of more than 99%. The abrasion resistance is a value measured as follows in accordance with the American Penney Attrition Test (US Pat. No. 2,973,327 to WJ Mitchell et al., 1956). is there. 3 g of a completely cylindrical zeolite-based pellet (D = 5 mm, L / D = 1.5) is introduced into a plastic container and closed. The vessel is vibrated for 20 minutes at a frequency of 60 scale units on a Retsch model 3D vibrating sieve. To simulate increased wear and true load, the plastic container further includes a piece of Pennig coin. The resulting worn material is then separated on a 500 μm mesh screen at a frequency of 20 scale units for 2 minutes.
[0088]
The molded article of the present invention can be manufactured in the form of a tube, a cylinder, a bead, a tablet, a ring, a sheet, or the like, but preferably has a honeycomb shape. The honeycomb-shaped molded body has a high cell density, has an extremely large surface area as compared with other molded bodies, for example, in the form of a sheet, and the catalyst and absorption characteristics of the molded body of the present invention, in particular, the absorption are remarkably improved. Is done.
[0089]
The molded zeolite according to the present invention can be manufactured at extremely low cost, has high stability against mechanical stress, and can be used for various applications.
[0090]
In addition, since the clogging or breakage of the molded product device or the downstream side of the machine due to abrasion, which occurs particularly in a bulk fixed bed of zeolite, does not occur, it is suitable for long-term use in industrial equipment. Furthermore, no change in the zeolite material occurs in the bulk fixed bed, the operating costs of the apparatus are reduced, and the use of the shaped bodies according to the invention makes it possible to achieve a very low pressure loss.
[0091]
The molded zeolite of the present invention can be used for a wide range of applications such as drying and refining of gas and liquid, refining, purification and separation. The compacts used can be regenerated by either an alternating pressing process, heat treatment, or washing and drying with a solvent.
[0092]
Further, the zeolite molded article of the present invention can be used, for example, in a rotary absorber (Rotor Absorber) to remove residual moisture. Furthermore, the zeolite compact of the present invention can be used for drying compressed air. Moisture entering the compressed air system with fresh air is condensed during the compression / pressure relief and can corrode equipment etc. and impair the functioning of the system. In this case, by incorporating the molded zeolite according to the present invention as an absorbent, water can be removed from an air brake system, a pneumatic drive and control device, and thereby corrosion can be suppressed.
[0093]
Further, the molded article of the present invention can be used for refrigerant drying in a CFC-free refrigeration apparatus. In this case, since the capacity of the molded article of the present invention is 10 to 15 years, regeneration of the molded article is not necessary. If the refrigeration unit is closed during assembly, moisture is regularly introduced and the disadvantages caused by using the shaped bodies according to the invention for drying the refrigerant are avoided.
[0094]
Drying and recycling of the used refrigerant can be performed by using the molded article of the present invention as an absorbent. Regeneration of the absorbent can be performed by heat treatment.
[0095]
The shaped bodies according to the invention can also be used for the desulfurization (odor control) of liquid hydrocarbons as spray can high pressure gas (eg butane).
[0096]
Furthermore, the shaped bodies according to the invention can be used in air separation devices, absorb nitrogen and result, for example, in oxygen enrichment of the intake air. Regeneration can be performed by heat treatment.
[0097]
The moldings according to the invention can also be used in air conditioning devices. In this case, the absorption and vaporization enthalpies are used for heat generation or cooling.
[0098]
The shaped body according to the present invention can be used as an ion exchanger in a water softening device. In this case, the desired effect is achieved by calcium-sodium exchange.
[0099]
【The invention's effect】
By using the silanol group-containing polysiloxane or the water-soluble polysiloxane according to the present invention as a binder, it is possible to obtain a zeolite compact having high compressive strength even when calcined at a low temperature. In addition, since there is no or very small amount of alcohol by-produced, safety is high and explosion-proof equipment is not required, which reduces costs. Absent.
[0100]
【Example】
Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples,% indicates% by weight, and part indicates parts by weight.
[0101]
[Synthesis Example 1] Production of silanol group-containing polysiloxane 1
408 g (3.0 mol) of methyltrimethoxysilane and 300 g of toluene were charged into a 2 L flask, and 97 g of a 2% hydrochloric acid aqueous solution was dropped and mixed over 1 hour while stirring at 40 ° C., and hydrolyzed. Further, the mixture was aged while stirring at 40 ° C. for 1 hour. Next, a water washing operation of adding 100 g of a 10% aqueous sodium sulfate solution, stirring the mixture for 10 minutes, and then allowing it to stand to separate and remove the aqueous layer was repeated three times. From the obtained silanol group-containing polysiloxane, methanol was distilled off under reduced pressure at 50 ° C. and 6.7 kPa, and then filtered to obtain a silanol group-containing polysiloxane. As a result of GPC measurement, the number average molecular weight of this silanol group-containing polysiloxane was 2,000. When the amount of the silanol group was determined, the content was 4.2% (based on the silanol group-containing polysiloxane). When the amount of the methoxy group was determined by the cracking method, the content was 1.4% (based on the silanol group-containing polysiloxane). Siloxane). From the above, it was recognized that the obtained silanol group-containing polysiloxane 1 can be represented by the following composition.
(CH₃)_1.0Si (OH)_0.17(OCH₃)_0.03O_1.40
[0102]
[Synthesis Example 2] Production of silanol group-containing polysiloxane 2
408 g (3.0 mol) of methyltrimethoxysilane was charged into a 2 L flask, 786 g of water was added at 0 ° C. under a nitrogen atmosphere and mixed well, and 216 g of a 0.05 N hydrochloric acid aqueous solution was added under ice cooling over 40 minutes. After completion of the dropwise addition, the mixture was stirred at 10 ° C. or lower for 1 hour and further at room temperature for 2 hours to complete the hydrolysis reaction. Next, the produced methanol and water were distilled off under reduced pressure at 70 ° C. and 8.0 kPa, and the process was continued until no methanol was detected in the distillate. At the time of the initial concentration of 88%, methanol was not detected, and at the same time, the solution began to become cloudy. When the solution was allowed to stand for one day, the solution was separated into two layers, and the silanol group-containing polysiloxane precipitated. Water was separated from the silanol group-containing polysiloxane, and the content of the silanol group and the number average molecular weight were measured. The content was 8.2% (based on the silanol group-containing polysiloxane), and the number average molecular weight was 1,800. Was. As a result of infrared absorption spectrum analysis, since no methoxy group remained, it was recognized that the obtained silanol group-containing polysiloxane 2 could be represented by the following composition.
(CH₃)_1.0Si (OH)_0.34O_1.33
[0103]
[Synthesis Example 3] Production of water-soluble polysiloxane 1
246 g (13.7 mol) of water was put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler and stirred. Where H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃44.4 g (0.2 mol) and Si (OCH₂CH₃)₄When a mixture of 20.8 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature increased from 25 ° C to 56 ° C. Further, the mixture was heated to 60 to 70 ° C. in an oil bath and stirred for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and by-produced methanol and ethanol were removed to obtain 250 g of water-soluble polysiloxane 1. The nonvolatile content (105 ° C./3 hours) of this product was 14.9%. The number average molecular weight was 1,800.
[0104]
[Synthesis Example 4] Production of water-soluble polysiloxane 2
278 g (15.4 mol) of water was put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler and stirred. Here H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃55.6 g (0.25 mol) and Si (OCH₂CH₃)₄When a mixture of 10.4 g (0.05 mol) was added dropwise at room temperature over 10 minutes, the internal temperature increased from 27 ° C to 49 ° C. Further, the mixture was heated to 60 to 70 ° C. in an oil bath and stirred for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 98 ° C., and by-produced methanol and ethanol were removed to obtain 274 g of water-soluble polysiloxane 2. The nonvolatile content (105 ° C./3 hours) of this product was 15.1%. The number average molecular weight was 1,600.
[0105]
[Synthesis Example 5] Production of water-soluble polysiloxane 3
202 g (11.2 mol) of water was put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler, and mixed by stirring. Here H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃33.3 g (0.15 mol) and Si (OCH₂CH₃)₄When a mixture of 31.2 g (0.15 mol) was added dropwise over 10 minutes at room temperature, the internal temperature increased from 25 ° C to 51 ° C. Further, the mixture was heated to 60 to 70 ° C. in an oil bath and stirred for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and by-produced methanol and ethanol were removed to obtain 210 g of water-soluble polysiloxane 3. The nonvolatile content (105 ° C./3 hours) of this product was 15.3%. The number average molecular weight was 1,100.
[0106]
[Synthesis Example 6] Production of water-soluble polysiloxane 4
308 g (17.1 mol) of water was put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler, and mixed by stirring. Here H₂NCH₂CH₂HNCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃53.1 g (0.2 mol) and Si (OCH₃)₄When a mixture of 15.2 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature increased from 28 ° C to 53 ° C. Further, the mixture was heated to 60 to 70 ° C. in an oil bath and stirred for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol produced as a by-product was removed to obtain 300 g of water-soluble polysiloxane 4. The nonvolatile content (105 ° C./3 hours) of this product was 15.4%. The number average molecular weight was 2,000.
[0107]
[Synthesis Example 7] Production of water-soluble polysiloxane 5
253 g (14.1 mol) of water was put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler, and mixed by stirring. Here H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃44.4 g (0.2 mol) and CH₃Si (OCH₃)₃When a mixture of 13.6 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature increased from 26 ° C to 42 ° C. Further, the mixture was heated to 60 to 70 ° C. in an oil bath and stirred for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and methanol as a by-product was removed to obtain 244 g of water-soluble polysiloxane 5. The nonvolatile content (105 ° C./3 hours) of this product was 15.6%. The number average molecular weight was 1,600.
[0108]
[Synthesis Example 8] Production of water-soluble polysiloxane 6
241 g (13.4 mol) of water was put into a 500 ml reactor equipped with a stirrer, a thermometer and a cooler, and mixed by stirring. Here H₂NCH₂CH₂HNCH₂CH₂CH₂Si (OCH₃)₃44.4 g (0.2 mol), Si (OCH₂CH₃)₄18.7 g (0.09 mol) and CH₃Si (OCH₃)₃When a mixture of 1.4 g (0.01 mol) was added dropwise at room temperature over 10 minutes, the internal temperature increased from 26 ° C. to 49 ° C. Further, the mixture was heated to 60 to 70 ° C. in an oil bath and stirred for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 99 ° C., and by-produced methanol and ethanol were removed to obtain 241 g of water-soluble polysiloxane 6. The nonvolatile content (105 ° C./3 hours) was 15.7%. The number average molecular weight was 1,500.
[0109]
[Synthesis Example 9] Production of water-soluble polysiloxane 7
85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer), 154 g of methanol and 5.1 g of acetic acid are placed in a 500 ml four-necked flask equipped with a condenser, a thermometer and a dropping funnel, and are stirred. Then, 6.8 g (0.37 mol) of water was added to the mixture, and the mixture was stirred at 25 ° C. for 2 hours. There, 8.9 g (0.04 mol) of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added dropwise. Thereafter, the mixture was heated to the reflux temperature of methanol and reacted for 1 hour. Then, methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C.²/ S of a pale yellow transparent solution (81 g) (number average molecular weight 1,100). This was diluted with water to 15% by weight to obtain a light yellow transparent water-soluble polysiloxane 7.
[0110]
[Synthesis Example 10] Production of water-soluble polysiloxane 8
The reaction was performed in the same manner as in Synthesis Example 9 except that N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was changed to 17.7 g (0.08 mol) of 3-aminopropyltriethoxysilane, and the viscosity was 220 mm.²/ S of 90 g of a pale yellow transparent solution (number average molecular weight 1,300). This was diluted with water to 15% by weight to obtain a transparent water-soluble polysiloxane 8.
[0111]
(Examples, Comparative Examples)
Compressive strength
Measurements were made using a Zwick tensile / pressure tester model UP1455.
A perfectly cylindrical extrudate with a test material diameter of 5 mm was cut to a test material length of 7 mm. For accurate and reproducible measurements, it must be ensured that both front faces of the extrudate are plane-parallel. The measurement was performed at room temperature at a test pressure of 1 N and a test speed of 1 mm / min. The test force acts on both fronts.
[0112]
[Example 1]
Twin screw extrusion of a reaction mixture containing 200 g of synthetic zeolite A-3 powder (manufactured by Wako Pure Chemical Industries, Ltd.), 25 g of methylcellulose MC @ 12000 (manufactured by Aqualon) as a plasticizer, 63 g of silanol-containing porosiloxane 1 and 160 g of water Using a machine ZSK (manufactured by Werner & Freidler), the mixture was formed at a rotation speed of 50 rpm and formed into a honeycomb-shaped body. The temperature of the barrel of the extruder was 15 degrees. Methylcellulose gels by heat at temperatures above 40 ° C. and loses its water retention properties, so proper cooling of the barrel section must be ensured during processing. Then, it was baked at a temperature of 225 ° C. for 60 minutes without preliminary drying. The compression strength of the obtained molded body is 50.1 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0113]
[Example 2]
Using 200 g of synthetic zeolite A-4 powder (manufactured by Wako Pure Chemical Industries, Ltd.), 25 g of methylcellulose MC # 12000, 35 g of silanol group-containing porosiloxane 2 and 100 g of water, a honeycomb-like and pellet-like molded body was produced. This reaction mixture was extruded at a temperature of 14 ° C. with the twin screw extruder used in Example 1. Next, a honeycomb formed body was manufactured at 200 ° C. for 60 minutes. The compression strength of the obtained molded body is 57 N / mm²Met. No dimensional change or shrinkage was observed during and after molding.
[0114]
[Example 3]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 1 was treated in the same manner as in Example 1 to produce a molded article. The compression strength of the obtained molded body is 43.7 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0115]
[Example 4]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 2 was treated in the same manner as in Example 1 to produce a molded article. The compression strength of the obtained molded body is 41.7 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0116]
[Example 5]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 3 was treated in the same manner as in Example 1 to produce a molded product. The compressive strength of the obtained molded body is 45.9 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0117]
[Example 6]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 4 was treated in the same manner as in Example 1 to produce a molded product. The compression strength of the obtained molded body is 42.5 N / mm²Met. No dimensional change or shrinkage was observed during and after molding.
[0118]
[Example 7]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 5 was treated in the same manner as in Example 1 to produce a molded article. The compression strength of the obtained molded body is 44.3 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0119]
Example 8
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 6 was treated in the same manner as in Example 1 to produce a molded article. The compression strength of the obtained molded body is 47.7 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0120]
[Example 9]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 7 was treated in the same manner as in Example 1 to produce a molded article. The compressive strength of the obtained molded body is 48.1 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0121]
[Example 10]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000 and 250 g of water-soluble polysiloxane 8 was treated in the same manner as in Example 1 to produce a molded article. The compression strength of the obtained molded body is 47.9 N / mm.²Met. No dimensional change or shrinkage was observed during and after molding.
[0122]
[Comparative Example 1]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000, 63 g of methylsiloxane ether {MSE} 100 as a binder and 160 g of water was treated in the same manner as in Example 1 to produce a molded article. Here, methyl siloxane ether {MSE} 100 is a mixture of various oligomers of methyl silicate, which reacts by hydrolysis and condensation to give a hard silicon resin. The compression strength of the obtained molded body is 46.7 N / mm.²However, shrinkage was observed during molding.
[0123]
[Comparative Example 2]
A reaction mixture containing 200 g of synthetic zeolite A-3 powder, 25 g of methylcellulose MC # 12000, 100 g of ethyl orthosilicate and 160 g of water was treated in the same manner as in Example 1 to produce a molded product, but the firing temperature was low. The compressive strength of the obtained molded product was 18.1 N / mm²There was only.

Claims (13)

A molded zeolite obtained from a reaction mixture containing a zeolite, a plasticizer and a binder, wherein the binder has the following average composition formula (1)
_{^{R 1 m Si (OH) p}} (OR 2) q O (4-m-p-q) / 2 (1)
(Wherein R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or acyl) M, p and q represent 0.5 ≦ m ≦ 1.8, 0 <p ≦ 2.0, 0 ≦ q ≦ 0.5, 0 <p + q ≦ 2.0, 0.5 ≦ m + p + q ≦ It is a number that satisfies 3.3.)
A zeolite molded article, characterized by being a silanol group-containing polysiloxane represented by the formula: The binder has the following general formula (2)
R ¹ _n Si (OR ³ ) _4-n (2)
(Wherein, R ¹ is as described above, and R ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group or an acyl group having 2 to 6 carbon atoms. N is 0, 1 or 2) Is.)
The zeolite molded product according to claim 1, which is a silanol group-containing polysiloxane obtained by hydrolyzing at least one kind of hydrolyzable silane represented by the following formula or a partial hydrolyzate thereof. The binder has the following general formula (3)
YR ⁴ _a Si (OR ³ ) _3-a (3)
(In the formula, Y is a nitrogen atom-containing organic group, R ⁴ is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is as described above. A is 0 or 1.)
And 100 parts by weight of a hydrolyzable silane (A) or a partial hydrolyzate thereof containing a nitrogen atom-containing organic group represented by the following general formula (4):
R ⁴ _b Si (OR ³ ) _4-b (4)
(In the formula, R ³ and R ⁴ are as described above. B is 0, 1 or 2.)
The zeolite molded product according to claim 2, which is a polysiloxane obtained by hydrolyzing 5 to 200 parts by weight of a hydrolyzable silane (B) or a partial hydrolyzate thereof. The binder has the following average composition formula (5)
_{^{R 5 c (OR 3) d}} SiO (4-c-d) / 2 (5)
(Wherein, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group or an acyl group having 2 to 6 carbon atoms, and 75 to 1.5, d is 0.2 to 3 and a positive number satisfying 0.9 <c + d <4.)
100 parts by weight of an organosilicon compound (C) represented by the following general formula (3)
YR ⁴ _a Si (OR ³ ) _3-a (3)
(In the formula, Y is a nitrogen atom-containing organic group, R ⁴ is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is as described above. A is 0 or 1.)
Is obtained by co-hydrolyzing and condensing a hydrolyzable silane containing a nitrogen atom-containing organic group represented by the following formula or a partially hydrolyzed product thereof (A) in an amount of 0.5 to 49 parts by weight in the presence of an organic acid or an inorganic acid. 2. The zeolite molded product according to claim 1, which is a polysiloxane obtained. 5. The zeolite molded product according to claim 3, wherein a polysiloxane diluted and dissolved in water is used as a binder. The zeolite according to any one of claims 1 to 5, wherein the zeolite is selected from zeolite 3A, zeolite 4A, zeolite 5A, zeolite X, and any mixture thereof, and the plasticizer is methylcellulose. Molded body. The zeolite molded product according to any one of claims 1 to 6, wherein the plasticizer is selected from cellulose ether, polysaccharide, polyvinyl alcohol, starch, and an arbitrary mixture thereof. The zeolite molded product according to any one of claims 1 to 7, wherein the reaction mixture contains 40 to 90% by weight of zeolite, 5 to 40% by weight of a plasticizer, and 1 to 35% by weight of a binder. 9. The molded zeolite according to claim 1, wherein the reaction mixture comprises a wax emulsion and / or a fatty acid mixture. The zeolite molded product according to any one of claims 1 to 9, wherein the obtained molded product has a honeycomb shape. The zeolite molded product according to any one of claims 1 to 10, wherein the molded product has a compressive strength of 20 N / mm ² or more. The zeolite formed body according to any one of claims 1 to 11, wherein the formed body is formed by firing the reaction mixture at a firing temperature of 180 to 280 ° C. A method for producing a zeolite molded body, comprising extruding the reaction mixture according to any one of claims 1 to 9, and then calcining the extrudate at a temperature of 180 to 280 ° C.