JPS63291809A - Production of film-shaped synthetic zeolite - Google Patents
Production of film-shaped synthetic zeoliteInfo
- Publication number
- JPS63291809A JPS63291809A JP62126954A JP12695487A JPS63291809A JP S63291809 A JPS63291809 A JP S63291809A JP 62126954 A JP62126954 A JP 62126954A JP 12695487 A JP12695487 A JP 12695487A JP S63291809 A JPS63291809 A JP S63291809A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- zeolite
- source
- film
- hydrothermal reaction
- 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.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000012528 membrane Substances 0.000 abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 19
- 239000007789 gas Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000758 substrate Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- -1 polydimethylsiloxane Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052665 sodalite Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
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
- 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
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は膜状合成ゼオライトの製造方法に関し、詳しく
はアルミナ多孔質担体上にゼオライトを膜状に形成して
、気体分離膜等に利用できる膜状の合成ゼオライトを効
率良く製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a synthetic zeolite in the form of a membrane, and more specifically, a method for producing zeolite in the form of a membrane on a porous alumina carrier, which can be used for gas separation membranes, etc. The present invention relates to a method for efficiently producing membrane-like synthetic zeolite.
〔従来の技術及び発明が解決しようとする問題点〕従来
から、気体の分離膜にはポリジメチルシロキサンやセル
ロース誘導体などの高分子材料に代表される有機質材料
が使用されているが、耐熱性。[Prior art and problems to be solved by the invention] Conventionally, organic materials such as polymeric materials such as polydimethylsiloxane and cellulose derivatives have been used for gas separation membranes, but they lack heat resistance.
耐久性さらには分離の際の気体の選択性や気体の透過速
度などに問題が残されている。Problems remain in durability, gas selectivity during separation, gas permeation rate, etc.
近年、このような有機質材料の問題点を解決するために
、無機質材料の気体分離膜が研究されつつあり、その中
でも膜状のゼオライトが注目されている。これまでに開
発された膜状ゼオライトの製造方法としては、アルミナ
基板をアルカリ処理した後、水ガラス、水酸化ナトリウ
ム溶液に浸漬し、引き上げたものをオートクレーブで処
理する方法（特開昭６０−１２９１１９号公報）、ある
いはアルミナ基板上にシリカの薄膜をコーティングし、
アルカリ処理後オートクレーブ中で加熱する方法（特開
昭６０−２８８２６号公報）などがある。In recent years, in order to solve the problems of organic materials, gas separation membranes made of inorganic materials have been studied, and among them, membrane-shaped zeolites are attracting attention. The method for producing membrane zeolite that has been developed so far is to treat an alumina substrate with alkali, immerse it in water glass or sodium hydroxide solution, and then treat it in an autoclave (Japanese Patent Laid-Open No. 129119/1989). (No. Publication), or by coating a thin film of silica on an alumina substrate,
There is a method of heating in an autoclave after alkali treatment (Japanese Unexamined Patent Publication No. 60-28826).
しかし、これらの方法で得られる膜状ゼオライトは、い
ずれも膜にピンホールが生じたり、膜厚が均一にならな
いなどの欠点をあった。However, the membrane zeolites obtained by these methods all have drawbacks such as pinholes in the membrane and non-uniform membrane thickness.
（問題点を解決するための手段〕
本発明者は、上述の如き従来方法で得られる膜状ゼオラ
イトの欠点を解消し、膜厚が均一で、しかもピンホール
などのない緻密な膜状ゼオライトを効率よく製造する方
法を開発すべく鋭意研究を重ねた。(Means for Solving the Problems) The present inventor has solved the drawbacks of the membrane zeolite obtained by the conventional method as described above, and has created a dense membrane zeolite with a uniform thickness and no pinholes. We conducted extensive research to develop an efficient manufacturing method.
その結果、ゼオライトの製造原料を含む水性混合物を、
アルミナ多孔質担体の存在下で水熱反応させることによ
って、上記課題を解決しうろことを見出した。本発明は
かかる知見に基いて完成したものである。As a result, the aqueous mixture containing the raw materials for zeolite production is
We have solved the above problems by conducting a hydrothermal reaction in the presence of an alumina porous carrier. The present invention was completed based on this knowledge.
すなわち、本発明は少なくとも（Ａ）シリカ源および（
Ｂ）アルカリ金属源あるいはアルカリ土類金属源を含む
水性混合物を、アルミナ多孔質担体の存在下で水熱反応
させることを特徴とする膜状合成ゼオライトの製造方法
を提供するものである。That is, the present invention provides at least (A) a silica source and (
B) Provides a method for producing a membranous synthetic zeolite characterized by subjecting an aqueous mixture containing an alkali metal source or an alkaline earth metal source to a hydrothermal reaction in the presence of an alumina porous carrier.
本発明の方法に用いられる水性混合物には、ゼオライト
の製造原料のうちの少な（とも二成分、つまり（Ａ）シ
リカ源および（Ｂ）アルカリ金属源あるいはアルカリ土
類金属源が含有されている。The aqueous mixture used in the method of the present invention contains a small amount of two of the raw materials for producing zeolite, namely (A) a silica source and (B) an alkali metal source or an alkaline earth metal source.
また、この水性混合物には、（Ｃ）アルミナ源を含有さ
せることもできるが、これは水熱反応の反応系に存在さ
せるアルミナ多孔質担体で代用できるため、必ずしも必
要としない。Further, this aqueous mixture can also contain (C) an alumina source, but this is not necessarily necessary since it can be substituted with an alumina porous carrier that is present in the reaction system of the hydrothermal reaction.
上記（Ａ）シリカ源（ケイ素源）としては様々なものが
使用可能であり、例えばシリカ粉末、珪酸、コロイド状
シリカ、溶解シリカなどをあげることができる。この溶
解シリカとしては、酸化ナトリウムまたは酸化カリウム
１モルに対して酸化ケイ素１〜５モルを含有する水ガラ
ス珪酸、アルカリ金属珪酸塩などがある。ここで、シリ
カ源として上述の溶解シリカなどを用いれば、（Ｂ）成
分であるアルカリ金属源を兼ねることができる。Various sources can be used as the silica source (A), such as silica powder, silicic acid, colloidal silica, and dissolved silica. Examples of the dissolved silica include water glass silicates and alkali metal silicates containing 1 to 5 moles of silicon oxide per mole of sodium oxide or potassium oxide. Here, if the above-mentioned dissolved silica or the like is used as the silica source, it can also serve as the alkali metal source which is the component (B).
一方、（Ｂ）アルカリ土類金属源としては、塩化ナトリ
ウム、塩化カリウム、塩化カルシウム。On the other hand, (B) alkaline earth metal sources include sodium chloride, potassium chloride, and calcium chloride.
塩化マグネシウム等様々なものをあげることができる。Various substances can be mentioned, such as magnesium chloride.
また、必要に応じて用いる（Ｃ）アルミナ源（アルミニ
ウム源）としては種々あるが、硫酸アルミニウム、アル
ミン酸ナトリウム、コロイド状アルミナ、アルミナ等を
あげることができる。ここで、アルミナ源としてアルミ
ン酸ナトリウムなどを用いれば、上述のアルカリ金属源
を兼ねることができる。There are various types of alumina source (aluminum source) (C) that can be used as needed, and examples include aluminum sulfate, sodium aluminate, colloidal alumina, and alumina. Here, if sodium aluminate or the like is used as the alumina source, it can also serve as the above-mentioned alkali metal source.
本発明の方法に用いられる水性混合物には、上記の各成
分が含有されているが、（Ａ）、 （Ｂ）、 （Ｃ）成
分の合計量に対する各威容の割合は、通常は（Ａ）成分
であるシリカ源をＳｉｎｇに換算して１〜８０モル％、
好ましくは１５〜４０モル％であり、（Ｂ）成分である
アルカリ土類金属源をＭ 、、ｆｉＯ（Ｍはアルカリ金
属またはアルカリ土類金属を示し、ｎはＭの原子価を示
す。）に換算して２０〜９９モル％、好ましくは２０〜
５０モル％である。The aqueous mixture used in the method of the present invention contains each of the above components, but the proportion of each component to the total amount of components (A), (B), and (C) is usually (A). The silica source as a component is converted to Sing and is 1 to 80 mol%,
It is preferably 15 to 40 mol %, and the alkaline earth metal source as component (B) is M, , fiO (M represents an alkali metal or an alkaline earth metal, and n represents the valence of M). 20 to 99 mol%, preferably 20 to 99 mol%
It is 50 mol%.
また、（Ｃ）成分であるアルミナ源をＡ ｌ ｚ Ｏ３
に換算して０〜２０モル％、好ましくは５〜１５モル％
である。In addition, the alumina source which is the component (C) is A l z O3
0 to 20 mol%, preferably 5 to 15 mol% in terms of
It is.
さらに、この水性混合物中の各成分の濃度は、水／ Ｍ
２／、 Ｏとして２０〜３００（モル比）となるよう
な範囲を目安として定めればよい。Furthermore, the concentration of each component in this aqueous mixture is water/M
2/, O may be set in a range of 20 to 300 (mole ratio) as a guide.
ところで、本発明の方法は、上記の水性混合物をアルミ
ナ多孔質担体の存在下で水熱反応させるわけであるが、
このアルミナ多孔質担体としては、−ａに数十乃至数千
人の細孔を有し、アルカリで溶解できるアルミナ、例え
ばγ−９θ−１χ−９に一９δ−あるいはα−アルミナ
などが好適に用いられる。また、このアルミナ多孔質担
体は、通常はγ−３θ−１χ−９に一１δ−あるいはα
−アルミナまたはベーマイトアルミナなどの各種アルミ
ナを２０〜２０００ｋｇ／ｃｔＡで圧縮成形し、５００
〜１２００°Ｃで焼成することによって得られる。なお
、水熱反応の反応系に存在させる上記アルミナ多孔質担
体の量は特に制限はなく、要するに水性混合物が反応し
てその上にゼオライトの結晶が薄膜状に形成されるに足
る量であればよい。By the way, in the method of the present invention, the above aqueous mixture is subjected to a hydrothermal reaction in the presence of an alumina porous carrier.
As this alumina porous carrier, alumina having tens to thousands of pores and soluble in alkali, such as γ-9θ-1χ-9-9δ- or α-alumina, is preferable. used. In addition, this alumina porous support is usually γ-3θ-1χ-9, -1δ- or α
- Compression molding of various aluminas such as alumina or boehmite alumina at 20 to 2000 kg/ctA,
Obtained by firing at ~1200°C. There is no particular limit to the amount of the alumina porous carrier present in the reaction system of the hydrothermal reaction, as long as the amount is sufficient to cause the aqueous mixture to react and form a thin film of zeolite crystals thereon. good.
また、水熱反応の条件は、ゼオライトが生成するに必要
な温度、圧力および時間で加熱すればよい。具体的には
温度４０〜１２０°Ｃ２圧力Ｏ〜１０ｋｇ／ｃｆｆｌＧ
の範囲で３０分〜６時間撹拌処理することが好ましい。Moreover, the conditions for the hydrothermal reaction may be heating at a temperature, pressure, and time necessary to generate zeolite. Specifically, temperature 40-120°C2 pressure O-10kg/cfflG
It is preferable to stir the mixture for 30 minutes to 6 hours.
雰囲気は必要により不活性ガスで置換してもよい。さら
に、水熱反応に先立って予めアルミナ多孔質担体をアル
カリで浸漬処理しておくと、水性混合物中のアルカリ土
類金属源の量を減らすことができ経済的であるとともに
、水熱反応の時間も短くてすみ、しかも生成するゼオラ
イトも緻密なものとなる。The atmosphere may be replaced with an inert gas if necessary. Furthermore, if the porous alumina support is immersed in an alkali prior to the hydrothermal reaction, it is economical to reduce the amount of alkaline earth metal source in the aqueous mixture, and it also reduces the time required for the hydrothermal reaction. The length can be shortened, and the zeolite produced is also dense.
以上のように、アルミナ多孔質担体の存在下で水熱反応
を行うと、該担体上に合成ゼオライト、特にＡ型、ソー
ダライト型あるいはＸ型の合成ゼオライトが厚さ１００
人〜１００μｍの薄膜状に形成される。なお、この水熱
反応にあたっては、水性媒体中にはゼオライトの生成は
全く認められず、アルミナ多孔質担体上に選択的にゼオ
ライトが生成する。As described above, when a hydrothermal reaction is carried out in the presence of an alumina porous carrier, synthetic zeolite, especially A-type, sodalite-type or
It is formed into a thin film with a thickness of 100 μm. In this hydrothermal reaction, no zeolite is observed in the aqueous medium, and zeolite is selectively produced on the alumina porous carrier.
次に、本発明を実施例によりさらに詳しく説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ビーカーに水酸化ナトリウム３２．５ｇを水１７２ｄに
溶かした溶液を入れ、シリカゾル（スノーチック１ｓｉ
ｏｚ３０重景％）４．３ｇを添加して３０分間撹拌した
。Example 1 A solution of 32.5 g of sodium hydroxide dissolved in 172 d of water was placed in a beaker, and silica sol (Snowtic 1si
4.3 g of oz30 heavy weight%) were added and stirred for 30 minutes.
次いで、得られた溶液に直径１２閣、厚さ１ ｍｍの円
板状のアルミナ多孔質基板を浸漬し、ビーカーごと恒温
槽に入れ、９５℃で２時間加熱して水熱反応を行った。Next, a disc-shaped alumina porous substrate with a diameter of 12 mm and a thickness of 1 mm was immersed in the obtained solution, and the beaker was placed in a constant temperature bath and heated at 95° C. for 2 hours to perform a hydrothermal reaction.
その結果、アルミナ多孔質基板上にＡ型ゼオライトの膜
が生成していることが、Ｘ線回折から確認された。なお
、溶液中にはゼオライトの存在は全く認められなかった
。As a result, it was confirmed by X-ray diffraction that a film of type A zeolite was formed on the alumina porous substrate. Note that no zeolite was observed in the solution.
実施例２
アルミン酸ナトリウムＣＡＲ／Ｎａ＝ ０．６１（原子
比））１１．６ｇおよび水酸化ナトリウム４．２ｇを水
１００ｍに溶かしてＡ液を調製した。Example 2 Solution A was prepared by dissolving 11.6 g of sodium aluminate (CAR/Na = 0.61 (atomic ratio)) and 4.2 g of sodium hydroxide in 100 ml of water.
次に、ビーカーに水３９−を入れ、撹拌機で激しく撹拌
しながら、これに前記Ａ液とシリカゾル（スノーチック
；Ｓｉ０□３０重世％）５１．３ｇを徐々に添加し、添
加終了後、さらに３０分間撹拌した。Next, water 39- was put in a beaker, and while stirring vigorously with a stirrer, the above-mentioned liquid A and 51.3 g of silica sol (Snowtic; Si0□30%) were gradually added thereto, and after the addition was completed, The mixture was stirred for an additional 30 minutes.
次いで、得られた溶液に実施例１と同様の円板状のアル
ミナ多孔質基板を浸漬し、ビーカーごと恒温槽に入れ、
９５°Ｃで２時間加熱して水熱反応を行った。Next, a disc-shaped alumina porous substrate similar to that in Example 1 was immersed in the obtained solution, and the beaker was placed in a constant temperature bath.
A hydrothermal reaction was carried out by heating at 95°C for 2 hours.
その結果、アルミナ多孔質基板上にＡ型ゼオライトの膜
が生成していることが、Ｘ線回折から確認された。なお
、溶液中にはゼオライトの存在は全く認められなかった
。As a result, it was confirmed by X-ray diffraction that a film of type A zeolite was formed on the alumina porous substrate. Note that no zeolite was observed in the solution.
実施例３
アルミン酸ナトリウム（Ａｌ／Ｎａ＝ ０．５８（原子
比））６．１ｇおよび水酸化ナトリウム９．１ｇを水１
０５＃！１！に溶かしてＡ液とし、また、シリカゾル（
スノーチック； ＳｉＯ□３０重量％）２９．１ｇに水
酸化ナトリウム９ｇを溶かしてＢ液とした。Example 3 6.1 g of sodium aluminate (Al/Na = 0.58 (atomic ratio)) and 9.1 g of sodium hydroxide were added to 1 g of water.
05#! 1! to make solution A, and also silica sol (
Snowtic; 9 g of sodium hydroxide was dissolved in 29.1 g of SiO□30% by weight to prepare liquid B.
次に、ビーカーに水５０ｍ１を入れ、撹拌機で激しく撹
拌しながら、これに前記Ａ液とＢ液をを徐々に添加し、
添加終了後、さらに３０分間撹拌した。Next, put 50ml of water in a beaker, and while stirring vigorously with a stirrer, gradually add the liquids A and B to it,
After the addition was complete, the mixture was stirred for an additional 30 minutes.
次いで、得られた溶液に実施例１と同様の円板状のアル
ミナ多孔質基板を浸漬し、ビーカーごと恒温槽に入れ、
９５°Ｃで２時間加熱して水熱反応を行った。Next, a disc-shaped alumina porous substrate similar to that in Example 1 was immersed in the obtained solution, and the beaker was placed in a constant temperature bath.
A hydrothermal reaction was carried out by heating at 95°C for 2 hours.
その結果、アルミナ多孔質基板上にＡ型ゼオライトの膜
が生成していることが、Ｘ線回折から確認された。なお
、溶液中にはゼオライトの存在は全く認められなかった
。As a result, it was confirmed by X-ray diffraction that a film of type A zeolite was formed on the alumina porous substrate. Note that no zeolite was observed in the solution.
実施例４
実施例１と同様のアルミナ多孔質基板を、１０規定の水
酸化ナトリウム水溶液に８０’Ｃで１０分間浸漬した後
、実施例３で調製した溶液に、このアルミナ多孔質基板
を浸漬し、ビーカーごと恒温槽に入れ、９５℃で２時間
加熱して水熱反応を行った。Example 4 An alumina porous substrate similar to that in Example 1 was immersed in a 10N aqueous sodium hydroxide solution at 80'C for 10 minutes, and then this alumina porous substrate was immersed in the solution prepared in Example 3. The whole beaker was placed in a constant temperature bath and heated at 95° C. for 2 hours to perform a hydrothermal reaction.
その結果、アルミナ多孔質基板上にＡ型ゼオライトの膜
が生成していることが、Ｘ線回折から確認された。また
、これを電子顕微鏡で観察したところ、アルミナ多孔質
基板上にはＡ型ゼオライト膜が緻密に生成しているとか
わかった。このＡ型ゼオライト膜の表面構造の電子顕微
鏡写真を第１図に示す。As a result, it was confirmed by X-ray diffraction that a film of type A zeolite was formed on the alumina porous substrate. Further, when this was observed using an electron microscope, it was found that a type A zeolite film was densely formed on the alumina porous substrate. An electron micrograph of the surface structure of this A-type zeolite membrane is shown in FIG.
なお、溶液中にはゼオライトの存在は全く認められなか
った。Note that no zeolite was observed in the solution.
実施例５
テフロン製の容器に水３３５ｍを入れ、これにアルミン
酸ナトリウム（Ａｆ／Ｎａ＝ ６．１ （原子比））１
１．０８ｇおよび水酸化ナトリウム０、７９ ｇを溶か
し、さらにシリカゾル（スノーチック：５ｉＯｚ３０重
量％）３２．５ｇを、撹拌機で激しく撹拌しながら、徐
々に添加した。添加終了後、さらに１時間撹拌し、容器
ごとオートクレーブで１２０°Ｃ，２時間加熱して水熱
反応を行った。Example 5 Put 335 m of water in a Teflon container, and add 1 ml of sodium aluminate (Af/Na = 6.1 (atomic ratio)).
1.08 g and 0.79 g of sodium hydroxide were dissolved, and 32.5 g of silica sol (Snowtic: 5iOz 30% by weight) was gradually added while vigorously stirring with a stirrer. After the addition was completed, the mixture was further stirred for 1 hour, and the entire container was heated in an autoclave at 120°C for 2 hours to carry out a hydrothermal reaction.
その結果、アルミナ多孔質基板上にソーダライト型ゼオ
ライトの膜が生成していることが、Ｘ線回折から確認さ
れた。なお、溶液中にはゼオライトの存在は全く認めら
れなかった。As a result, it was confirmed by X-ray diffraction that a membrane of sodalite type zeolite was formed on the alumina porous substrate. Note that no zeolite was observed in the solution.
本発明の方法によれば、アルミナの担体上に緻密なゼオ
ライト膜、特にＡ型、Ｘ型あるいはソーダライト型のゼ
オライト膜が極めて効率よく製造される。According to the method of the present invention, a dense zeolite membrane, particularly an A-type, X-type or sodalite type zeolite membrane, can be produced extremely efficiently on an alumina carrier.
またこのゼオライト膜には、ピンホール等の欠陥がなく
、しかも膜厚も均一であって、気体の分離膜として有効
に利用される。そのうえ、水熱反応条件等を適宜選定す
ることによって、ゼオライト膜の膜厚や密度を自在に調
節することができるため、気体分離膜としての性能を目
的に応じて様々に設定することも可能である。Furthermore, this zeolite membrane has no defects such as pinholes and has a uniform thickness, so it can be effectively used as a gas separation membrane. Furthermore, by appropriately selecting the hydrothermal reaction conditions, etc., the thickness and density of the zeolite membrane can be adjusted freely, so the performance as a gas separation membrane can be set in various ways depending on the purpose. be.
【図面の簡単な説明】
第１図は、実施例４で得られたＡ型ゼオライト膜の表面
構造を示す電子顕微鏡写真（倍率３０００倍）である。
手続補正書（自発）
昭和６３年４月２１日BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an electron micrograph (3000x magnification) showing the surface structure of the A-type zeolite membrane obtained in Example 4. Procedural amendment (voluntary) April 21, 1988
Claims (2)
金属源あるいはアルカリ土類金属源を含む水性混合物を
、アルミナ多孔質担体の存在下で水熱反応させることを
特徴とする膜状合成ゼオライトの製造方法。(1) A membranous synthetic zeolite characterized by hydrothermally reacting an aqueous mixture containing at least (A) a silica source and (B) an alkali metal source or an alkaline earth metal source in the presence of an alumina porous carrier. Production method.
る特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the aqueous mixture contains (C) an alumina source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62126954A JP2501825B2 (en) | 1987-05-26 | 1987-05-26 | Method for producing membranous synthetic zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62126954A JP2501825B2 (en) | 1987-05-26 | 1987-05-26 | Method for producing membranous synthetic zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291809A true JPS63291809A (en) | 1988-11-29 |
| JP2501825B2 JP2501825B2 (en) | 1996-05-29 |
Family
ID=14948009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62126954A Expired - Lifetime JP2501825B2 (en) | 1987-05-26 | 1987-05-26 | Method for producing membranous synthetic zeolite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2501825B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5258339A (en) * | 1992-03-12 | 1993-11-02 | Worcester Polytechnic Institute | Formation of zeolite membranes from sols |
| US5362522A (en) * | 1990-10-19 | 1994-11-08 | The British Petroleum Company, P.L.C. | Process for the production of a membrane |
| EP0695215B2 (en) † | 1993-04-23 | 2002-03-27 | ExxonMobil Chemical Patents Inc. | Process for the manufacture of molecular sieve layers |
| JP2002533216A (en) * | 1998-12-30 | 2002-10-08 | コーニング インコーポレイテッド | Zeolite membrane and method for producing the same |
| WO2005087356A1 (en) * | 2004-03-17 | 2005-09-22 | Bussan Nanotech Research Institute, Inc. | Separation membrane |
| WO2006132237A1 (en) | 2005-06-10 | 2006-12-14 | Bussan Nanotech Research Institute, Inc. | Manufacturing device for zeolite membrane |
| JP2008517751A (en) * | 2004-10-29 | 2008-05-29 | ゾルテッヒ アーゲー | Method for producing a substrate coated with a zeolite layer |
| DE102008050926A1 (en) | 2008-10-10 | 2010-04-15 | Nanoscape Ag | Adsorber element and method for producing an adsorber element |
| US7811359B2 (en) | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
| US7951738B2 (en) | 2005-09-28 | 2011-05-31 | Mitsubishi Chemical Corporation | Process for producing zeolite separation membrane |
| US8258069B2 (en) | 2005-09-01 | 2012-09-04 | Mitsubishi Chemical Corporation | Zeolitic separation membrane and process for producing the same |
| US8263179B2 (en) | 2006-02-24 | 2012-09-11 | Mitsubishi Chemical Corporation | Process for producing zeolite separation membrane |
-
1987
- 1987-05-26 JP JP62126954A patent/JP2501825B2/en not_active Expired - Lifetime
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362522A (en) * | 1990-10-19 | 1994-11-08 | The British Petroleum Company, P.L.C. | Process for the production of a membrane |
| US5605631A (en) * | 1990-10-19 | 1997-02-25 | The British Petroleum Company, P.L.C. | Membranes |
| US5258339A (en) * | 1992-03-12 | 1993-11-02 | Worcester Polytechnic Institute | Formation of zeolite membranes from sols |
| EP0695215B2 (en) † | 1993-04-23 | 2002-03-27 | ExxonMobil Chemical Patents Inc. | Process for the manufacture of molecular sieve layers |
| JP2002533216A (en) * | 1998-12-30 | 2002-10-08 | コーニング インコーポレイテッド | Zeolite membrane and method for producing the same |
| WO2005087356A1 (en) * | 2004-03-17 | 2005-09-22 | Bussan Nanotech Research Institute, Inc. | Separation membrane |
| US8053032B2 (en) | 2004-10-29 | 2011-11-08 | Sortech Ag | Method for production of a substrate coated with a zeolite layer |
| JP4939423B2 (en) * | 2004-10-29 | 2012-05-23 | ゾルテッヒ アーゲー | Method for producing a substrate coated with a zeolite layer |
| JP2008517751A (en) * | 2004-10-29 | 2008-05-29 | ゾルテッヒ アーゲー | Method for producing a substrate coated with a zeolite layer |
| JPWO2006132237A1 (en) * | 2005-06-10 | 2009-01-08 | 三菱化学株式会社 | Zeolite membrane production equipment |
| JP4650489B2 (en) * | 2005-06-10 | 2011-03-16 | 三菱化学株式会社 | Zeolite membrane production equipment |
| US8105548B2 (en) | 2005-06-10 | 2012-01-31 | Mitsubishi Chemical Corporation | Manufacturing device for zeolite membrane |
| WO2006132237A1 (en) | 2005-06-10 | 2006-12-14 | Bussan Nanotech Research Institute, Inc. | Manufacturing device for zeolite membrane |
| US8258069B2 (en) | 2005-09-01 | 2012-09-04 | Mitsubishi Chemical Corporation | Zeolitic separation membrane and process for producing the same |
| US7951738B2 (en) | 2005-09-28 | 2011-05-31 | Mitsubishi Chemical Corporation | Process for producing zeolite separation membrane |
| US8263179B2 (en) | 2006-02-24 | 2012-09-11 | Mitsubishi Chemical Corporation | Process for producing zeolite separation membrane |
| US7811359B2 (en) | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
| WO2010040335A2 (en) | 2008-10-10 | 2010-04-15 | Viessmann Werke Gmbh & Co. Kg | Adsorber element and method for producing an adsorber element |
| DE102008050926A1 (en) | 2008-10-10 | 2010-04-15 | Nanoscape Ag | Adsorber element and method for producing an adsorber element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2501825B2 (en) | 1996-05-29 |
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