WO1998005414A1 - Composite membrane comprising a polyether-polyester block copolymer coating for separating polar gases from gaseous mixtures - Google Patents
Composite membrane comprising a polyether-polyester block copolymer coating for separating polar gases from gaseous mixtures Download PDFInfo
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- WO1998005414A1 WO1998005414A1 PCT/DE1997/001618 DE9701618W WO9805414A1 WO 1998005414 A1 WO1998005414 A1 WO 1998005414A1 DE 9701618 W DE9701618 W DE 9701618W WO 9805414 A1 WO9805414 A1 WO 9805414A1
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- 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
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- 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
- B01D71/06—Organic material
- B01D71/48—Polyesters
- B01D71/481—Polyarylates
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- 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
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/521—Aliphatic polyethers
- B01D71/5211—Polyethylene glycol or polyethyleneoxide
Definitions
- the invention relates to a composite membrane consisting of a microporous carrier membrane and a separating layer applied thereon, and to the use thereof for separating polar gases from gas mixtures.
- Absorption processes such as gas drying using glycol scrubbers (TEG, DEG) are used on an industrial scale to process natural gas.
- TOG glycol scrubbers
- DEG glycol scrubbers
- a disadvantage of these known absorption processes is the complex process control, which entails a high level of personnel and high investment costs.
- corrosion and fouling, especially in the heat exchangers lead to problems in the operation of these known processes.
- Glycol also causes losses and the necessary additives, such as defoamers and chemicals for pH adjustment, cause additional costs.
- adsorbents for example molecular sieves or silica gel
- the adsorbent is loaded with water in the first step and regenerated in a second step using heat, pressure changes or a dry gas flow.
- This known method is particularly suitable for drying low-load streams. In addition, particularly low residual moisture levels can be achieved.
- a disadvantage of this known method is the fact that the adsorbent has to be regenerated cyclically, so that the process control is discontinuous is.
- this known method for the separation of high water loads is too complex.
- Refrigeration dryers are used for the continuous separation of water vapor from gas mixtures.
- the dew points that can be achieved are around 2 ° C, since below this temperature the cooling coils start to freeze.
- lower dew points can be achieved with two devices connected in parallel, one of which is automatically defrosted.
- this mode of operation requires a high investment cost and an additional energy requirement. The limits of use of this known method are therefore close to the freezing point.
- Hydrogen sulfide is currently mainly separated from natural gases by absorption processes using amine scrubbers.
- the loaded absorbent is regenerated in a second process step.
- the disadvantage of this known method is the high cost.
- the membrane processes known to date can in principle also be used for dehumidifying and desulphurizing large amounts of gas.
- the membrane separation always produces two outlet streams, namely the purified product stream and the water-laden permeate stream. Depending on the application, these currents can be fed back into the process or else discarded. In any case, a high permeate flow leads to increased operating costs.
- the object of the present invention is to provide a new membrane which has high separation factors for polar gases, in particular for hydrogen and hydrogen sulfide, and which has a good mechanical and has chemical stability.
- the composite membrane according to the invention is made up of a microporous carrier membrane and a polymeric separating layer applied thereon.
- This separating layer consists of block copolyetherester or polyether-polyester block copoly eren.
- the polyether block copolymer is preferably a polyalkylene glycol block.
- the Al yl enei nhei t which may be straight or branched, preferably has up to 6 carbon atoms. Polyethylene glycol blocks are particularly preferably used.
- the polyester block copolymer is preferably polyalkyl enterephthalate blocks and in particular polyethylenterephthalate blocks and polybutyl 1 entherephthalate blocks.
- a further preferred polymer block copolymer are poly allyl phthalate and in particular polydimethyltherephthalate.
- the invention is not limited to the polymers mentioned, which are only preferred embodiments. Rather, all polymers suitable for membranes can be used which have several ether bonds and several ester bonds and give block copolymers.
- the mechanical stability of the membrane according to the invention is achieved by the construction of different materials (composite membrane).
- the composite membrane according to the invention can be produced inexpensively, since commercially available polymers can be used.
- production is simple since the composite membrane according to the invention can be obtained by a dipping process or by pouring or spraying on the polymers that make up the separating layer. There is therefore no need for complex interfacial polymerization. In this way, particularly thin selective layers ⁇ 3 ⁇ m are obtained. Due to the thin layers and the polymers used, high separation factors and a high flow rate can be achieved.
- the thickness of the separating layer is preferably chosen such that the water vapor / gas selectivity is 100 to 30000.
- the composite membrane according to the invention enables water vapor and / or hydrogen sulfide to be separated from gas mixtures. Furthermore, the composite membrane according to the invention can be used to separate carbon dioxide, ammonia and ethylene oxide from gas mixtures. However, it has a low flux density for other gases, for example N ? , 0 «and CH .. This leads to a particularly high selectivity, which results in only minor product losses. In addition, the membrane area required is small or small.
- the membrane according to the invention thus enables the selective separation of polar gases from gas mixtures. It can thus be used, for example, for drying natural gas before it is fed into a central pipeline network and for processing compressed air.
- the inventive Membrane if used for natural gas cleaning, in addition to the water vapor, hydrogen sulfide and carbon dioxide are simultaneously separated. This means that the known glycol and amine scrubbers can be replaced by a single membrane stage when cleaning natural gas.
- the membrane according to the invention can also be used to dehumidify inert gases which are used to dry sensitive products. By using a circuit, the inert gas consumption can be significantly reduced.
- the membrane according to the invention also has a high ammonia / nitrogen selectivity.
- Another advantage of the membrane according to the invention is that it is stable against condensates.
- the known Cel 1 ul oseacetatmembranen show, for example, an irreversible change in flow performance after contact in liquid water.
- the support membrane preferably consists of polyether iid, polyethyl vinyl idene fluoride or polyacrylic nitrite 1.
- a block copolymer ester which consists of 70 wt. -7.
- Polyethylene terephthalate and 30% by weight polyethylene glycol commercially available as Sympatex (R) (Akzo)
- 49.5 g of 1, 1, 2-trichloroethane were added and the mixture was heated under reflux at the boiling point for 12 h.
- a microporous polyacrylic nitri 1 membrane manufactured by GKSS
- GKSS microporous polyacrylic nitri 1 membrane
- Sympatex film a water vapor permeabi 1 i tat of approx. 2
- Example 1 In accordance with the instructions in Example 1, a 0.5% by weight Sympatex solution in 1, 1, 2-trichloroethane was prepared. This solution was used to coat a microporous PVDF membrane on a polypropylene base (manufacturer GKSS) with a solution that was 50 ° C.
- GKSS polypropylene base
- Figures 1 and 2 show the nitrogen and water vapor permeabilities against the water vapor part i al pressure.
- Figure 3 shows the corresponding selectivity.
- the three figures also contain the values obtained with a commercial Sympatex film.
- the resulting water vapor / nitrogen selectivity was 14,700.
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Kompositmembran mit einer Beschichtung aus Polyether- Polyester-Bl ock-Copolymeren zur Abtrennung von polaren Gasen aus GasgemischenComposite membrane with a coating of polyether-polyester block copolymers for the separation of polar gases from gas mixtures
Beschrei bunqDescribe bunq
Die Erfindung betrifft eine Kompositmembran aus einer mikroporösen Trägermembran und einer darauf aufgebrachten Trennschicht sowie deren Verwendung zur Abtrennung von polaren Gasen aus Gasgemischen.The invention relates to a composite membrane consisting of a microporous carrier membrane and a separating layer applied thereon, and to the use thereof for separating polar gases from gas mixtures.
Die Abtrennung von Wasserdampf aus Prozeßgasgemischen erfolgt im technischen Maßstab derzeit mit Hilfe von Absorptionsverfahren (z.B. Glykol trocknen) , mit Hilfe von Adsorptionsverfahren (beispielsweise Molekularsieben, aktiviertem Aluminiumoxid oder Silikagel) oder mit Hilfe von Kältetrocknern. Auch werden bereits Membranverfahren zur Gastrocknung eingesetzt. Letztere werden jedoch aufgrund der geringen Flußdichten und der hohen Produktionsverluste nur bei geringen und mittleren Volumenströmen zur Anwendung gebracht.The separation of water vapor from process gas mixtures is currently carried out on an industrial scale with the aid of absorption processes (for example drying glycol), with the aid of adsorption processes (for example molecular sieves, activated aluminum oxide or silica gel) or with the aid of refrigeration dryers. Membrane processes are already used for gas drying. However, the latter are due to the low flux densities and high production losses are only used for low and medium volume flows.
Absorptionsverfahren, beispielsweise die Gastrocknung mittels Glykol Wäschern (TEG, DEG), werden großtechnisch zur Aufbereitung von Erdgas eingesetzt. Das beladeneAbsorption processes, such as gas drying using glycol scrubbers (TEG, DEG), are used on an industrial scale to process natural gas. The loaded
Absorptionsmittel wird in einem zweiten Prozeßschritt regeneriert. Dieses bekannte Verfahren führt zu hohenAbsorbent is regenerated in a second process step. This known method leads to high
Abrei nigungsgraden und wird daher besonders bei derDegrees of abrasion and is therefore particularly in the
Trocknung von Erdgasen eingesetzt.Drying of natural gases used.
Nachteilig bei diesen bekannten Absorptionsverfahren ist die komplexe Prozeßführung, die einen hohen Personaleinsatz sowie große Investitionskosten nach sich zieht. Zudem führen Korrosion und Fouling, insbesondere in den Wärmetauschern, zu Problemen bei Betrieb dieser bekannten Verfahren. Außerdem werden durch Glykol verl uste und die erforderlichen Zusatzstoffe, wie Entschäumer und Chemikalien zur pH-Werteinstellung, zusätzliche Kosten verursacht .A disadvantage of these known absorption processes is the complex process control, which entails a high level of personnel and high investment costs. In addition, corrosion and fouling, especially in the heat exchangers, lead to problems in the operation of these known processes. Glycol also causes losses and the necessary additives, such as defoamers and chemicals for pH adjustment, cause additional costs.
Bei der bekannten Adsorptionstrocknung werden Adsorben- tien, be spielsweise Molekularsiebe oder Silikagel zyklisch mit Feuchtigkeit be- und entladen. Das Adsorp- tionsmittel wird dabei im ersten Schritt mit Wasser beladen und in einem zweiten, mit Hilfe von Wärme, Druckwechsel oder einem trockenen Gasstrom regeneriert. Dieses bekannte Verfahren eignet sich besonders zur Trocknung von gering beladenen Strömen. Zudem lassen sich besonders geringe Restfeuchtegehalte erzielen.In the known adsorption drying, adsorbents, for example molecular sieves or silica gel, are cyclically loaded and unloaded with moisture. The adsorbent is loaded with water in the first step and regenerated in a second step using heat, pressure changes or a dry gas flow. This known method is particularly suitable for drying low-load streams. In addition, particularly low residual moisture levels can be achieved.
Nachteilig bei diesem bekannten Verfahren ist die Tatsache, daß das Adsorptionsmittel zyklisch regeneriert werden muß, so daß die Prozeßführung diskontinuierlich ist. Außerdem wird dadurch dieses bekannte Verfahren zur Abtrennung von hohen Wasserbeladungen zu aufwendig.A disadvantage of this known method is the fact that the adsorbent has to be regenerated cyclically, so that the process control is discontinuous is. In addition, this known method for the separation of high water loads is too complex.
Kältetrockner werden zur kontinuierlichen Abtrennung von Wasserdampf aus Gasgemischen eingesetzt. Die erreichbaren Taupunkte liegen dabei bei etwa 2°C, da unterhalb dieser Temperatur eine Vereisung der Kühlschlangen einsetzt. Niedrigere Taupunkte können jedoch mit zwei parallel geschalteten Geräten erreicht werden, von denen jeweils eines automatisch abgetaut wird. Diese Betriebsweise erfordert aber einen hohen Investitionskostenaufwand und einen zusätzlichen Energiebedarf. Die Einsatzgrenzen dieses bekannten Verfahrens liegen also in der Nähe des Gef ierpunktes.Refrigeration dryers are used for the continuous separation of water vapor from gas mixtures. The dew points that can be achieved are around 2 ° C, since below this temperature the cooling coils start to freeze. However, lower dew points can be achieved with two devices connected in parallel, one of which is automatically defrosted. However, this mode of operation requires a high investment cost and an additional energy requirement. The limits of use of this known method are therefore close to the freezing point.
Schwefelwasserstoff wird aus Erdgasen derzeit überwiegend durch Absorptionsverfahren mittels Aminwäschern abgetrennt. Das beladene Absorptionsmittel wird in einem zweiten Prozeßschritt regeneriert. Nachteilig an diesem bekannten Verfahren sind die hohen Kosten.Hydrogen sulfide is currently mainly separated from natural gases by absorption processes using amine scrubbers. The loaded absorbent is regenerated in a second process step. The disadvantage of this known method is the high cost.
Die bisher bekannten Membranverfahren können im Prinzip auch zur Entfeuchtung und zur Entschwefelung von größeren Gasmengen eingesetzt werden. Bei der Membrantrennung entstehen jedoch immer zwei Austrittsströme, nämlich der gereinigte Produktstrom und der wasserbela- dene Permeatstrom. Je nach Anwendungsfal können diese Ströme in den Prozeß zurückgeführt oder aber auch verworfen werden. In jedem Fall führt ein hoher Permeatstrom zu erhöhten Betriebskosten.The membrane processes known to date can in principle also be used for dehumidifying and desulphurizing large amounts of gas. However, the membrane separation always produces two outlet streams, namely the purified product stream and the water-laden permeate stream. Depending on the application, these currents can be fed back into the process or else discarded. In any case, a high permeate flow leads to increased operating costs.
Aufgabe der vorliegenden Erfindung ist es, eine neue Membran bereitzustellen, die hohe Trennfaktoren für polare Gase, insbesondere für Wasserstoff und Schwefelwasserstoff, besitzt und über eine gute mechanische und chemische Stabilität verfügt.The object of the present invention is to provide a new membrane which has high separation factors for polar gases, in particular for hydrogen and hydrogen sulfide, and which has a good mechanical and has chemical stability.
Gelöst wird diese Aufgabe durch die Lehre der Ansprüche.This task is solved by teaching the claims.
Die erfindungsgemäße Kompositmembran ist aus einer mikroporösen Trägermembran und einer darauf aufgebrachten polymeren Trennschicht aufgebaut. Diese Trennschicht besteht aus Block-Copolyetherester bzw. Poly- ether-Polyester-Bl ock-Copoly eren . Bei dem Polyether- Bl ock-Copolymer handelt es sich vorzugsweise um Poly- al kyl englykol -B öcke . Die AI yl enei nhei t , die gerade oder verzweigt sein kann, weist vorzugsweise bis zu 6 Kohl enstoff atome auf. Besonders bevorzugt werden Poly- ethyl englykol -Bl öcke zum Einsatz gebracht.The composite membrane according to the invention is made up of a microporous carrier membrane and a polymeric separating layer applied thereon. This separating layer consists of block copolyetherester or polyether-polyester block copoly eren. The polyether block copolymer is preferably a polyalkylene glycol block. The Al yl enei nhei t, which may be straight or branched, preferably has up to 6 carbon atoms. Polyethylene glycol blocks are particularly preferably used.
Bei dem Polyester-Bl ock-Copolymer handelt es sich vorzugsweise um Polyal kyl entherephthal at-Bl öcke und insbesondere um Pol yethyl entherephthal at- und Polybuty- 1 entherephthal at-Bl öcke.The polyester block copolymer is preferably polyalkyl enterephthalate blocks and in particular polyethylenterephthalate blocks and polybutyl 1 entherephthalate blocks.
Ein weiterhin bevorzugtes Pol yether-Bl ock-Copolymer sind Pol ydi al kyl herepththal at und insbesondere Polydimethyl - therephthal at .A further preferred polymer block copolymer are poly allyl phthalate and in particular polydimethyltherephthalate.
Die Erfindung ist jedoch nicht auf die genannten Polymere beschränkt, die lediglich bevorzugte Ausführungsformen darstellen. Vielmehr können alle für Membranen geeignete Polymere eingesetzt werden, die über mehrere Etherbindungen und mehrere Esterbindungen verfügen und Bl ock-Copoly ere ergeben.However, the invention is not limited to the polymers mentioned, which are only preferred embodiments. Rather, all polymers suitable for membranes can be used which have several ether bonds and several ester bonds and give block copolymers.
Die mechanische Stabilität der erfindungsgemäßen Membran wird durch den Aufbau aus unterschiedlichen Materialien erreicht (Kompositmembran). Die erfindungsgemäße Kompositmembran läßt sich kostengünstig herstellen, da kommerziell erhältliche Polymere eingesetzt werden können. Zudem ist die Herstellung einfach, da die erfindungsgemäße Kompositmembran durch ein Tauchverfahren oder durch Aufgießen oder Sprühen der die Trennschicht ausmachenden Polymere erhalten werden kann. Es ist somit keine aufwendige Grenzflächenpolymerisation erforderlich. Auf diese Weise werden besonders dünne selektive Schichten < 3 μm erhalten. Durch die dünnen Schichten und die zum Einsatz gebrachten Polymere können hohe Trennfaktoren sowie eine hohe Flußleistung erzielt werden.The mechanical stability of the membrane according to the invention is achieved by the construction of different materials (composite membrane). The composite membrane according to the invention can be produced inexpensively, since commercially available polymers can be used. In addition, production is simple since the composite membrane according to the invention can be obtained by a dipping process or by pouring or spraying on the polymers that make up the separating layer. There is therefore no need for complex interfacial polymerization. In this way, particularly thin selective layers <3 μm are obtained. Due to the thin layers and the polymers used, high separation factors and a high flow rate can be achieved.
Die Dicke der Trennschicht ird vorzugsweise derart gewählt, daß die Wasserdampf/Gas-Selektivi ät 100 bis 30000 beträgt.The thickness of the separating layer is preferably chosen such that the water vapor / gas selectivity is 100 to 30000.
Die erfindungsgemäße Kompositmembran ermöglicht die Abtrennung von Wasserdampf und/oder Schwefelwasserstoff aus Gasgemischen. Ferner kann die erfindungsgemäße Kompositmembran zur Abtrennung von Kohlendioxid, Ammoniak und Ethylenoxid aus Gasgemischen eingesetzt werden. Sie besitzt jedoch eine geringe Flußdichte für andere Gase, beispielsweise N?, 0« und CH.. Dies führt zu einer besonders hohen Selektivität, die nur geringe Produktverluste nach sich zieht. Außerdem ist die erforderliche Membranfläche klein bzw. gering.The composite membrane according to the invention enables water vapor and / or hydrogen sulfide to be separated from gas mixtures. Furthermore, the composite membrane according to the invention can be used to separate carbon dioxide, ammonia and ethylene oxide from gas mixtures. However, it has a low flux density for other gases, for example N ? , 0 «and CH .. This leads to a particularly high selectivity, which results in only minor product losses. In addition, the membrane area required is small or small.
Die erfindungsgemäße Membran ermöglicht somit die selektive Abtrennung von polaren Gasen aus Gasgemischen. Sie kann somit beispielsweise bei der Trocknung von Erdgas vor der Einspeisung in ein zentrales Leitungsnetz sowie bei der Aufbereitung von Druckluft zum Einsatz gebracht werden. Im Gegensatz zu den bekannten Gastrocknungsmembranen kann mit der erfindungsgemäßen Membran, wenn sie zur Erdgasreinigung verwendet wird, neben dem Wasserdampf simultan auch Schwefelwasserstoff und Kohlendioxid abgetrennt werden. Somit können bei der Erdgasreinigung die bekannten Glykol- und Aminwäscher durch eine einzige Membranstufe ersetzt werden. Die erfindungsgemäße Membran kann ferner zur Entfeuchtung von Inertgasen eingesetzt werden, die zur Trocknung von empfindlichen Produkten dienen. Durch eine Kreislaufführung kann so der Inertgasverbrauch deutlich reduziert werden .The membrane according to the invention thus enables the selective separation of polar gases from gas mixtures. It can thus be used, for example, for drying natural gas before it is fed into a central pipeline network and for processing compressed air. In contrast to the known gas drying membranes, the inventive Membrane, if used for natural gas cleaning, in addition to the water vapor, hydrogen sulfide and carbon dioxide are simultaneously separated. This means that the known glycol and amine scrubbers can be replaced by a single membrane stage when cleaning natural gas. The membrane according to the invention can also be used to dehumidify inert gases which are used to dry sensitive products. By using a circuit, the inert gas consumption can be significantly reduced.
Die erfindungsgemäße Membran weist zudem auch eine hohe Ammoni ak/Stickstoff-Selektivität auf.The membrane according to the invention also has a high ammonia / nitrogen selectivity.
Ein weiterer Vorteil der erfindungsgemäßen Membran liegt darin, daß sie gegen Kondensate stabil ist. Die bekannten Cel 1 ul oseacetatmembranen zeigen beispielsweise nach Kontakt im flüssigem Wasser eine irreversible Veränderung der Flußleistung.Another advantage of the membrane according to the invention is that it is stable against condensates. The known Cel 1 ul oseacetatmembranen show, for example, an irreversible change in flow performance after contact in liquid water.
Als mikroporöse Trägermembran für die erfindungsgemäße Trägermembran kann jedes bekannte, für derartige Zwecke geeignetes Material eingesetzt werden. Vorzugsweise besteht die Trägermembran jedoch aus Polyetheri i d , Polyethyl vinyl idenfl uorid oder Polyacryl ni tri 1.Any known material suitable for such purposes can be used as the microporous support membrane for the support membrane according to the invention. However, the support membrane preferably consists of polyether iid, polyethyl vinyl idene fluoride or polyacrylic nitrite 1.
Die erfindungsgemäße Kompositmembran wird im folgenden anhand der bevorzugte Ausführungsformen beschreibenden Beispiele näher erläutert.The composite membrane according to the invention is explained in more detail below with reference to the examples describing preferred embodiments.
BEISPIEL 1EXAMPLE 1
0,5 g eines Bl ock-Copol yetheresters , der aus 70 Gew. -7. Polyethylentherephthalat und 30 Gew.-% Polyethyl englykol bestand (kommerziell als Sympatex(R) (Akzo) erhältlich), wurden mit 49,5 g 1 , 1 , 2-Trichl orethan versetzt und 12 h unter Rückfluß beim Siedepunkt erhitzt. Nach Abkühlung auf 45°C wurde mit dieser Lösung eine mikroporöse Polyacryl nitri 1 membran (Hersteller GKSS) im Tauchverfahren beschichtet. Nach Abdampfen des Lösemittels bei Raumtemperatur wurde eine Kompositmembran erhalten, deren selektive Trennschicht aus einer ca. 1 μm dünnen Sy patexschi cht bestand. Mit dieser Membran wurden folgende Gaspermeabilitäten gemessen.0.5 g of a block copolymer ester, which consists of 70 wt. -7. Polyethylene terephthalate and 30% by weight polyethylene glycol (commercially available as Sympatex (R) (Akzo)), 49.5 g of 1, 1, 2-trichloroethane were added and the mixture was heated under reflux at the boiling point for 12 h. After cooling to 45 ° C., a microporous polyacrylic nitri 1 membrane (manufacturer GKSS) was coated with this solution using the immersion method. After the solvent had been evaporated off at room temperature, a composite membrane was obtained, the selective separation layer of which consisted of an approx. 1 μm thin sypatex layer. The following gas permeabilities were measured with this membrane.
Stickstoff Sauerstoff Methan Kohlen- Schwefel- Wasser- dioxid Wasserstoff stoffNitrogen Oxygen Methane Coal Sulfur Water Hydrogen Hydrogen
1,07 2,41 2,2 50,8 185 200001.07 2.41 2.2 50.8 185 20,000
Permeabi 1 i täten in 10 m /m h barPermeabi 1 i at 10 m / m h bar
Im Vergleich dazu wies ein kommerzieller 10 μm dickerIn comparison, a commercial showed 10 μm thicker
Sympatexfilm eine Wasserdampfpermeabi 1 i tat von ca. 2Sympatex film a water vapor permeabi 1 i tat of approx. 2
3 2 m /m h bar auf. Dieser Fluß der bekannten Membran ist für eine technische Gastrocknungsmembran zu niedrig.3 2 m / m h bar. This flow of the known membrane is too low for a technical gas drying membrane.
BEISPIEL 2EXAMPLE 2
Entsprechend der Vorschrift in Beispiel 1 wurde eine 0,5 Gew.-%-ige Sympatexl ösung in 1 , 1 , 2-Tri chl orethan hergestellt. Mit dieser Lösung wurde eine mikroporöse PVDF- Membran auf Polypropylenunterlage (Hersteller GKSS) mit einer 50"C warmen Lösung beschichtet. Nach Abdampfen des Lösemittels entstand wiederum ein ca. 1 μm dünner Sympatexfilm mit sehr guter Haftung auf PVDF. Mit dieser Kompositmembran wurden bei 20°C Messungen mit Stickstoff/Wasserdampf-Mischungen durchgeführt. Es resultierte eine Wasserdampfpermeabilität, die abhängig vom Partialdruck des Wasserdampfes war. Bei 8 mbar Wasserdampf-Parti aldruck wurde eine Permeabilität von 22 m3/m2 h bar gemessen, bei 22 mbar Wasserdampf-Part i al -In accordance with the instructions in Example 1, a 0.5% by weight Sympatex solution in 1, 1, 2-trichloroethane was prepared. This solution was used to coat a microporous PVDF membrane on a polypropylene base (manufacturer GKSS) with a solution that was 50 ° C. After evaporation of the solvent, an approximately 1 μm thin Sympatex film with very good adhesion to PVDF was formed ° C Measurements carried out with nitrogen / water vapor mixtures, resulting in a water vapor permeability which was dependent on the partial pressure of the water vapor at 8 mbar Water vapor partial pressure a permeability of 22 m 3 / m 2 h bar was measured, at 22 mbar water vapor part i al -
3 2 druck stieg dieser Wert auf 40 m /m h bar. Die mittlere3 2 pressure this value rose to 40 m / m h bar. The middle
Wasserdampf/Stickstoff-Selektivität lag bei 25000.Water vapor / nitrogen selectivity was 25,000.
Figuren 1 und 2 zeigen die Stickstoff- bzw. Wasserdampfpermeabilitäten gegen den Wasserdampf-Part i al druck . Figur 3 zeigt die entsprechende Selektivität. Zum Vergleich enthalten die drei Figuren auch die Werte, die mit einem kommerziellen Sympatexfilm erhalten wurden.Figures 1 and 2 show the nitrogen and water vapor permeabilities against the water vapor part i al pressure. Figure 3 shows the corresponding selectivity. For comparison, the three figures also contain the values obtained with a commercial Sympatex film.
BEISPIEL 3EXAMPLE 3
0,5 g eines Bl ock-Copol ymers bestehend aus 84,5 Ma- Polyethylenglykol und 15,5 Ma-% Polydimethyl therephtha- 1 at wurden mit 99,5 g einer Lösung versetzt, die folgende Zusammensetzung hatte:0.5 g of a block copolymer consisting of 84.5% polyethylene glycol and 15.5% by weight polydimethyl therephthalate was mixed with 99.5 g of a solution which had the following composition:
Aceteon 16 Gew.-% iso-Propanol 77 Gew.-% Wasser 7 Gew.-1/.Aceteon 16 wt .-% iso-propanol, 77 wt .-% water 7 wt 1 /.
Nach 3 h Kochen unter Rückfluß wurde die Lösung abgekühlt und filtriert. Mit dieser Lösung wurde dann eine mikroporöse Polyetherimidmembran auf Polyesterunterlage (Hersteller GKSS) beschichtet. Nach Abdampfen des Lösemittels wurde eine ca. 0,7 μm dünne Schicht des Bl ock-Copolymers auf Polyetheri id erhalten. Mit dieser Kompositmembran wurden folgende Gasflüsse ermittelt.After refluxing for 3 hours, the solution was cooled and filtered. A microporous polyetherimide membrane on a polyester base (manufacturer GKSS) was then coated with this solution. After evaporation of the solvent, an approximately 0.7 μm thin layer of the block copolymer on polyether i id was obtained. The following gas flows were determined with this composite membrane.
Stickstoff Kohlendioxid Schwefel asserstoff Wasserdampf 5 124 495 21000 Permeabilitäten in 10~3 x m / h bar Die resultierende Wasserdampf/Stickstoff-Selektivität beträgt 4200.Nitrogen Carbon Dioxide Sulfur Oxygen Water vapor 5 124 495 21000 Permeabilities in 10 ~ 3 xm / h bar The resulting water vapor / nitrogen selectivity is 4200.
BEISPIEL 4EXAMPLE 4
Mit einer 0,5 Gew.-%-igen Sympatex! ösung in 1,1,2-Tri- chlorethan wurde ein mikroporöser Polypropyl en-Hohl faden (Hersteller Akzo) beschichtet, indem die Lösung durch das Lumen der Hohlfäden gepumpt wurde. Anschließend wurde das Lösemittel durch einen Stickstoff-Strom verdampft. Es bildete sich eine ca. 1 μm dünne Sympatex- schicht im Inneren der Hohlfäden. Folgende Gaspermeabilitäten wurden ermittelt:With a 0.5% by weight Sympatex! Solution in 1,1,2-trichloroethane was coated on a microporous polypropylene hollow thread (manufacturer Akzo) by pumping the solution through the lumen of the hollow thread. The solvent was then evaporated using a stream of nitrogen. An approximately 1 μm thin Sympatex layer was formed in the interior of the hollow fibers. The following gas permeabilities were determined:
C02 Methan Ammoniak Schwefel was ser- Wasserstoff dampfC0 2 methane ammonia sulfur water hydrogen vapor
2,59 5,08 80 4,53 280 148 380002.59 5.08 80 4.53 280 148 38000
-3 3 2 Permeabilitäten in 10 x m /m h bar-3 3 2 permeabilities in 10 x m / m h bar
Die resultierende Wasserdampf/Stickstoff-Selektivität betrug 14700. The resulting water vapor / nitrogen selectivity was 14,700.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97935495A EP0946271A1 (en) | 1996-08-07 | 1997-07-30 | Composite membrane comprising a polyether-polyester block copolymer coating for separating polar gases from gaseous mixtures |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19631841A DE19631841C2 (en) | 1996-08-07 | 1996-08-07 | Composite membrane with a coating of polyether-polyester block copolymers for the separation of polar gases from gas mixtures |
| DE19631841.6 | 1996-08-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998005414A1 true WO1998005414A1 (en) | 1998-02-12 |
Family
ID=7802002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE1997/001618 Ceased WO1998005414A1 (en) | 1996-08-07 | 1997-07-30 | Composite membrane comprising a polyether-polyester block copolymer coating for separating polar gases from gaseous mixtures |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0946271A1 (en) |
| DE (1) | DE19631841C2 (en) |
| WO (1) | WO1998005414A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2488089C1 (en) * | 2012-03-14 | 2013-07-20 | Общество С Ограниченной Ответственностью Научно-Техническая Фирма "Бакс" | Sampling device for collecting hydrogen sulphide from molten sulphur |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10101295A1 (en) * | 2001-01-12 | 2002-07-18 | Linde Ag | Process for liquefying a hydrocarbon-rich stream, especially natural gas, comprises purifying the hydrocarbon-rich stream, cooling and partially condensing the purified stream, and removing higher hydrocarbons and carbon dioxide |
| US6860920B2 (en) * | 2002-03-28 | 2005-03-01 | L'air Liquide-Societe Anoyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes George Claude | Block polyester-ether gas separation membranes |
Citations (8)
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|---|---|---|---|---|
| US3653180A (en) * | 1970-11-02 | 1972-04-04 | Gen Electric | Block copolymer membrane for separating polar contaminants from gaseous mixtures |
| JPS4973384A (en) * | 1972-11-14 | 1974-07-16 | ||
| EP0111360A1 (en) * | 1982-12-02 | 1984-06-20 | Akzo N.V. | Flexible layered product |
| EP0315981A2 (en) * | 1987-11-12 | 1989-05-17 | Nitto Denko Corporation | Process for separating methane using permeable membrane |
| WO1989006158A1 (en) * | 1987-12-31 | 1989-07-13 | Membrane Technology & Research, Inc. | Process for separating higher hydrocarbons from natural or produced gas streams |
| US5407466A (en) * | 1993-10-25 | 1995-04-18 | Membrane Technology And Research, Inc. | Sour gas treatment process including membrane and non-membrane treatment steps |
| WO1995024260A1 (en) * | 1994-03-11 | 1995-09-14 | Akzo Nobel Nv | Device for separating mixtures of substances or for purifying substances by pervaporation |
| DE4432482A1 (en) * | 1994-09-13 | 1996-03-14 | Akzo Nobel Nv | Long-life drier for gas, esp. compressed air with low energy requirement |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS594417A (en) * | 1982-07-01 | 1984-01-11 | Teijin Ltd | Moisture barrier article |
| JPH04227827A (en) * | 1987-07-20 | 1992-08-17 | Mitsubishi Rayon Co Ltd | Porous hollow-fiber membrane and its production |
| DE4306276A1 (en) * | 1992-10-07 | 1994-04-14 | Wolff Walsrode Ag | Water vapor permeable, breathable films and their use |
| US5628179A (en) * | 1993-11-04 | 1997-05-13 | General Electric Co. | Steam attemperation circuit for a combined cycle steam cooled gas turbine |
-
1996
- 1996-08-07 DE DE19631841A patent/DE19631841C2/en not_active Expired - Fee Related
-
1997
- 1997-07-30 EP EP97935495A patent/EP0946271A1/en not_active Withdrawn
- 1997-07-30 WO PCT/DE1997/001618 patent/WO1998005414A1/en not_active Ceased
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3653180A (en) * | 1970-11-02 | 1972-04-04 | Gen Electric | Block copolymer membrane for separating polar contaminants from gaseous mixtures |
| JPS4973384A (en) * | 1972-11-14 | 1974-07-16 | ||
| EP0111360A1 (en) * | 1982-12-02 | 1984-06-20 | Akzo N.V. | Flexible layered product |
| EP0315981A2 (en) * | 1987-11-12 | 1989-05-17 | Nitto Denko Corporation | Process for separating methane using permeable membrane |
| WO1989006158A1 (en) * | 1987-12-31 | 1989-07-13 | Membrane Technology & Research, Inc. | Process for separating higher hydrocarbons from natural or produced gas streams |
| US5407466A (en) * | 1993-10-25 | 1995-04-18 | Membrane Technology And Research, Inc. | Sour gas treatment process including membrane and non-membrane treatment steps |
| WO1995024260A1 (en) * | 1994-03-11 | 1995-09-14 | Akzo Nobel Nv | Device for separating mixtures of substances or for purifying substances by pervaporation |
| DE4432482A1 (en) * | 1994-09-13 | 1996-03-14 | Akzo Nobel Nv | Long-life drier for gas, esp. compressed air with low energy requirement |
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| CHEMICAL ABSTRACTS, vol. 82, no. 18, 5 May 1975, Columbus, Ohio, US; abstract no. 113570, XP002048758 * |
| DATABASE WPI Week 7526, 1975 Derwent World Patents Index; AN 75-43177w, XP002048512 * |
| DONALD J. LYMAN: "New Synthetic Membranes for Dialysis. I. A Copolyether-Ester Membrane System", BIOCHEMISTRY, vol. 3, no. 7, July 1964 (1964-07-01), pages 985 - 990, XP002048508 * |
| MARK H.F.: "Kirk-Othmer Encyclopedia of Chemical Technology", 1978, WILEY & SONS, NEW-YORK, XP002048509, 160940 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2488089C1 (en) * | 2012-03-14 | 2013-07-20 | Общество С Ограниченной Ответственностью Научно-Техническая Фирма "Бакс" | Sampling device for collecting hydrogen sulphide from molten sulphur |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0946271A1 (en) | 1999-10-06 |
| DE19631841A1 (en) | 1998-02-12 |
| DE19631841C2 (en) | 1998-11-05 |
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