JPS60129119A - Gas separating membrane - Google Patents
Gas separating membraneInfo
- Publication number
- JPS60129119A JPS60129119A JP58236666A JP23666683A JPS60129119A JP S60129119 A JPS60129119 A JP S60129119A JP 58236666 A JP58236666 A JP 58236666A JP 23666683 A JP23666683 A JP 23666683A JP S60129119 A JPS60129119 A JP S60129119A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- membrane
- pores
- carrier
- powder
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000004115 Sodium Silicate Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- 239000010409 thin film Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01D71/0281—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は混合気体から任意の気体を連続的に分離するだ
めの気体分離膜に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a gas separation membrane for continuously separating any gas from a gas mixture.
従来例の構成とその問題点
従来気体分離膜はけい素樹脂や弗化炭素樹脂などを代表
として、高分子有機化合物の薄膜で構成されている。こ
れらの有機高分子による気体分離膜はいずれも分離系数
が低く、気体透過速度が遅い、かつ機械的に弱く、また
熱・光に対して不安定であるなどの問題を有している。Conventional Structures and Problems Conventional gas separation membranes are composed of thin films of high-molecular organic compounds, typically silicone resins and fluorocarbon resins. All of these gas separation membranes made of organic polymers have problems such as a low separation number, a slow gas permeation rate, mechanical weakness, and instability with respect to heat and light.
発明の目的
本発明は従来の気体分離膜が有していた前述の問題点を
全て克服した高性能の気体分離膜を提供することを目的
とする。OBJECTS OF THE INVENTION An object of the present invention is to provide a high-performance gas separation membrane that overcomes all of the above-mentioned problems that conventional gas separation membranes had.
発明の構成
本発明は無機質であるゼオライトで薄膜を気体分離膜と
して使用するものである。この膜の片面から混合気体を
加圧すると膜の反対側の血から特定の気体成分のみが優
先的に透過して出て来る。Structure of the Invention The present invention uses a thin film made of inorganic zeolite as a gas separation membrane. When a mixed gas is pressurized from one side of this membrane, only specific gas components will preferentially permeate and come out from the blood on the other side of the membrane.
この様なゼオライト薄膜は、セラミックスなどの多孔質
担体の面上の細孔にゼオライトの微粉を望ましくはバイ
ンダーと共に埋め込み、固定することでも得られるが、
よシ望ましくは無機物を焼結して得た平板状の多孔体の
面上でゼオライトの合成反応を行ない担体上にゼオライ
ト結晶を析出、固定することによって得ることができる
。さらにこの様な担体にアルミナの焼結多孔体を用い、
水酸化ナトリウムなどでアルカリ処理を行ない、一部を
アルミン酸ナトリウムとした上で、これにけい酸ナトリ
ウム（水ガラス）、水酸化ナトリウムを反応させて、表
面をゾル化し、その後水熱反応を行なうことにより良好
なゼオライト膜が得られる。Such a zeolite thin film can also be obtained by embedding and fixing fine zeolite powder, preferably together with a binder, into the pores on the surface of a porous carrier such as ceramics.
More preferably, it can be obtained by carrying out a zeolite synthesis reaction on the surface of a flat porous body obtained by sintering an inorganic substance, and precipitating and fixing zeolite crystals on a carrier. Furthermore, using a sintered porous alumina material as such a carrier,
After performing alkali treatment with sodium hydroxide etc., a portion is made into sodium aluminate, which is then reacted with sodium silicate (water glass) and sodium hydroxide to form a sol on the surface, followed by a hydrothermal reaction. As a result, a good zeolite membrane can be obtained.
実施例の説明
アルミナ微粉（直径約１０μｍ）を成型・焼結して厚さ
０．５ｍｍ、直径６０祁の薄板を得た。この薄板を以下
の２種の方法で処理してゼオライト薄膜を得た。Description of Examples Fine alumina powder (about 10 μm in diameter) was molded and sintered to obtain a thin plate with a thickness of 0.5 mm and a diameter of 60 μm. This thin plate was treated by the following two methods to obtain a zeolite thin film.
ゼオライ１−４Ａ微粉末（直径１０μｍ以下）にベント
ナイト１０％を加えた後、混合粉末と同電量の水を加え
て練合し、薄板に塗布し、１０Ｋｑ／ｃ１ｎの圧力でプ
レスした後６００℃で１時間焼結した。After adding 10% bentonite to zeolite 1-4A fine powder (diameter 10 μm or less), knead with the same amount of water as the mixed powder, apply on a thin plate, press at a pressure of 10 Kq/c1n, and then heat at 600°C. It was sintered for 1 hour.
薄板を１ＯＮの水酸化ナトリウム溶液に６０℃で１時間
浸透させた後水ガラス１０Ｃ１，水酸化ナトリウム５グ
、水３００９を混合した溶液に浸した後ゆっくりと引き
上げ゛、オートクレーブ中で１２０℃、６時間加熱する
と、ゼオライトがアルミナ表面に一様に析出した。The thin plate was immersed in a 1ON sodium hydroxide solution at 60°C for 1 hour, then immersed in a solution containing 10C1 of water glass, 5 g of sodium hydroxide, and 3009 water, and then slowly pulled up. When heated for a period of time, zeolite was uniformly precipitated on the alumina surface.
これとは別にチタニア微粉（直径約１０μｍ）を用いて
上記と同様な薄板を作り、アルミン酸ナトリウム１Ｑ２
．水ガラス３０ｆ、水酸化ナトリウム２７．水７０？を
混合した溶液に浸し溶液と共にオートフレニブ中で１２
０℃、６時間加熱してゼオライト薄膜を得た。Separately, a thin plate similar to the above was made using titania fine powder (about 10 μm in diameter), and sodium aluminate 1Q2
．． Water glass 30f, sodium hydroxide 27. Water 70? Soaked in a mixed solution and placed in an autoflenib with the solution for 12
A zeolite thin film was obtained by heating at 0° C. for 6 hours.
以上の３種の方法で得だゼオライト薄膜をそれぞれ試料
へ〜試料Ｃと呼ぶことにする。比較のため、従来例とし
て通気性セルロース膜（ミリポアフィルタ−３Ｍタイプ
）にシリコンＲＴ Ｖ ：ｌ”ムを塗布し、１ｏＫｙ／
ｃａの圧力でプレスした後固化したものを試料りとしだ
。The zeolite thin films obtained using the above three methods were each used as a sample. These will be referred to as sample C. For comparison, as a conventional example, a silicone RT V:1" membrane was applied to a breathable cellulose membrane (Millipore filter - 3M type), and the film was 1oKy/
After pressing at a pressure of ca, take a sample of the solidified material.
計４種の試料について、酸素と窒素の透過係数を測定し
た結果を禾に示して・）る。第１表から本発明は３種（
試料Ａ、Ｂ、Ｃ）とも従来例よりも圧 □倒的に気体透
過係数が優れているといえる。また分離係数も全て従来
より向上したが特に試料Ｂは顕著であった。この２つの
条件を考えると、試料Ｂが気体分離膜として最も優れて
いると結論できる。またゼオライトは１１１℃機質であ
り、本質的な長所として、化学的・熱的に安定で機械強
度も優れている。I will show you the results of measuring the oxygen and nitrogen permeability coefficients for a total of four types of samples. From Table 1, the present invention has three types (
It can be said that samples A, B, and C) all have far superior gas permeability coefficients than the conventional example. In addition, the separation coefficients were all improved compared to the conventional ones, but sample B was particularly remarkable. Considering these two conditions, it can be concluded that sample B is the most excellent as a gas separation membrane. In addition, zeolite has a temperature of 111°C, and its essential advantages are that it is chemically and thermally stable and has excellent mechanical strength.
発明の効果
以上のように、本発明により飛躍的に大きな透過係数を
有し、さらに分離係数も優れ、化学的・熱的に安定で機
械強度も大きい気体分＄ ｒ＋Ｇｓが？４ｊられる。As described above, the present invention provides a gas component $r+Gs that has a dramatically large permeability coefficient, an excellent separation coefficient, is chemically and thermally stable, and has high mechanical strength. 4j is received.
Claims (3)
ことを特徴とする特許請求の範囲第１項記載の気体分離
膜。(2) The gas separation membrane according to claim 1, wherein the zeolite membrane is fixed on the surface of a porous carrier.
ことによって得たゼオライト膜を構成要素とする特許請
求の範囲第２項または第９項記載の気体分離膜。(3) The gas separation membrane according to claim 2 or 9, which comprises a zeolite membrane obtained by embedding zeolite powder in the pores of a porous carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236666A JPS60129119A (en) | 1983-12-15 | 1983-12-15 | Gas separating membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58236666A JPS60129119A (en) | 1983-12-15 | 1983-12-15 | Gas separating membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60129119A true JPS60129119A (en) | 1985-07-10 |
Family
ID=17003986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58236666A Pending JPS60129119A (en) | 1983-12-15 | 1983-12-15 | Gas separating membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60129119A (en) |
Cited By (13)
| 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 |
| US5429743A (en) * | 1991-02-07 | 1995-07-04 | Technische Universiteit Delft | Inorganic composite membrane comprising molecular sieve crystals |
| EP0778075A1 (en) | 1995-12-08 | 1997-06-11 | Institut Francais Du Petrole | Process for the preparation of porous glass supported zeolite membranes and zeolite membranes obtained thereby |
| US5672388A (en) * | 1994-07-08 | 1997-09-30 | Exxon Research & Engineering Company | Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition |
| US5824617A (en) * | 1994-07-08 | 1998-10-20 | Exxon Research & Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
| US5871650A (en) * | 1994-07-08 | 1999-02-16 | Exxon Research And Engineering Company | Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer |
| US5972079A (en) * | 1996-06-28 | 1999-10-26 | University Of Delaware | Supported carbogenic molecular sieve membrane and method of producing the same |
| US6471745B1 (en) * | 1996-06-28 | 2002-10-29 | University Of Delaware | Nanoporous carbon catalytic membranes and method for making the same |
| US6472016B1 (en) * | 1998-12-04 | 2002-10-29 | Societe Des Ceramiques Techniques | Membrane comprising a porous carrier and a layer of a molecular sieve and its preparation |
| US7811359B2 (en) | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
| US8168129B2 (en) | 2005-04-29 | 2012-05-01 | Vlaamse Instelling Voor Technologisch Onderzoek (Vito) | Apparatus and method for purification and disinfection of liquid, solid or gaseous substances |
| US20140239225A1 (en) * | 2011-11-11 | 2014-08-28 | Ngk Insulators, Ltd. | Water-Selective Adsorbent and Method for Producing Same |
| CN111530241A (en) * | 2020-04-13 | 2020-08-14 | 北京科技大学 | SO is separated and recovered from flue gas2With NOxApparatus and method of |
-
1983
- 1983-12-15 JP JP58236666A patent/JPS60129119A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753121A (en) * | 1991-02-07 | 1998-05-19 | Exxon Chemical Patents Inc. (Ecpi) | Inorganic composite membrane comprising molecular sieve crystals |
| US5429743A (en) * | 1991-02-07 | 1995-07-04 | Technische Universiteit Delft | Inorganic composite membrane comprising molecular sieve crystals |
| US5258339A (en) * | 1992-03-12 | 1993-11-02 | Worcester Polytechnic Institute | Formation of zeolite membranes from sols |
| US5849980A (en) * | 1994-07-08 | 1998-12-15 | Exxon Research And Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
| US5672388A (en) * | 1994-07-08 | 1997-09-30 | Exxon Research & Engineering Company | Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition |
| US5824617A (en) * | 1994-07-08 | 1998-10-20 | Exxon Research & Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
| US5871650A (en) * | 1994-07-08 | 1999-02-16 | Exxon Research And Engineering Company | Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer |
| EP0778075A1 (en) | 1995-12-08 | 1997-06-11 | Institut Francais Du Petrole | Process for the preparation of porous glass supported zeolite membranes and zeolite membranes obtained thereby |
| US5972079A (en) * | 1996-06-28 | 1999-10-26 | University Of Delaware | Supported carbogenic molecular sieve membrane and method of producing the same |
| US6471745B1 (en) * | 1996-06-28 | 2002-10-29 | University Of Delaware | Nanoporous carbon catalytic membranes and method for making the same |
| US6472016B1 (en) * | 1998-12-04 | 2002-10-29 | Societe Des Ceramiques Techniques | Membrane comprising a porous carrier and a layer of a molecular sieve and its preparation |
| US8168129B2 (en) | 2005-04-29 | 2012-05-01 | Vlaamse Instelling Voor Technologisch Onderzoek (Vito) | Apparatus and method for purification and disinfection of liquid, solid or gaseous substances |
| US7811359B2 (en) | 2007-01-18 | 2010-10-12 | General Electric Company | Composite membrane for separation of carbon dioxide |
| US20140239225A1 (en) * | 2011-11-11 | 2014-08-28 | Ngk Insulators, Ltd. | Water-Selective Adsorbent and Method for Producing Same |
| CN111530241A (en) * | 2020-04-13 | 2020-08-14 | 北京科技大学 | SO is separated and recovered from flue gas2With NOxApparatus and method of |
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