JP7130072B2 - Mfiゼオライト分離膜中の欠陥構造を調節する方法 - Google Patents
Mfiゼオライト分離膜中の欠陥構造を調節する方法 Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
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- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 claims description 2
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Description
実施例1:MFI粒子の製造
分離膜を合成するための種として用いられるMFI粒子を合成するために、既存に報告された方法を用いて100nm程度の粒子を得た(Choi et al.,Adsorption,2006,12,339-360)。このように得た粒子を支持台上に蒸着させ、種層を形成する。均一に形成されたMFIゼオライト種層は、水熱合成を経て支持台上に分離膜を形成する。
二次成長のためにMFI粒子を合成する時に用いられる有機構造指向剤であるTPAOHを用いて二次成長溶液を作製した(Choi et al.,Adsorption,2006,12,339-360)。用意した溶液に種層を入れ、二次成長のための水熱合成を行うことで、MFIゼオライト分離膜を得ることができる。この時、二次成長は、2つの条件で行った。90℃の温度で5日間水熱合成をして1~2μm厚のMFI分離膜(MFI分離膜A)を合成し、140℃の温度で1日間水熱合成をして4~6μ厚のMFI分離膜(MFI分離膜B)を合成した。
MFI分離膜AとBを合成した後、2つの方法で焼成を行った。まず第一に、一般焼成は、空気を200cc/minで流しながら480℃で10時間維持しつつ行った。この時、480℃まで昇温速度は0.5℃/minに維持した。第二に、オゾン焼成は、100~300℃で12時間行った。オゾンはオゾン発生器で生成されるが、このとき、酸素は1L/minで流し、合計0.1g/min(5vol%)のオゾンが焼成時に分離膜に注入された。この時、100~300℃までの昇温速度は0.5℃/minに維持した。
MFI分離膜AとMFI分離膜Bとを合成し、一般焼成及びオゾン焼成を行って、p-キシレンとo-キシレン混合物の分離性能を測定し、図1に示した。MFI分離膜Aは、一般焼成を行う場合、150℃で2.2×10-7mol・m-2・s-1・Pa-1のp-キシレンの透過度と3.2の分離係数を得た。しかし、200℃で12時間オゾン焼成を行う場合、150℃で2.0×10-7mol・m-2・s-1・Pa-1のp-キシレンの透過度と608の分離係数を得た。MFI分離膜Bは、一般焼成を行う場合、150℃で1.3×10-7mol・m-2・s-1・Pa-1のp-キシレンの透過度と6.2の分離係数を得た。しかし、150℃で12時間オゾン焼成を行う場合、150℃で1.06×10-7mol・m-2・s-1・Pa-1のp-キシレンの透過度と4,103の分離係数を得た。
実施例1~3の方法で作製されたMFI分離膜AとBの欠陥特性を把握するためにFCOM測定を行った。~1nmサイズを有する染料を用いて分離膜を染色する場合、分離膜において1nm以上のサイズを有する欠陥を、FCOMを用いて選択的に分析することができる。このことから、分離膜中の欠陥構造を確認することができる。FCOMを用いてオゾン焼成を行って作製されたMFI分離膜と一般焼成によって作製されたMFI分離膜の欠陥構造を確認し、それを図5に示した。FCOM分析から、一般焼成を行ったMFI分離膜Aの欠陥を確認する場合、分離膜全般にわたって欠陥が分布していることが確認できた。しかし、MFI分離膜Aをオゾン焼成する場合、一般焼成におけるように連結されている欠陥ではなく、点状の欠陥が低い密度で形成された。また、MFI分離膜Bでは、一般焼成を行う場合、大きいサイズを有するクラック(crack)状の欠陥が形成されていることが確認できた。しかし、オゾン焼成を行う場合、小さいサイズの粒子界面(grain boundary)欠陥が形成された。
Claims (9)
- MFIゼオライト分離膜を150~300℃の温度及びオゾン雰囲気下で焼成させる段階を含む、MFIゼオライト分離膜の欠陥構造を調節するMFIゼオライト分離膜の欠陥構造の調節方法であって、
0.001~1.5g/minのオゾンの注入速度でオゾンの総注入量が注入気体の総量に対して0.05~75vol%となるように注入され、0.1~20℃/minの昇温速度で0.5~168時間焼成させ、
前記MFIゼオライト分離膜が10~4100のp-キシレン/o-キシレン分離係数を有する、前記方法。 - 前記MFIゼオライト分離膜は、MFI種層が形成された支持体上に、有機構造指向剤:SiO2:H2O:Al2O3:Na2O=1~100:5~500:1,000~50,000:0~100:0~1,000のモル比で構成された二次成長溶液を添加し、水熱合成させる段階を含む方法によって製造されることを特徴とする、請求項1に記載のMFIゼオライト分離膜の欠陥構造の調節方法。
- 前記有機構造指向剤は、TPAOH(tetrapropylammonium hydroxide)、TPABr(tetrapropylammonium bromide)、TPAF(tetrapropylammonium fluoride)、TPACl(tetrapropylammonium chloride)、TPAI(tetrapropylammonium iodide)、TEAOH(tetraethylammonium hydroxide)、TEABr(tetraethylammonium bromide)、TEAF(tetraethylammonium fluoride)、TEACl(tetraethylammonium chloride)及びTEAI(tetraethylammonium iodide)からなる群から選ばれる1種以上であることを特徴とする、請求項2に記載のMFIゼオライト分離膜の欠陥構造の調節方法。
- 前記水熱合成は、80~200℃の温度で12~240時間行われることを特徴とする、請求項2に記載のMFIゼオライト分離膜の欠陥構造の調節方法。
- 前記水熱合成後に、分離膜を30~200℃の温度で1~24時間乾燥させる段階をさらに含む、請求項2に記載のMFIゼオライト分離膜の欠陥構造の調節方法。
- 前記支持体は、α-アルミナ、ポリプロピレン、ポリエチレン、ポリテトラフルオロエチレン、ポリスルホン、ポリイミド、シリカ、ガラス、ガンマアルミナ、ムライト(mullite)、ジルコニア(zirconia)、チタニア(titania)、イットリア(yttria)、セリア(ceria)、バナジア(vanadia)、シリコン、ステンレススチール及びカーボンからなる群から選ばれる1種以上であることを特徴とする、請求項2に記載のMFIゼオライト分離膜の欠陥構造の調節方法。
- 請求項1~6のいずれか一項に記載の方法によって製造されたMFIゼオライト分離膜を用いて、C8芳香族異性体の混合物からp-キシレンを分離する、p-キシレンの分離方法。
- 前記C8芳香族異性体は、p-キシレン、m-キシレン、o-キシレン、またはエチルベンゼンであることを特徴とする、請求項7に記載のp-キシレンの分離方法。
- 50℃以上の温度で行われることを特徴とする、請求項7に記載のp-キシレンの分離方法。
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