JP5852963B2 - Composite zeolite membrane and method for producing the same - Google Patents
Composite zeolite membrane and method for producing the same Download PDFInfo
- Publication number
- JP5852963B2 JP5852963B2 JP2012537615A JP2012537615A JP5852963B2 JP 5852963 B2 JP5852963 B2 JP 5852963B2 JP 2012537615 A JP2012537615 A JP 2012537615A JP 2012537615 A JP2012537615 A JP 2012537615A JP 5852963 B2 JP5852963 B2 JP 5852963B2
- Authority
- JP
- Japan
- Prior art keywords
- zeolite membrane
- oxygen
- membered ring
- ring structure
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010457 zeolite Substances 0.000 title claims description 208
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 205
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 204
- 239000012528 membrane Substances 0.000 title claims description 192
- 239000002131 composite material Substances 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 92
- 239000001301 oxygen Substances 0.000 claims description 91
- 229910052760 oxygen Inorganic materials 0.000 claims description 91
- 239000000843 powder Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000012013 faujasite Substances 0.000 description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- 238000000926 separation method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000011148 porous material Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000005371 permeation separation Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
Description
本発明は、高機能化した複合ゼオライト膜、およびその製造方法に関する。 The present invention relates to a highly functional composite zeolite membrane and a method for producing the same.
近年、ゼオライト膜は、分子篩や吸着特性による分子レベルでの分離が可能であることから、分離膜、膜反応器、化学センサー等への応用が考えられている。 In recent years, zeolite membranes can be separated at the molecular level by molecular sieves or adsorption characteristics, and therefore, application to separation membranes, membrane reactors, chemical sensors, and the like has been considered.
ゼオライトの中でもＡ型ゼオライト（ＬＴＡ）は強い親水性を示すことから、アルコールの脱水用分離膜としてＡ型ゼオライト膜が１９９８年頃に実用化されている（非特許文献１）。また、例えばエタノール脱水（水１０ｗｔ％，温度１３０ｏＣ）において、水透過流束５０ｋｇ・ｍ−２・ｈ-１を超える高性能Ａ型ゼオライト膜が開発され（非特許文献２）、実用化に至っている。
一方で、Ａ型ゼオライト膜は、ゼオライトの中では耐性に乏しく、その適応範囲が限られている。そのため、より耐性に富む親水性ＦＡＵ（フォージャサイト）型（主にＹ型）ゼオライト膜が開発されている（特許文献３）。Among zeolites, A-type zeolite (LTA) exhibits strong hydrophilicity, and therefore, an A-type zeolite membrane was put into practical use around 1998 as a separation membrane for alcohol dehydration (Non-patent Document 1). For example, in ethanol dehydration (
On the other hand, the A-type zeolite membrane has poor resistance among zeolites, and its application range is limited. For this reason, a hydrophilic FAU (faujasite) type (mainly Y type) zeolite membrane with higher resistance has been developed (Patent Document 3).
ＦＡＵ型ゼオライト膜については、Ａ型ゼオライト膜が適用できない過酷な条件でも脱水膜として高い透過分離性能を発揮することが確認されており（非特許文献３）、今後、需要が高まることが予想される。なお、結晶間空隙の少ない緻密なＹ型ゼオライト膜の合成法（特許文献２）など、ゼオライト膜の製膜技術は、精力的に研究されている。 Regarding FAU-type zeolite membranes, it has been confirmed that high permeation separation performance is exhibited as a dehydration membrane even under severe conditions where A-type zeolite membranes cannot be applied (Non-patent Document 3), and demand is expected to increase in the future. The In addition, techniques for producing a zeolite membrane, such as a method for synthesizing a dense Y-type zeolite membrane having few intercrystalline voids (Patent Document 2), have been energetically studied.
また一般に、ＦＡＵ型ゼオライト膜は、大きな酸素１２員環細孔（約０．７４ｎｍ）をもち、ＦＡＵ型ゼオライトの吸着特性に由来する分離能と、拡散が容易な比較的大きな細孔構造に由来する高透過度が期待される。 In general, the FAU type zeolite membrane has large oxygen 12-membered ring pores (about 0.74 nm), and is derived from the separation ability derived from the adsorption characteristics of the FAU type zeolite and the relatively large pore structure that is easy to diffuse. High transparency is expected.
例えば、水、ＣＯ２（二酸化炭素）、ＣＨ４（メタン）などの各種の分子の大きさは、下記の通りである。
分子名 分子サイズ
水： ０．３０ ｎｍ
ＣＯ２ ： ０．３３ ｎｍ
ＣＨ４ ： ０．３８ ｎｍ
エタノール： ０．４３ ｎｍ
酢酸： ０．４３ ｎｍ
ＩＰＡ（イソプロピルアルコール）：約０．４７ ｎｍ
ここで、例えば、水（０．３０ｎｍ）／エタノール（０．４３ｎｍ）、水／ＩＰＡ（約０．４７ｎｍ）、ＣＯ２（０．３３ｎｍ）／ＣＨ４（０．３８ｎｍ）などの組み合わせによる混合物における分子分離など、ゼオライト膜を透過させたくない分子の大きさが、ＦＡＵ型ゼオライト細孔径よりも小さい場合、あるいはまた高温や、透過させる分子の濃度が小さい条件下では、ゼオライト膜による分離は困難であるため、吸着による分離を行う必要があるが、吸着による分離能が機能しにくいため、分離能の低下が避けられない。For example, the sizes of various molecules such as water, CO 2 (carbon dioxide), and CH 4 (methane) are as follows.
Molecular name Molecular size Water: 0.30 nm
CO 2 : 0.33 nm
CH 4: 0.38 nm
Ethanol: 0.43 nm
Acetic acid: 0.43 nm
IPA (isopropyl alcohol): about 0.47 nm
Here, for example, in a mixture by a combination of water (0.30 nm) / ethanol (0.43 nm), water / IPA (about 0.47 nm), CO 2 (0.33 nm) / CH 4 (0.38 nm), etc. Separation with a zeolite membrane is difficult when the size of the molecule that you do not want to permeate through the zeolite membrane, such as molecular separation, is smaller than the FAU-type zeolite pore diameter, or at high temperatures and conditions where the concentration of permeated molecules is small. Therefore, it is necessary to perform separation by adsorption, but since the separation ability by adsorption is difficult to function, a reduction in separation ability is inevitable.
上記のように吸着による分離能が低い条件では、分子篩を利用した分離が有効になることが多い。例えば水（０．３０ｎｍ）のみを膜透過させてＩＰＡ（０．４７ｎｍ）などの分子を透過させたくない場合、分離膜を、酸素８員環構造を有するゼオライト（細孔径０．２８〜０．４２ ｎｍ）によって構築することで、分子篩能が期待できる。 As described above, separation using a molecular sieve is often effective under conditions where the separation ability by adsorption is low. For example, when it is not desired to allow only water (0.30 nm) to permeate through the membrane and not to permeate molecules such as IPA (0.47 nm), the separation membrane is made of zeolite having an oxygen 8-membered ring structure (pore diameter 0.28-0. 42 nm), molecular sieving ability can be expected.
ここで、酸素８員環構造を有するゼオライト膜としては、近年、ＣＨＡ（チャバサイト）型膜（非特許文献４）、ＭＥＲ（マーリノアイト）型膜（特許文献３）、ＰＨＩ（フィリップサイト）型膜（特許文献４）などが開発されている。 Here, as a zeolite membrane having an oxygen 8-membered ring structure, in recent years, a CHA (Chabasite) type membrane (Non-patent Document 4), a MER (Marlinoite) type membrane (Patent Document 3), a PHI (Philip Site) type membrane. (Patent Document 4) has been developed.
しかしながら、細孔径の大きな酸素１２員環構造を有するＦＡＵ型ゼオライトに比べて、細孔径の小さな酸素８員環構造を有するＣＨＡ型ゼオライト膜では、分子の拡散が遅くなるため、その膜厚が厚い場合、十分な透過流束が得られないという問題があった。 However, the CHA-type zeolite membrane having an oxygen 8-membered ring structure with a small pore diameter has a larger film thickness because the diffusion of the molecules is slow compared to the FAU-type zeolite having an oxygen 12-membered ring structure with a large pore diameter. In this case, there is a problem that a sufficient permeation flux cannot be obtained.
本発明の目的は、上記の従来技術の問題を解決し、ＦＡＵ型ゼオライト膜などの酸素１２員環構造を有するゼオライト膜の表面を、ＣＨＡ型ゼオライト膜などの酸素８員環構造を有するゼオライト膜に転換させることにより、従来の合成方法に比べて、酸素８員環構造を有するゼオライト膜層の大幅な薄膜化が可能により構成され、分子分離能に優れた複合ゼオライト膜を提供すること、および該複合ゼオライト膜の製造方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a zeolite membrane having an oxygen 8-membered ring structure such as a CHA-type zeolite membrane on the surface of a zeolite membrane having an oxygen 12-membered ring structure such as a FAU-type zeolite membrane. Providing a composite zeolite membrane that has a structure capable of drastically reducing the thickness of a zeolite membrane layer having an oxygen 8-membered ring structure and having excellent molecular separation performance compared to the conventional synthesis method, and An object of the present invention is to provide a method for producing the composite zeolite membrane.
本発明者らは、上記の点に鑑み鋭意研究を重ねた結果、酸素１２員環構造を有するゼオライト粉末を添加したアルカリ水溶液中に、支持体上に製膜された酸素１２員環構造を有するゼオライト膜を浸漬し、所定の条件下で加熱加圧処理をすることで、支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面の一部を、酸素８員環構造を有するゼオライト膜に転換させることができ、酸素１２員環構造を有するゼオライト膜の表面に酸素８員環構造を有するゼオライト膜が設けられた複合ゼオライト膜を形成することを見出し、本発明を完成するに至ったものである。 As a result of intensive studies in view of the above points, the present inventors have an oxygen 12-membered ring structure formed on a support in an alkaline aqueous solution to which zeolite powder having an oxygen 12-membered ring structure is added. A part of the surface of the zeolite membrane having an oxygen 12-membered ring structure formed on the support is immersed in the zeolite membrane and subjected to heat and pressure treatment under predetermined conditions. The present invention is completed by finding that a composite zeolite membrane having a zeolite membrane having an oxygen 8-membered ring structure is formed on the surface of the zeolite membrane having an oxygen 12-membered ring structure can be converted to a zeolite membrane having Has been reached.
上記の目的を達成するために、請求項１の複合ゼオライト膜の発明は、支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面に、酸素８員環構造を有するゼオライト膜が設けられていることを特徴としている。 In order to achieve the above object, the invention of a composite zeolite membrane according to claim 1 is directed to a zeolite membrane having an oxygen 8-membered ring structure on the surface of a zeolite membrane having an oxygen 12-membered ring structure formed on a support. It is characterized by being provided.
請求項２の発明は、請求項１に記載の複合ゼオライト膜であって、酸素１２員環構造を有するゼオライト膜が、ＦＡＵ型ゼオライト膜により構成され、酸素８員環を有するゼオライト膜が、ＣＨＡ型ゼオライト膜により構成されることを特徴としている。 The invention according to claim 2 is the composite zeolite membrane according to claim 1, wherein the zeolite membrane having an oxygen 12-membered ring structure is constituted by a FAU type zeolite membrane, and the zeolite membrane having an oxygen 8-membered ring is CHA. It is characterized by comprising a type zeolite membrane.
請求項３の発明は、請求項１又は２に記載の複合ゼオライト膜であって、酸素１２員環構造を有するゼオライト膜の厚さが、０．１μｍ〜１０μｍであり、酸素８員環を有するゼオライト膜の厚さが、１０ｎｍ〜２μｍであることを特徴としている。 The invention according to claim 3 is the composite zeolite membrane according to claim 1 or 2, wherein the zeolite membrane having an oxygen 12-membered ring structure has a thickness of 0.1 μm to 10 μm and has an oxygen 8-membered ring The zeolite membrane has a thickness of 10 nm to 2 μm.
請求項４の発明は、複合ゼオライト膜の製造方法であって、酸素１２員環構造を有するゼオライト粉末を添加したアルカリ水溶液中に、支持体上に製膜された酸素１２員環構造を有するゼオライト膜を浸漬し、所定の条件下で加熱加圧処理することで、支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面の一部を、酸素８員環構造を有するゼオライト膜に転換させることにより、酸素１２員環構造を有するゼオライト膜の表面に酸素８員環構造を有するゼオライト膜が設けられた複合ゼオライト膜を形成することを特徴としている。 The invention of claim 4 is a method for producing a composite zeolite membrane, wherein the zeolite has an oxygen 12-membered ring structure formed on a support in an alkaline aqueous solution to which zeolite powder having an oxygen 12-membered ring structure is added. A part of the surface of the zeolite membrane having an oxygen 12-membered ring structure formed on the support by immersing the membrane and subjecting it to heat and pressure treatment under a predetermined condition is used for the zeolite having an oxygen 8-membered ring structure. By converting to a membrane, a composite zeolite membrane in which a zeolite membrane having an oxygen 8-membered ring structure is provided on the surface of a zeolite membrane having an oxygen 12-membered ring structure is characterized.
請求項５の発明は、請求項４に記載の複合ゼオライト膜の製造方法であって、酸素１２員環構造を有するゼオライト粉末を０.０１〜２０ｗｔ％の割合で添加した０．０１〜３ｍｏｌ／Ｌの水酸化カリウム水溶液中に、支持体上に製膜された酸素１２員環構造を有するゼオライト膜を浸漬し、温度８０〜１５０℃、圧力０．０５〜２ＭＰａの条件下で、１〜１２０時間、加熱加圧処理することを特徴としている。
Invention of
請求項６の発明は、請求項４または５に記載の複合ゼオライト膜の製造方法であって、酸素１２員環構造を有するゼオライト膜が、ＦＡＵ型ゼオライト膜により構成され、酸素８員環を有するゼオライト膜が、ＣＨＡ型ゼオライト膜により構成されることを特徴としている。
The invention of claim 6 is the method for producing a composite zeolite membrane according to
請求項１の複合ゼオライト膜の発明は、支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面に、酸素８員環構造を有するゼオライト膜が設けられているもので、請求項１の発明によれば、ＦＡＵ型ゼオライト膜の表面の一部が酸素８員環構造を有するゼオライト膜に転換されるため、従来の合成方法に比べて、酸素８員環を有するゼオライト膜層の大幅な薄膜化が可能であり、分子分離能に優れた複合ゼオライト膜を得ることができるという効果を奏する。 The invention of the composite zeolite membrane of claim 1 is such that a zeolite membrane having an oxygen 8-membered ring structure is provided on the surface of a zeolite membrane having an oxygen 12-membered ring structure formed on a support. According to the invention of item 1, since a part of the surface of the FAU type zeolite membrane is converted to a zeolite membrane having an oxygen 8-membered ring structure, the zeolite membrane layer having an oxygen 8-membered ring as compared with the conventional synthesis method Therefore, it is possible to obtain a composite zeolite membrane excellent in molecular separation ability.
請求項４の複合ゼオライト膜の製造方法の発明は、酸素１２員環構造を有するゼオライト粉末を添加したアルカリ水溶液中に、支持体上に製膜された酸素１２員環構造を有するゼオライト膜を浸漬し、所定の条件下で加熱加圧処理することで、支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面の一部を、酸素８員環構造を有するゼオライト膜に転換させることにより、酸素１２員環構造を有するゼオライト膜の表面に酸素８員環構造を有するゼオライト膜が設けられた複合ゼオライト膜を形成することを特徴とするもので、請求項４の発明によれば、酸素１２員環構造を有するゼオライト膜の表面の一部が酸素８員環構造を有するゼオライト膜に転換されるため、従来の合成方法に比べて、酸素８員環を有するゼオライト膜層の大幅な薄膜化が可能であり、分子分離能に優れた複合ゼオライト膜を製造することができるという効果を奏する。 The invention of the method for producing a composite zeolite membrane according to claim 4 immerses the zeolite membrane having an oxygen 12-membered ring structure formed on a support in an alkaline aqueous solution to which zeolite powder having an oxygen 12-membered ring structure is added. Then, a part of the surface of the zeolite membrane having an oxygen 12-membered ring structure formed on the support is converted into a zeolite membrane having an oxygen 8-membered ring structure by heat and pressure treatment under predetermined conditions. And forming a composite zeolite membrane in which a zeolite membrane having an oxygen 8-membered ring structure is provided on the surface of the zeolite membrane having an oxygen 12-membered ring structure. For example, since a part of the surface of a zeolite membrane having an oxygen 12-membered ring structure is converted into a zeolite membrane having an oxygen 8-membered ring structure, the zeolite having an oxygen 8-membered ring as compared with the conventional synthesis method It is possible significant thinning of the layer, an effect that can be produced an excellent composite zeolite membrane on the molecular resolution.
つぎに、本発明の実施の形態を説明するが、本発明はこれらに限定されるものではない。 Next, embodiments of the present invention will be described, but the present invention is not limited thereto.
本発明による複合ゼオライト膜は、多孔質アルミナ等の支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面に、酸素８員環構造を有するゼオライト膜が設けられていることを特徴としている。 The composite zeolite membrane according to the present invention is such that a zeolite membrane having an oxygen 8-membered ring structure is provided on the surface of a zeolite membrane having an oxygen 12-membered ring structure formed on a support such as porous alumina. It is a feature.
ここで、本発明に用いられる多孔質支持体としては、例えばアルミナ、シリカ、コージェライト、ジルコニア、チタニア、バイコールガラス、焼結金属などの多孔質体が挙げられるが、これらに限らず、種々の多孔質体を用いることができる。多孔質支持体の形状は、通常は、チューブ状もしくは板状である。多孔質支持体の孔径は、通常、０．０１〜５μｍであり、好ましくは０．０５〜２μｍである。 Here, examples of the porous support used in the present invention include porous bodies such as alumina, silica, cordierite, zirconia, titania, Vycor glass, and sintered metal. A porous body can be used. The shape of the porous support is usually a tube shape or a plate shape. The pore diameter of the porous support is usually from 0.01 to 5 μm, preferably from 0.05 to 2 μm.
酸素１２員環構造を有するゼオライト膜の形成は、例えば、多孔質支持体の表面にゼオライトの粉末（種結晶）の懸濁水溶液を塗布したのち、所定の温度で乾燥したのち、水熱合成させることによって行われる。 Formation of a zeolite membrane having an oxygen 12-membered ring structure is performed, for example, by applying an aqueous suspension of a zeolite powder (seed crystal) on the surface of a porous support, drying at a predetermined temperature, and then hydrothermally synthesizing. Is done by.
原料として用いるゼオライトの種類は、特に限定されず、例えばＹ型ゼオライト（ＦＡＵ）、ベータ型ゼオライト（ＢＥＡ）、モルデナイト（ＭＯＲ）などが挙げられる。ゼオライト膜の形成のための塗布方法は、特に限定されないが、ラビング（擦り込み）法や浸漬法が好ましい。 The type of zeolite used as a raw material is not particularly limited, and examples thereof include Y-type zeolite (FAU), beta-type zeolite (BEA), and mordenite (MOR). A coating method for forming the zeolite membrane is not particularly limited, but a rubbing (rubbing) method or a dipping method is preferable.
ラビング（擦り込み）法は、多孔質支持体の表面にゼオライト粉末懸濁液を擦り込み、次いで所望により乾燥することにより、ゼオライトの粉末（種結晶）を均一塗布する方法である。 The rubbing (rubbing) method is a method in which a zeolite powder suspension (seed crystal) is uniformly coated by rubbing a zeolite powder suspension on the surface of a porous support and then drying it if desired.
また、浸漬法は、ゼオライト粉末懸濁液内に、多孔質支持体を浸し、表面にゼオライトの粉末（種結晶）を均一塗布する方法である。 The dipping method is a method in which a porous support is dipped in a zeolite powder suspension, and a zeolite powder (seed crystal) is uniformly applied to the surface.
ゼオライト粉末の塗布および乾燥ののち、水熱合成させるが、この水熱合成により、多孔質支持体上に塗布したゼオライトの粉末からゼオライト膜を形成することができる。水熱合成の温度は、特に限定されないが、多孔質支持体上にゼオライト膜がより均一に生成するという観点から、８０〜３００℃が好ましく、反応時間は、通常２〜７２０時間、好ましくは６〜１２０時間である。 After the zeolite powder is applied and dried, hydrothermal synthesis is performed. By this hydrothermal synthesis, a zeolite membrane can be formed from the zeolite powder coated on the porous support. The temperature of the hydrothermal synthesis is not particularly limited, but is preferably 80 to 300 ° C. from the viewpoint that a zeolite membrane is more uniformly formed on the porous support, and the reaction time is usually 2 to 720 hours, preferably 6 ~ 120 hours.
本発明の複合ゼオライト膜は、上記のように、多孔質アルミナ等の支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面に、酸素８員環構造を有するゼオライト膜が設けられているものである。 The composite zeolite membrane of the present invention is provided with a zeolite membrane having an oxygen 8-membered ring structure on the surface of the zeolite membrane having an oxygen 12-membered ring structure formed on a support such as porous alumina as described above. It is what has been.
本発明の複合ゼオライトにおいて、酸素１２員環構造を有するゼオライト膜が、ＦＡＵ型ゼオライト膜により構成され、酸素８員環を有するゼオライト膜が、ＣＨＡ型ゼオライトまたはＭＥＲ型ゼオライト膜、好ましくはＣＨＡ型ゼオライトにより構成されることが好ましい。 In the composite zeolite of the present invention, the zeolite membrane having an oxygen 12-membered ring structure is constituted by a FAU type zeolite membrane, and the zeolite membrane having an oxygen 8-membered ring is a CHA type zeolite or MER type zeolite membrane, preferably a CHA type zeolite. It is preferable that it is comprised.
ここで、Ｙ型ゼオライト（ＦＡＵ）は、天然ゼオライトであるホージャサイトと同じ結晶構造を有するゼオライトであり、酸素の１２員環を含む多面体によって形成されているとともに、酸素１２員環の細孔径は０．７４ｎｍであることが知られている。 Here, Y-type zeolite (FAU) is a zeolite having the same crystal structure as faujasite, which is a natural zeolite, and is formed by a polyhedron including a 12-membered ring of oxygen. It is known to be 0.74 nm.
一方、ＣＨＡ型ゼオライトは、その細孔が酸素８員環を含む多面体によって形成されているとともに、酸素８員環の細孔径は０．３８ｎｍであることが知られている。このような構造上の特徴を有するＣＨＡ型ゼオライトは、ゼオライトの中では比較的細孔径が小さいものである。 On the other hand, CHA-type zeolite is known to have a pore formed by a polyhedron containing an oxygen 8-membered ring, and the pore diameter of the oxygen 8-membered ring is 0.38 nm. The CHA-type zeolite having such structural characteristics has a relatively small pore size among zeolites.
また、本発明の複合ゼオライト膜において、転換処理を行う前の酸素１２員環構造を有するゼオライト膜の膜厚は、高い膜透過度を維持するために、１０μｍ以下が望ましく、０．１μｍ〜１０μｍが好ましい。また転換した酸素８員環構造を有するゼオライト層の膜厚は、耐久性の観点からは１０ｎｍ以上、膜透過度の観点からは２μｍ以下が好ましい。 Further, in the composite zeolite membrane of the present invention, the thickness of the zeolite membrane having an oxygen 12-membered ring structure before the conversion treatment is desirably 10 μm or less, and preferably 0.1 μm to 10 μm in order to maintain high membrane permeability. Is preferred. The film thickness of the converted zeolite layer having an oxygen 8-membered ring structure is preferably 10 nm or more from the viewpoint of durability and 2 μm or less from the viewpoint of membrane permeability.
本発明による複合ゼオライト膜の製造方法は、酸素１２員環構造を有するゼオライト粉末を添加したアルカリ水溶液中に、支持体上に製膜された酸素１２員環構造を有するゼオライト膜を浸漬し、所定の条件下で加熱加圧処理することで、支持体上に製膜された酸素１２員環構造を有するゼオライト膜の表面の一部を、酸素８員環構造を有するゼオライト膜に転換させることにより、酸素１２員環構造を有するゼオライト膜の表面に酸素８員環構造を有するゼオライト膜が設けられた複合ゼオライト膜を形成することを特徴とする。 In the method for producing a composite zeolite membrane according to the present invention, a zeolite membrane having an oxygen 12-membered ring structure formed on a support is immersed in an alkaline aqueous solution to which zeolite powder having an oxygen 12-membered ring structure is added, By converting the part of the surface of the zeolite membrane having an oxygen 12-membered ring structure formed on the support into a zeolite membrane having an oxygen 8-membered ring structure by heat and pressure treatment under the conditions of The composite zeolite membrane is characterized in that a zeolite membrane having an oxygen 8-membered ring structure is formed on the surface of the zeolite membrane having an oxygen 12-membered ring structure.
本発明による複合ゼオライト膜の製造方法において、酸素１２員環構造を有するゼオライト粉末を０．０１〜２０ｗｔ％、好ましくは１〜１０ｗｔ％の割合で添加した０．０１〜３ｍｏｌ／Ｌ、好ましくは０．１〜１ｍｏｌ／Ｌの水酸化カリウム水溶液中に、支持体上に製膜された酸素１２員環構造を有するゼオライト膜を浸漬し、温度８０〜１５０℃、好ましくは９５〜１２５℃、圧力０．０５〜２ＭＰａ、好ましくは０．１〜１ＭＰａの条件下で、１〜１２０時間、好ましくは６〜３６時間、加熱加圧処理することが好ましい。 In the method for producing a composite zeolite membrane according to the present invention, a zeolite powder having an oxygen 12-membered ring structure is added in an amount of 0.01 to 20 wt%, preferably 1 to 10 wt%, and 0.01 to 3 mol / L, preferably 0. A zeolite membrane having an oxygen 12-membered ring structure formed on a support is immersed in a 1 to 1 mol / L potassium hydroxide aqueous solution, and the temperature is 80 to 150 ° C., preferably 95 to 125 ° C., and the pressure is 0 It is preferable to heat and pressure-treat under the condition of 0.05 to 2 MPa, preferably 0.1 to 1 MPa for 1 to 120 hours, preferably 6 to 36 hours.
本発明による複合ゼオライト膜の製造方法において、酸素１２員環構造を有するゼオライト膜が、ＦＡＵ型ゼオライト膜により構成され、酸素８員環を有するゼオライト膜が、ＣＨＡ型ゼオライト膜により構成されることが、特に、好ましい。 In the method for producing a composite zeolite membrane according to the present invention, the zeolite membrane having an oxygen 12-membered ring structure is constituted by a FAU type zeolite membrane, and the zeolite membrane having an oxygen 8-membered ring is constituted by a CHA type zeolite membrane. Particularly preferred.
本発明によれば、多孔質アルミナ管等の基体上に製膜したＦＡＵ型ゼオライト膜の表面を、酸素８員環構造を有するゼオライト膜に転換させることにより、従来の合成方法に比べて、酸素８員環構造を有するゼオライト膜層の大幅な薄膜化が可能であり、分子篩機能を付与した複合ゼオライト膜を合成することができる。 According to the present invention, the surface of a FAU-type zeolite membrane formed on a substrate such as a porous alumina tube is converted to a zeolite membrane having an oxygen 8-membered ring structure, so that oxygen can be produced compared to conventional synthesis methods. A zeolite membrane layer having an eight-membered ring structure can be greatly reduced in thickness, and a composite zeolite membrane having a molecular sieve function can be synthesized.
特に、基体上に製膜したＦＡＵ膜表面のみを、８員環ゼオライトに転換させることで、高い膜透過度を維持したまま分子篩能を維持させる。さらに高い膜透過度を維持するためには、転換処理を行う前のＦＡＵ型ゼオライト膜の膜厚は、０．１μｍ〜１０μｍが望ましい。また転換した８員環構造を有するＣＨＡ型ゼオライト層の膜厚については、耐久性の観点からは１０ｎｍ以上、膜透過度の観点からは２μｍ以下が好ましい。 In particular, the molecular sieving ability is maintained while maintaining high membrane permeability by converting only the FAU membrane surface formed on the substrate into 8-membered ring zeolite. In order to maintain a higher membrane permeability, the film thickness of the FAU type zeolite membrane before the conversion treatment is desirably 0.1 μm to 10 μm. The film thickness of the converted CHA-type zeolite layer having an 8-membered ring structure is preferably 10 nm or more from the viewpoint of durability and 2 μm or less from the viewpoint of membrane permeability.
ここで、ゼオライト層の膜厚は、断面を電子顕微鏡によって観察するか、または、ゼオライト膜表面から所定の厚さの層を研削・除去した後、ＸＲＤ（Ｘ線回折）パターンを調べることによって測定することができる。 Here, the thickness of the zeolite layer is measured by observing a cross section with an electron microscope or by examining a XRD (X-ray diffraction) pattern after grinding and removing a layer having a predetermined thickness from the surface of the zeolite membrane. can do.
つぎに、本発明の実施例を説明するが、本発明は、これらの実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples.
実施例１
本実施例では、定法により、多孔質アルミナ管（基体）（Hitz日立造船社製）表面にＦＡＵ型ゼオライト粉末（種結晶）（東ソー社製）の懸濁水溶液を塗布乾燥したのち、温度１００℃で４．７５時間、水熱合成させることによってＦＡＵ型ゼオライト膜を合成した。転換処理を行う前の多孔質アルミナ管表面のＦＡＵ型ゼオライト膜の膜厚は、２〜６μｍであった。Example 1
In this example, a suspension of FAU-type zeolite powder (seed crystal) (manufactured by Tosoh Corporation) was applied and dried on the surface of a porous alumina tube (substrate) (manufactured by Hitachi Zosen) by a conventional method, and then the temperature was 100 ° C. The FAU type zeolite membrane was synthesized by hydrothermal synthesis for 4.75 hours. The film thickness of the FAU type zeolite membrane on the surface of the porous alumina tube before the conversion treatment was 2 to 6 μm.
つぎに、本発明のゼオライト膜の転換処理により、本発明による複合ゼオライト膜を、つぎのようにして製造した。 Next, the composite zeolite membrane according to the present invention was produced as follows by the conversion treatment of the zeolite membrane of the present invention.
すなわち、オートクレーブ内で、ＦＡＵ型ゼオライト粉末を、１０ｗｔ％の割合で添加した０．５ｍｏｌ／Ｌの水酸化カリウム水溶液中に、上記多孔質アルミナ管よりなる支持体上に製膜された酸素１２員環構造を有するＦＡＵ型ゼオライト膜を浸漬し、温度９５℃、圧力０．１ＭＰａの条件下で、２４時間、静置することで加熱加圧処理し、支持体上に製膜されたＦＡＵ型ゼオライト膜の表面を、酸素８員環構造を有するＣＨＡ型ゼオライト膜に転換させることにより、ＦＡＵ型ゼオライト膜の表面にＣＨＡ型ゼオライト膜が設けられた複合ゼオライト膜を形成した。 In other words, in an autoclave, a 12-membered oxygen film formed on a support made of the above porous alumina tube in a 0.5 mol / L potassium hydroxide aqueous solution to which FAU type zeolite powder was added at a rate of 10 wt%. FAU-type zeolite film immersed on a support, immersed in a FAU-type zeolite membrane having a ring structure, left to stand for 24 hours under conditions of a temperature of 95 ° C. and a pressure of 0.1 MPa. By converting the surface of the membrane to a CHA-type zeolite membrane having an oxygen 8-membered ring structure, a composite zeolite membrane in which a CHA-type zeolite membrane was provided on the surface of the FAU-type zeolite membrane was formed.
本発明の方法によれば、多孔質アルミナ管（基体）上に製膜した酸素１２員環構造を有するＦＡＵ型ゼオライト膜の表面のみを、酸素８員環構造を有するＣＨＡ型ゼオライト膜に転換させることで、高い膜透過度を維持したまま分子篩能を付与したゼオライト膜を合成することができた。なお、転換した酸素８員環構造を有するゼオライト層の膜厚は、０．０１〜２μｍであると推定され、酸素８員環構造を有するＣＨＡ型ゼオライト膜層の大幅な薄膜化を果たすことができた。 According to the method of the present invention, only the surface of a FAU type zeolite membrane having an oxygen 12-membered ring structure formed on a porous alumina tube (substrate) is converted into a CHA type zeolite membrane having an oxygen 8-membered ring structure. Thus, it was possible to synthesize a zeolite membrane imparted with molecular sieving ability while maintaining high membrane permeability. The film thickness of the converted zeolite layer having an oxygen 8-membered ring structure is estimated to be 0.01-2 μm, and the CHA-type zeolite membrane layer having an oxygen 8-membered ring structure can be greatly thinned. did it.
ここで、図１Ａは、転換処理前後のＦＡＵ型ゼオライト粉末のＸＲＤ（Ｘ線回折）パターンを示すグラフである。図１Ｂは、アルミナ支持体上に製膜された酸素１２員環構造を有するＦＡＵ型ゼオライト膜表面を、酸素８員環構造を有するＣＨＡ型ゼオライト膜に転換させ、その転換処理前後のＸＲＤパターンを示すグラフである。 Here, FIG. 1A is a graph showing XRD (X-ray diffraction) patterns of the FAU-type zeolite powder before and after the conversion treatment. FIG. 1B shows that the surface of an FAU type zeolite membrane having an oxygen 12-membered ring structure formed on an alumina support is converted into a CHA type zeolite membrane having an oxygen 8-membered ring structure, and XRD patterns before and after the conversion treatment are converted. It is a graph to show.
同図に示すＸＲＤ測定の結果より、ＦＡＵ型ゼオライト膜（細孔径０．７４ｎｍ）を上記の処理条件で２４時間、加熱加圧処理することで、酸素１２員環構造を有するＦＡＵ型ゼオライト膜（細孔径０．７４ｎｍ）の表面を、酸素８員環構造を有するＣＨＡ型ゼオライト膜（細孔径０．３８ｎｍ）に転換したＣＨＡ／ＦＡＵ複合ゼオライト膜を合成できることが確認された。 From the results of the XRD measurement shown in the figure, a FAU type zeolite membrane having an oxygen 12-membered ring structure is obtained by subjecting the FAU type zeolite membrane (pore diameter 0.74 nm) to heat and pressure treatment under the above treatment conditions for 24 hours. It was confirmed that a CHA / FAU composite zeolite membrane in which the surface having a pore diameter of 0.74 nm was converted to a CHA-type zeolite membrane having an oxygen 8-membered ring structure (pore diameter: 0.38 nm) could be synthesized.
また、同図に示すように、同条件で処理時間を長くすると、多孔質アルミナ管上のＦＡＵ型ゼオライト膜は、最終的には、完全なＣＨＡ型ゼオライト膜に転換するが、処理条件を変えることで、ＭＥＲ型ゼオライト膜など他の８員環ゼオライトへの転換も可能である。 Moreover, as shown in the figure, when the treatment time is lengthened under the same conditions, the FAU type zeolite membrane on the porous alumina tube is finally converted into a complete CHA type zeolite membrane, but the treatment conditions are changed. Thus, conversion to other 8-membered ring zeolite such as MER type zeolite membrane is also possible.
また図２は、従来型のゼオライト膜構造と、本発明の複合ゼオライト膜構造を示す部分拡大断面図である。 FIG. 2 is a partially enlarged sectional view showing a conventional zeolite membrane structure and a composite zeolite membrane structure of the present invention.
同図に示すように、本発明によれば、酸素１２員環構造を有するＦＡＵ型ゼオライト膜の表面のみが、酸素８員環構造を有するゼオライト膜に転換されるため、従来の合成方法に比べて、酸素８員環構造を有するゼオライト膜層の大幅な薄膜化が可能である。 As shown in the figure, according to the present invention, only the surface of the FAU type zeolite membrane having an oxygen 12-membered ring structure is converted to a zeolite membrane having an oxygen 8-membered ring structure, so that it is compared with the conventional synthesis method. Thus, the zeolite membrane layer having an oxygen 8-membered ring structure can be greatly reduced in thickness.
つぎに図３は、ゼオライト膜の透過分離性能の試験装置のフローシートであり、この装置を用いてゼオライト膜の透過分離性能の評価として、水−ＩＰＡの蒸気透過分離試験を行った。 Next, FIG. 3 is a flow sheet of a test apparatus for permeation separation performance of a zeolite membrane, and a water-IPA vapor permeation separation test was performed as an evaluation of the permeation separation performance of the zeolite membrane using this apparatus.
同図に示すように、まず長さ３ｃｍに切断した管状の膜を、ステンレス製の膜モジュールにグラファイトリングを用いて取り付けた。その後、膜モジュールを恒温槽内に設置し、所定の温度に保持した。さらに、ポンプを用いて水−ＩＰＡの混合液１ｍｌ／ｍｉｎにて送液し、恒温槽内にて気化した蒸気を膜の外側に供給した。膜を透過しなかった成分は、凝縮後、再度ポンプにて送液し、ゼオライト膜の外側を循環させ、１〜２０時間後に、その組成をＧＣ（ガスクロマトグラフ）により測定した。また膜の内側は真空ポンプして減圧し、膜を透過する成分を液体窒素にて冷却したトラップにて捕集し、その重量および組成を測定した。水の透過量は、単位面積、単位時間、単位圧力あたりに透過する水の物質量である水透過度［ｍｏｌ／（ｍ２・ｓ・Ｐａ）］にて評価した。As shown in the figure, a tubular membrane cut to a length of 3 cm was first attached to a stainless steel membrane module using a graphite ring. Then, the membrane module was installed in a thermostat and kept at a predetermined temperature. Further, the solution was fed at a rate of 1 ml / min of a water-IPA mixed solution using a pump, and vapor vaporized in the thermostat was supplied to the outside of the membrane. The components that did not permeate the membrane were condensed and then pumped again to circulate the outside of the zeolite membrane. After 1 to 20 hours, the composition was measured by GC (gas chromatograph). The inside of the membrane was depressurized by a vacuum pump, and components that permeated the membrane were collected by a trap cooled with liquid nitrogen, and the weight and composition were measured. The amount of water permeated was evaluated by water permeability [mol / (m 2 · s · Pa)], which is the amount of water permeated per unit area, unit time, and unit pressure.
なお、分離性能の評価としては、下記式で定義する水分離係数：αにより評価した。 In addition, as evaluation of separation performance, it evaluated by the water separation coefficient: (alpha) defined by a following formula.
水分離係数：α＝（ＰＡ／ＰＢ）／（ＦＡ／ＦＢ）
上記式中、ＦＡ，ＦＢはそれぞれ供給蒸気中のＡ、Ｂの濃度（ｗｔ％）、ＰＡ，ＰＢはそれぞれ透過蒸気中のＡ，Ｂの濃度（ｗｔ％）を意味する。Water separation factor: α = (P A / P B ) / (F A / F B )
In the above formulas, F A and F B mean the concentrations (wt%) of A and B in the supplied steam, and P A and P B mean the concentrations (wt%) of A and B in the permeated steam, respectively.
図４に、本発明の方法により、ＦＡＵ型ゼオライト膜表面をＣＨＡ型に転換したＣＨＡ／ＦＡＵ複合膜の水−ＩＰＡ蒸気透過分離試験の結果（膜温度１３０ｏＣ、常圧）を示した。ＩＰＡの脱水濃縮とともに、ＦＡＵ型膜ではＩＰＡの透過量が増大することにより、水分離係数が５００から１００程度まで大きく低下したのに対し、膜表面をＣＨＡ型に転換したＣＨＡ／ＦＡＵ複合膜では、５００程度の高い水分離係数が維持された。FIG. 4 shows the results of the water-IPA vapor permeation separation test (membrane temperature 130 ° C., normal pressure) of the CHA / FAU composite membrane in which the surface of the FAU type zeolite membrane is converted to the CHA type by the method of the present invention. With the dehydration concentration of IPA, the amount of IPA permeation increased in the FAU type membrane, so that the water separation factor decreased greatly from about 500 to about 100, whereas in the CHA / FAU composite membrane whose membrane surface was converted to CHA type A high water separation factor of about 500 was maintained.
また水の透過性についても、ＣＨＡ／ＦＡＵ複合膜で、１０−６ｍｏｌ／（ｍ２・ｓ・Ｐａ）を超える高い水透過度を得ることができた。これは拡散抵抗となる酸素８員環構造を有するＣＨＡ型ゼオライト膜層が非常に薄いことに加え、分子篩能付与により、水の透過阻害となるＩＰＡが膜内部に侵入することを抑制できることなどが起因していると考えられる。Moreover, also about the water permeability, the high water permeability exceeding 10 <-6 > mol / (m < 2 > * s * Pa) was able to be obtained with the CHA / FAU composite membrane. This is because the CHA-type zeolite membrane layer having an oxygen 8-membered ring structure that provides diffusion resistance is very thin, and IPA that inhibits water permeation can be prevented from entering the membrane by providing molecular sieving ability. It is thought to be caused.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012537615A JP5852963B2 (en) | 2010-10-06 | 2011-09-13 | Composite zeolite membrane and method for producing the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010226832 | 2010-10-06 | ||
| JP2010226832 | 2010-10-06 | ||
| PCT/JP2011/070788 WO2012046545A1 (en) | 2010-10-06 | 2011-09-13 | Composite zeolite film and process for production thereof |
| JP2012537615A JP5852963B2 (en) | 2010-10-06 | 2011-09-13 | Composite zeolite membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2012046545A1 JPWO2012046545A1 (en) | 2014-02-24 |
| JP5852963B2 true JP5852963B2 (en) | 2016-02-03 |
Family
ID=45927542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012537615A Active JP5852963B2 (en) | 2010-10-06 | 2011-09-13 | Composite zeolite membrane and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5852963B2 (en) |
| WO (1) | WO2012046545A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5779397B2 (en) * | 2011-05-11 | 2015-09-16 | 日立造船株式会社 | Carbon dioxide membrane separation system in coal gasification process, and coal gasification combined power generation facility using the same |
| JP2014198308A (en) * | 2013-03-29 | 2014-10-23 | 日本碍子株式会社 | Ceramic separation filter and dehydration method |
| JP6785483B2 (en) * | 2013-09-30 | 2020-11-18 | 国立研究開発法人産業技術総合研究所 | Composite membrane with zeolite thin film and its manufacturing method |
| JP2015186776A (en) * | 2014-03-26 | 2015-10-29 | 三菱化学株式会社 | Zeolite membrane evaluation method |
| WO2016006564A1 (en) * | 2014-07-10 | 2016-01-14 | 日立造船株式会社 | Zeolite membrane, production method therefor, and separation method using same |
| US9938157B2 (en) * | 2014-07-23 | 2018-04-10 | Chevron U.S.A. Inc. | Interzeolite transformation and metal encapsulation in the absence of an SDA |
| JP6729387B2 (en) | 2014-11-25 | 2020-07-22 | 三菱ケミカル株式会社 | Porous support-zeolite membrane composite and method for producing porous support-zeolite membrane composite |
| JP6670825B2 (en) | 2015-03-31 | 2020-03-25 | 日本碍子株式会社 | Zeolite membrane structure and method for producing the same |
| JP6911354B2 (en) * | 2016-01-12 | 2021-07-28 | 東ソー株式会社 | Method for producing CHA-type zeolite |
| JP6861273B2 (en) | 2017-03-31 | 2021-04-21 | 日本碍子株式会社 | Zeolite Membrane Complex and Method for Producing Zeolite Membrane Complex |
| CN113490541B (en) * | 2019-03-04 | 2023-06-27 | 日本碍子株式会社 | Zeolite membrane composite, method for producing zeolite membrane composite, and separation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004532095A (en) * | 2001-02-17 | 2004-10-21 | アーフロウシステムズ・ゲーエムベーハー・ウント・コー・カーゲー | Filter body |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5569901B2 (en) * | 2009-06-08 | 2014-08-13 | 独立行政法人産業技術総合研究所 | Zeolite membrane, separation membrane module and manufacturing method thereof |
-
2011
- 2011-09-13 JP JP2012537615A patent/JP5852963B2/en active Active
- 2011-09-13 WO PCT/JP2011/070788 patent/WO2012046545A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004532095A (en) * | 2001-02-17 | 2004-10-21 | アーフロウシステムズ・ゲーエムベーハー・ウント・コー・カーゲー | Filter body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012046545A1 (en) | 2014-02-24 |
| WO2012046545A1 (en) | 2012-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5852963B2 (en) | Composite zeolite membrane and method for producing the same | |
| EP3167953B1 (en) | Zeolite membrane, production method therefor, and separation method using same | |
| US11731077B2 (en) | Method of gas separation using metal-organic framework membrane | |
| JP5569901B2 (en) | Zeolite membrane, separation membrane module and manufacturing method thereof | |
| Zhang et al. | Pervaporation dehydration of acetic acid through hollow fiber supported DD3R zeolite membrane | |
| JP2008074695A (en) | Porous substrate with seed crystal-containing layer for manufacturing zeolite membrane, zeolite membrane and method for manufacturing zeolite membrane | |
| JP4204273B2 (en) | DDR type zeolite membrane composite and method for producing the same | |
| US20210220779A1 (en) | Zeolite separation membrane and production method therefor | |
| Zhang et al. | Synthesis of silicalite-1 membranes with high ethanol permeation in ultradilute solution containing fluoride | |
| Raza et al. | HCl modification and pervaporation performance of BTESE membrane for the dehydration of acetic acid/water mixture | |
| Huang et al. | Stepwise synthesis of sandwich-structured composite zeolite membranes with enhanced separation selectivity | |
| WO2020195105A1 (en) | Zeolite membrane composite body, method for producing zeolite membrane composite body, method for processing zeolite membrane composite body, and separation method | |
| Zeynali et al. | Experimental evaluation of graphene oxide/TiO2-alumina nanocomposite membranes performance for hydrogen separation | |
| JP2007313390A (en) | Phillipsite type zeolite composite membrane and its manufacturing method | |
| JP2007313389A (en) | Marinoite type zeolite composite membrane and its manufacturing method | |
| Kong et al. | Preparation of silicalite-1 membranes on stainless steel supports by a two-stage varying-temperature in situ synthesis | |
| Banihashemi et al. | B-oriented MFI zeolite membranes for xylene isomer separation-Effect of xylene activity on separation performance | |
| JP2006326490A (en) | Inorganic separation membrane and its production method | |
| WO2017115454A1 (en) | Zeolite membrane composite body, method for producing same and gas separation method | |
| JP7321260B2 (en) | Zeolite membrane composite, manufacturing method thereof, and fluid separation method | |
| WO2010125898A1 (en) | Separation membrane for concentration of hydrochloric acid, method for concentration of hydrochloric acid, and apparatus for concentration of hydrochloric acid | |
| WO2017081841A1 (en) | Crystalline silica membrane complex and method for producing same, and fluid separation method | |
| Kiyozumi et al. | Synthesis of acid-resistant Phillipsite (PHI) membrane and its pervaporation performance | |
| JP2006176399A (en) | Phillipsite-type-zeolite membrane and its manufacturing method | |
| JP4348431B2 (en) | High silica type CDS-1 zeolite membrane and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AA64 | Notification of invalidation of claim of internal priority (with term) |
Free format text: JAPANESE INTERMEDIATE CODE: A241764 Effective date: 20130625 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150811 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150930 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20151110 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20151207 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5852963 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |