JP2011016123A5 - - Google Patents
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- JP2011016123A5 JP2011016123A5 JP2010056780A JP2010056780A JP2011016123A5 JP 2011016123 A5 JP2011016123 A5 JP 2011016123A5 JP 2010056780 A JP2010056780 A JP 2010056780A JP 2010056780 A JP2010056780 A JP 2010056780A JP 2011016123 A5 JP2011016123 A5 JP 2011016123A5
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本発明は、ゼオライト膜、その合成法及び用途に関するものであり、更に詳しくは、ゼオライト膜、分離膜モジュール、その製造方法、及び用途に関するものである。本発明は、複数本の管状分離膜を結束した分離膜モジュール及びその製造方法に関するものであり、複数本の管状分離膜を結束することで、透過に有効な膜面積を増大できるので、処理量が増大し、混合溶液、混合蒸気、混合気体を分離でき、加えて、反応器と分離器が一体となった膜型反応器としても利用できるものである。 The present invention relates to a zeolite membrane, a synthesis method and use thereof, and more particularly, to a zeolite membrane, a separation membrane module, a production method thereof and use. The present invention relates to a method for manufacturing a separation membrane module 及 patron who bundling a plurality of tubular separation membrane, by binding a plurality of tubular separation membrane, since the effective membrane area in the transmission can be increased, the amount of processing Thus, the mixed solution, the mixed vapor, and the mixed gas can be separated, and in addition, it can be used as a membrane reactor in which the reactor and the separator are integrated.
一般的に、無機膜は、支持基材の表面に分離膜を形成することにより製造される。支持基材には、孔径が０．１〜１０μｍ程度で、空隙率が１０〜６０％程度の多孔質なアルミナ、ムライト、ジルコニア、ＳＵＳ等の金属もしくは金属酸化物が利用される。分離層には、無孔質なパラジウム（特許文献３）、ペロブスカイト化合物（特許文献４）等の金属及び金属酸化物や、多孔質なシリカ（特許文献５）、アルミナ（特許文献６）、分子篩炭素（特許文献７）、ゼオライト（特許文献８）等で形成される。特に、ゼオライト膜は、水の選択的除去に有望であり、ＮａＡ型ゼオライト膜を利用した分離技術が開発されている（特許文献９）。 Generally, an inorganic membrane is manufactured by forming a separation membrane on the surface of a support substrate. For the support substrate, a porous metal or metal oxide such as alumina, mullite, zirconia, and SUS having a pore diameter of about 0.1 to 10 μm and a porosity of about 10 to 60% is used. The separation layer is non-porous palladium (Patent Document 3), a perovskite compound and (Patent Document 4), etc. of the metal 及 beauty metal oxide, porous silica (Patent Document 5), alumina (Patent Document 6), It is formed of molecular sieve carbon (Patent Document 7), zeolite (Patent Document 8), or the like. In particular, the zeolite membrane is promising for selective removal of water, and a separation technique using a NaA-type zeolite membrane has been developed (Patent Document 9).
しかし、単一の管状もしくは板状の分離膜は、分離処理に有効な膜面積が限定されるので、透過性、分離性だけでなく、耐薬品性、耐熱性等の優れた分離膜であっても、工業的に利用することは困難である。そのため、複数の分離膜を備えた分離膜モジュールの開発が不可欠である。特に、ゼオライト膜の場合、高温のアルカリ水溶液中で薄膜を形成すること、及び膜素材であるゼオライトの耐熱性等の問題から、複数の分離膜を連結するとともに、連結部からの漏れを防止するためには、非常に複雑な操作が必要であった（特許文献１０）。 However, since a single tubular or plate-like separation membrane has a limited membrane area effective for separation treatment, it is an excellent separation membrane not only in permeability and separation properties but also in chemical resistance and heat resistance. However, it is difficult to use industrially. Therefore, development of a separation membrane module provided with a plurality of separation membranes is indispensable. In particular, prevention case of zeolite membrane, by forming a thin film in a hot alkaline aqueous solution, from the zeolite such as heat resistance problem is 及 beauty membrane material, as well as connecting a plurality of the separation membrane, leakage from the connecting portion In order to do so, a very complicated operation was required (Patent Document 10).
このような状況の中で、本発明者らは、上記従来技術に鑑みて、ＣＨＡ型等のゼオライト膜の製造方法について鋭意検討した結果、上記従来技術の課題を解決できるＣＨＡ型等のゼオライト膜の開発に成功し、そして、より具体的には、多孔質基材の支持体に、予めＣＨＡ等の結晶粉末を付着させた後、その基材を、例えば、ストロンチウムを含むゼオライト成長水溶液とともに耐圧容器中で水熱処理することで、多孔質基材の支持体上に、比較的簡単に、ブロック状のＣＨＡ等の結晶だけが連結した多結晶薄膜を得ることに成功し、更に、単位容積当たりの有効面積を極めて大きくできる管状の分離膜を複数本結束させる接着法及び封止法について検討し、分離膜モジュール及び封止機能の優れた分離膜モジュールの製造方法を開発することに成功し、本発明を完成するに至った。 Under such circumstances, the present inventors have made extensive studies on a method for producing a CHA type zeolite membrane in view of the above prior art, and as a result, the CHA type zeolite membrane capable of solving the above-mentioned problems of the prior art. More specifically, after the crystal powder such as CHA is attached to the support of the porous base material in advance, the base material is pressure-resistant together with, for example, a zeolite growth aqueous solution containing strontium. By hydrothermally treating in a container, it succeeded in obtaining a polycrystalline thin film in which only crystals such as block-like CHA were connected relatively easily on the support of the porous substrate. effective area examined very large can gluing 及 beauty sealing method the separation membrane of tubular to a plurality of bundling, child develop a method of manufacturing the excellent separation membrane module of the separation membrane module 及 beauty sealing features Successful, which resulted in the completion of the present invention.
本発明は、ＣＨＡ型等のゼオライトだけで構成されたゼオライト膜を、有機鋳型剤を含まない合成水溶液を使用して製造した、優れた透過性、分離性、及び耐環境性を有するゼオライト膜を提供することを目的とするものである。また、本発明は、ＣＨＡ型等のゼオライトだけで構成されたゼオライト膜を、有機鋳型剤を含まない合成水溶液を使用して製造することを特徴とするＣＨＡ型ゼオライト膜の製造方法、及びその用途を提供することを目的とするものである。更に、本発明は、従来、複雑な操作が必要であった分離膜の連結及び封止を、簡便かつ確実に実施できる接着法及び封止法を開発し、分離膜モジュール及びその製造方法を提供することを目的とするものである。 The present invention provides a zeolite membrane having excellent permeability, separability, and environmental resistance, produced by using a synthetic aqueous solution containing no organic templating agent. It is intended to provide. In addition, the present invention provides a method for producing a CHA-type zeolite membrane, characterized by producing a zeolite membrane composed only of zeolite such as CHA-type using a synthetic aqueous solution not containing an organic templating agent, and uses thereof Is intended to provide. Furthermore, the invention conventionally consolidated 及 beauty seal complicated separation membrane operation has been necessary to develop a bonding method 及 beauty sealing method which can be carried out easily and reliably, the production method of the separation membrane module 及 benefactor Is intended to provide.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）多孔質基材の支持体上に作製されたゼオライトの多結晶薄膜であって、その結晶構造が、チャバザイトであることを特徴とするチャバザイト型ゼオライト膜。
（２）ゼオライトが、ＳｉＯ２：５２〜７７ｍｏｌ％、Ａｌ２Ｏ３：１１〜２２ｍｏｌ％、Ｋ２Ｏ：６〜２０ｍｏｌ％、及びＳｒＯ：０〜９ｍｏｌ％のゼオライトである、前記（１）に記載のゼオライト膜。
（３）多孔質基材の支持体が、金属及び／又は金属酸化物から構成される、前記（１）又は（２）に記載のゼオライト膜。
（４）多孔質基材の材料が、アルミナ、ムライト、ジルコニア、又はＳＵＳである、前記（１）から（３）のいずれか一項に記載のゼオライト膜。
（５）予めゼオライト結晶を付着させた多孔質基材の支持体を、アルミノシリケート水溶液中で加熱するゼオライト膜の製造方法であって、
多孔質基材の支持体に付着させるゼオライト結晶の構造が、チャバザイト（ＣＨＡ）又はＫＦＩであることを特徴とするチャバザイト型ゼオライト膜の製造方法。
（６）アルミノシリケート水溶液が、Ａｌが１ｍｏｌに対して、Ｓｉを１〜１７．５ｍｏｌ、アルカリ金属、及びアルカリ土類金属に由来する水酸化物イオンを０．５〜１６ｍｏｌ、水を６５〜１８００ｍｏｌ含んでいる、前記（５）に記載のゼオライト膜の製造方法。
（７）アルミノシリケート水溶液が、Ｓｉを１．５ｍｏｌ％、Ａｌを０．２５ｍｏｌ％、Ｋを１．５ｍｏｌ％、Ｓｒを０．１２ｍｏｌ％含む水溶液である、前記（５）に記載のゼオライト膜の製造方法。
（８）前記（１）から（４）のいずれかに記載のゼオライト膜からなることを特徴とする分離膜。
（９）複数本の管状分離膜を結束した分離膜モジュールであって、結束部材に接着剤により複数本の管状分離膜を接続して結束したこと、管状分離膜が、多孔質管とゼオライト膜との複合膜であること、を特徴とする分離膜モジュール。
（１０）ゼオライト膜が、チャバザイト型ゼオライト膜である、前記（９）に記載の分離膜モジュール。
（１１）前記（９）に記載の分離膜モジュールを製造する方法であって、複数の管状分離膜の一端もしくは両端を、接着剤により、結束部材に接続することを特徴とする分離膜モジュールの製造方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) A chabazite-type zeolite membrane, which is a polycrystalline thin film of zeolite produced on a support of a porous base material , the crystal structure of which is chabazite.
(2) The above (1), wherein the zeolite is a zeolite of S iO 2 : 52 to 77 mol%, Al 2 O 3 : 11 to 22 mol%, K 2 O: 6 to 20 mol%, and SrO: 0 to 9 mol%. The zeolite membrane described in 1.
(3) support the porous substrate, Ru consists metals and / or metal oxide, zeolite membrane according to (1) or (2).
(4) The zeolite membrane according to any one of (1) to (3), wherein the material of the porous substrate is alumina, mullite, zirconia, or SUS.
(5) A method for producing a zeolite membrane in which a support of a porous base material to which zeolite crystals have been previously attached is heated in an aluminosilicate aqueous solution,
A method for producing a chabazite-type zeolite membrane, wherein the structure of the zeolite crystal attached to the support of the porous substrate is chabazite (CHA) or KFI .
(6) The aluminosilicate aqueous solution has 1 to 17.5 mol of Si, 0.5 to 16 mol of hydroxide ions derived from alkali metal and alkaline earth metal, and 65 to 1800 mol of water with respect to 1 mol of Al. The manufacturing method of the zeolite membrane as described in said (5) which contains.
(7) The zeolite membrane according to (5), wherein the aqueous aluminosilicate solution is an aqueous solution containing 1.5 mol% Si, 0.25 mol% Al, 1.5 mol% K, and 0.12 mol% Sr. Production method.
(8) A separation membrane comprising the zeolite membrane according to any one of (1) to (4).
(9) A separation membrane module in which a plurality of tubular separation membranes are bundled, wherein a plurality of tubular separation membranes are connected to a bundling member with an adhesive, and the tubular separation membrane is formed by a porous tube and a zeolite membrane. separation membrane module, wherein it is a composite film of.
(10) The separation membrane module according to (9), wherein the zeolite membrane is a chabazite-type zeolite membrane .
(11) A method of manufacturing the separation membrane module according to (9), wherein one end or both ends of a plurality of tubular separation membranes are connected to a binding member by an adhesive. Production method.
次に、本発明について更に詳細に説明する。
本発明は、チャバザイト型ゼオライト膜であって、多孔質基材の支持体上に作製されたゼオライトの多結晶薄膜であり、その結晶構造が、チャバザイトであることを特徴とするものである。本発明では、ゼオライトが、ＳｉＯ２：７５ｍｏｌ％、Ａｌ２Ｏ３：１２ｍｏｌ％、Ｋ２Ｏ：１１ｍｏｌ％、及びＳｒＯ：２ｍｏｌ％のゼオライトであること、を好ましい実施の態様としている。本明細書では、多孔質基材の支持体を、多孔質支持体、多孔質な支持体、支持体、支持基材、多孔質管、あるいは支持管と記載することがある。
Next, the present invention will be described in more detail.
The present invention is a chabazite-type zeolite membrane, which is a polycrystalline thin film of zeolite produced on a support of a porous substrate , and its crystal structure is chabazite. In the present invention, a preferred embodiment is that the zeolite is a zeolite of S iO 2 : 75 mol%, Al 2 O 3 : 12 mol%, K 2 O: 11 mol%, and SrO: 2 mol%. In this specification, the support of a porous substrate may be described as a porous support, a porous support, a support, a support substrate, a porous tube, or a support tube.
また、本発明は、上記チャバザイト型ゼオライト膜の製造方法であって、予めゼオライト結晶を付着させた多孔質基材の支持体を、アルミノシリケート水溶液中で加熱するゼオライト膜の製造方法であり、多孔質基材の支持体に付着させるゼオライト結晶の構造が、チャバザイト（ＣＨＡ）又はＫＦＩであることを特徴とするものである。 Further, the present invention is a method for producing the above-mentioned chabazite-type zeolite membrane, which is a method for producing a zeolite membrane in which a porous substrate support to which zeolite crystals have been previously attached is heated in an aluminosilicate aqueous solution. structure of the zeolite crystals to be attached to the support of Shitsumoto material is characterized in that a chabazite (CHA) or KFI.
また、この結晶粉末は、多孔質支持体に付着していればよく、そのためには、多孔質支持体に、ＣＨＡ型ゼオライト結晶粉末を擦り込む方法、ＣＨＡ型ゼオライト結晶粉末の分散溶液に、多孔質支持体を含浸させた後に、多孔質支持体を乾燥させる方法、等を用いることができる。 Further, this crystalline powder, rather'll if adhered to a porous support, for this, the porous support, a method of rubbing a CHA-type zeolite crystal powder, the dispersion solution of CHA-type zeolite crystal powder, A method of drying the porous support after impregnating the porous support can be used.
本発明において、支持体に付着させたＣＨＡ型ゼオライト結晶の成長には、好適には、アルミノシリケート水溶液が用いられる。このアルミナシリケート水溶液は、Ａｌが１ｍｏｌに対して、Ｓｉを１〜１７．５ｍｏｌ、アルカリ金属、及びアルカリ土類金属に由来した水酸化物イオンを０．５〜１６ｍｏｌ、水を６５〜１８００ｍｏｌ含んでいればよく、好適には、アルミノシリケート水溶液が、Ｓｉを１．５ｍｏｌ％、Ａｌを０．２５ｍｏｌ％、Ｋを１．５ｍｏｌ％、Ｓｒを０．１２ｍｏｌ％含む水溶液である。 In the present invention, an aqueous aluminosilicate solution is preferably used for the growth of the CHA-type zeolite crystal attached to the support. This alumina silicate aqueous solution contains 1 to 17.5 mol of Si, 0.5 to 16 mol of hydroxide ions derived from alkali metal and alkaline earth metal, and 65 to 1800 mol of water with respect to 1 mol of Al. put it'll rather, preferably, aluminosilicate aqueous solution, Si and 1.5 mol%, Al of 0.25 mol%, 1.5 mol% of K, an aqueous solution containing 0.12 mol% of Sr.
実施例１及び実施例３２〜３５の結果から、支持体に付着させるゼオライト結晶としては、ＣＨＡ型ゼオライト以外に、ＫＦＩ型ゼオライトが有効であることが分かった。 From the results of Example 1 and Examples 32-35, it was found that KFI-type zeolite is effective as the zeolite crystal attached to the support, in addition to the CHA-type zeolite.
Claims (11)
多孔質基材の支持体に付着させるゼオライト結晶の構造が、チャバザイト（ＣＨＡ）又はＫＦＩであることを特徴とするチャバザイト型ゼオライト膜の製造方法。 A method for producing a zeolite membrane comprising heating a porous substrate support to which zeolite crystals have been attached in advance, in an aluminosilicate aqueous solution,
A method for producing a chabazite-type zeolite membrane, wherein the structure of the zeolite crystal attached to the support of the porous substrate is chabazite (CHA) or KFI .
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| JP2012067091A (en) * | 2010-08-25 | 2012-04-05 | Mitsubishi Chemicals Corp | Recovery method of alcohol from alcohol-water mixture |
| JP5852963B2 (en) * | 2010-10-06 | 2016-02-03 | 日立造船株式会社 | Composite zeolite membrane and method for producing the same |
| JP5858492B2 (en) * | 2011-03-14 | 2016-02-10 | 国立大学法人 岡山大学 | Zeolite bulk having machinability, reaction solution and production method thereof for hydrothermal synthesis, and use thereof |
| JP2012214387A (en) * | 2011-03-31 | 2012-11-08 | National Institute Of Advanced Industrial Science & Technology | Method for producing ester |
| JP5783527B2 (en) * | 2011-06-22 | 2015-09-24 | 三菱化学株式会社 | Method for producing aluminosilicate |
| JP6171151B2 (en) * | 2011-11-17 | 2017-08-02 | 国立研究開発法人産業技術総合研究所 | Zeolite membrane and method for producing the same |
| CN102600735B (en) * | 2012-03-29 | 2014-09-03 | 吉林大学 | Inorganic phase separation membrane and application of thereof to oil-water separation |
| JP6163715B2 (en) * | 2012-03-30 | 2017-07-19 | 三菱ケミカル株式会社 | Zeolite membrane composite |
| JP6107000B2 (en) * | 2012-03-30 | 2017-04-05 | 三菱化学株式会社 | Zeolite membrane composite |
| JP2014198308A (en) | 2013-03-29 | 2014-10-23 | 日本碍子株式会社 | Ceramic separation filter and dehydration method |
| CN106255545B (en) * | 2014-04-18 | 2019-08-27 | 三菱化学株式会社 | Porous support-zeolite film composite and porous support-zeolite film composite manufacturing method |
| WO2016067677A1 (en) * | 2014-10-30 | 2016-05-06 | 三菱化学株式会社 | Method for producing high-concentration alcohol |
| JP6400726B2 (en) * | 2014-11-07 | 2018-10-03 | 株式会社東芝 | Water treatment method, water treatment system and water treatment apparatus |
| JP6558947B2 (en) * | 2015-05-22 | 2019-08-14 | イビデン株式会社 | Method for manufacturing honeycomb catalyst |
| KR102033300B1 (en) | 2017-11-16 | 2019-10-17 | 고려대학교 산학협력단 | Method of Fabricating Organic Template-Free CHA Zeolite Membranes and Membranes Prepared Thereby |
| KR102205266B1 (en) * | 2018-12-28 | 2021-01-20 | 고려대학교 산학협력단 | CHA Zeolite Membranes and Method of Preparing the Same |
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| JP2002220208A (en) * | 2001-01-19 | 2002-08-09 | Nkk Corp | Method and device for manufacturing oxygen-enriched gas |
| JP2008521738A (en) * | 2004-12-01 | 2008-06-26 | 株式会社物産ナノテク研究所 | Zeolite membrane and method for producing the same |
| DE102005016397A1 (en) * | 2005-04-08 | 2006-10-12 | Forschungszentrum Jülich GmbH | Membrane for gas phase separation and suitable manufacturing process |
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| JP5585126B2 (en) * | 2009-02-27 | 2014-09-10 | 三菱化学株式会社 | Inorganic porous support-zeolite membrane composite, its production method and separation method using the same |
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