EP0880400A1 - Membrane composite a membrane support, en particulier a membrane support microporeuse - Google Patents

Membrane composite a membrane support, en particulier a membrane support microporeuse

Info

Publication number
EP0880400A1
EP0880400A1 EP97914083A EP97914083A EP0880400A1 EP 0880400 A1 EP0880400 A1 EP 0880400A1 EP 97914083 A EP97914083 A EP 97914083A EP 97914083 A EP97914083 A EP 97914083A EP 0880400 A1 EP0880400 A1 EP 0880400A1
Authority
EP
European Patent Office
Prior art keywords
composite membrane
water
membrane according
membrane
separating layer
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.)
Withdrawn
Application number
EP97914083A
Other languages
German (de)
English (en)
Inventor
Klaus-Viktor Peinemann
Detlev Fritsch
Ernst-Moritz Bellingen
Michael Deppe
Michael Schossig-Tiedemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GKSS Forshungszentrum Geesthacht GmbH
Original Assignee
GKSS Forshungszentrum Geesthacht GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by GKSS Forshungszentrum Geesthacht GmbH filed Critical GKSS Forshungszentrum Geesthacht GmbH
Publication of EP0880400A1 publication Critical patent/EP0880400A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01D53/26—Drying gases or vapours
    • B01D53/268—Drying gases or vapours by diffusion
    • 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
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/22—Cellulose ethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers

Definitions

  • the invention relates to a composite membrane composed of a microporous carrier membrane in particular and a separating layer applied thereon, a process for its production and the use of this composite membrane for separating water vapor from gas mixtures.
  • Absorption processes such as gas drying using glycol scrubbers (TEG, DEG), are used on a large industrial scale to process natural gas.
  • TOG glycol scrubbers
  • DEG glycol scrubbers
  • a disadvantage of this known absorption process 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 when operating 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, with the help of heat, pressure changes or a dry gas stream.
  • This known method is particularly suitable for drying low-loaded streams. In addition, particularly low residual moisture levels can be achieved.
  • a disadvantage of this known method is the fact that the adsorbent must be regenerated cyclically, so that the process is carried out discontinuously is.
  • this known method for the separation of high water loads is too expensive.
  • Refrigeration dryers are used for the continuous separation of water vapor from gas mixtures.
  • the dew points that can be achieved are approximately 2 ° C. since the cooling coils start to freeze below this temperature.
  • 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.
  • the membrane processes known to date can also be used to dehumidify larger amounts of gas.
  • the membrane separation there are always two outlet streams, namely the purified product stream and the water-laden permeate stream. Depending on the application, these streams 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, has good mechanical and chemical stability and can be used to separate water vapor from gas mixtures. This task is solved by teaching the claims.
  • the membrane according to the invention enables the selective separation of water vapor from gas mixtures.
  • the membrane according to the invention thus has a high flux density for water vapor and a very low one Flux density for other gases (e.g. N «, 0«, CO «, CH.). This leads to a particularly high selectivity, which results in only minor product losses.
  • the membrane area required is small or small.
  • the membrane according to the invention can be used, for example, in the drying of natural gas before it is fed into a central pipeline network and in the treatment of compressed air. It can also be used in room air conditioning since the natural composition of the breathing air is not changed.
  • Another application is the dehumidification of inert gases that are used to dry sensitive products. The inert gas consumption can be significantly reduced by a circular performance. This is partly due to the very low selectivity of the membrane according to the invention for oxygen / nitrogen.
  • the mechanical stability of the membrane according to the invention is achieved by the construction as a composite membrane and thus from different materials.
  • the high separation factors and also the flow rate are achieved by the polymers used according to the invention.
  • the polymers used according to the invention which were originally water-soluble and then made water-insoluble, for example by crosslinking with one or more di aldehyde (s), are Cel 1 ul osederi vate.
  • Cel 1 ul oseether in particular hydroxyethyl cellulose and hydroxypropylcel 1 ul ose, are preferably used.
  • a membrane with a selective separation layer based on these cellulose ethers is stable against condensates.
  • the membrane according to the invention can also be easily produced by an immersion process. There is therefore no need for complex interfacial polymerizations, as is the case with the known membranes.
  • the coating of the carrier membrane used can already be formed during the precipitation process of the carrier membrane by adding the membrane polymer into the precipitation bath.
  • the selectivity for the separation of water vapor / gas can be set up to a value of 20,000 as required by the choice of the coating thickness and thus the selective separation layer.
  • the membrane according to the invention is also inexpensive to produce, since commercially available polymers can be used.
  • a microporous PEI (polyetherimide) membrane is coated in an immersion bath.
  • the coating solution consists of 39.66% ethanol, 60% water, 0.24% glutardialdehyde and 0.1% ethyl cell ulose (Tylose 4000).
  • the membrane is dried at a temperature of 70 ° C in an oven and crosslinked.
  • the membrane is provided with a thin silicone layer. This second layer protects the extremely thin ethyl cel 1 ul and closes small pores.
  • a microporous polyetherimide membrane is coated in an immersion bath.
  • the coating solution consists of 37.2% ethanol, 61.9% water, 0.6% GI utardi al dehyd and 0.3% hydroxyethyl cel 1 ulose (Tylose H4000). Otherwise the procedure is as described in Example 1. The following permeabilities were determined for this membrane:
  • a microporous PEI (polyetherimide) membrane is coated in an immersion bath.
  • the coating solution consists of 37.61% ethanol, 62.05% water, 0.24% GI utardi aldehyde and 0.1% hydroxyethyl cell ul ose (Tylose 4000). Otherwise the procedure is as described in Example 1. The following permeabilities were determined for this membrane:
  • a microporous PEI (polyetherimide) membrane is coated in an immersion bath.
  • the coating solution consists of 39.65% ethanol, 60.0% water, 0.25% GI utardi aldehyde and 0.1% hydroxyethyl cel 1 ul ose (Tylose 10000). Otherwise the procedure is as described in Example 1. The following permeabilities were determined for this membrane:
  • PEI polyetherimide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane composite formée d'une membrane support, en particulier d'une membrane support microporeuse, et d'une couche active appliquée sur celle-ci. La couche active est fabriquée à partir d'au moins un dérivé cellulosique initialement soluble dans l'eau, lequel est rendu insoluble dans l'eau, notamment par réticulation avec un dialdéhyde. La membrane composite selon l'invention est utilisée en particulier pour séparer la vapeur d'eau de mélanges gazeux.
EP97914083A 1996-01-31 1997-01-24 Membrane composite a membrane support, en particulier a membrane support microporeuse Withdrawn EP0880400A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19603420 1996-01-31
DE19603420A DE19603420C1 (de) 1996-01-31 1996-01-31 Kompositmembran aus einer insbesondere mikroporösen Trägermembran
PCT/DE1997/000133 WO1997027934A1 (fr) 1996-01-31 1997-01-24 Membrane composite a membrane support, en particulier a membrane support microporeuse

Publications (1)

Publication Number Publication Date
EP0880400A1 true EP0880400A1 (fr) 1998-12-02

Family

ID=7784133

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97914083A Withdrawn EP0880400A1 (fr) 1996-01-31 1997-01-24 Membrane composite a membrane support, en particulier a membrane support microporeuse

Country Status (4)

Country Link
US (1) US6277483B1 (fr)
EP (1) EP0880400A1 (fr)
DE (1) DE19603420C1 (fr)
WO (1) WO1997027934A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19739144C2 (de) * 1997-09-06 2002-04-18 Geesthacht Gkss Forschung Vorrichtung zur Entfernung von Wasserdampf aus unter Druck befindlichen Gasen oder Gasgemischen
US6860772B2 (en) * 2000-01-10 2005-03-01 Vladimir M. Kabakov Transverse watercraft propeller
WO2002094555A1 (fr) * 2001-05-22 2002-11-28 Membrana Gmbh Lamine, procede de production du lamine et vetement contenant ce lamine
CA2493605A1 (fr) * 2001-07-25 2003-02-06 Richard A. Haase Procedes et appareil pour la fabrication de composes d'aluminium polycycliques et de desinfectants, et composes d'aluminium polycycliques et desinfectants obtenus par lesdits procedes et appareil
US6938853B2 (en) * 2002-03-15 2005-09-06 University Of Maryland, College Park Biomimetic mechanism for micro aircraft
MXPA04009982A (es) 2002-04-11 2006-02-22 Richard A Haase Metodos, procesos, sistemas y aparatos con tecnologia de combustiion de agua, para la combustion de hidrogeno y oxigeno.
US20040206693A1 (en) * 2003-04-16 2004-10-21 John Charkoudian Crosslinked cellulosic membrane
US20040206694A1 (en) * 2003-04-16 2004-10-21 John Charkoudian Epoxide-crosslinked, charged cellulosic membrane
US7517581B2 (en) * 2003-09-26 2009-04-14 Parker-Hannifin Corporation Semipermeable hydrophilic membrane
US8268269B2 (en) 2006-01-24 2012-09-18 Clearvalue Technologies, Inc. Manufacture of water chemistries
CN103879034B (zh) * 2013-01-30 2016-08-03 中国科学院宁波材料技术与工程研究所 一种高气密性全热交换膜及全热交换器
US9174164B2 (en) * 2013-12-30 2015-11-03 Gas Technology Institute Apparatus for dehumidifying gas and methods of use

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62241527A (ja) * 1986-04-14 1987-10-22 Daicel Chem Ind Ltd 空気の除湿方法
DK169616B1 (da) * 1986-08-27 1994-12-27 Dow Danmark Permeabel, porøs, polymerbehandlet plastmembran med hydrofil karakter, fremgangsmåder til fremstilling heraf samt anvendelse heraf
US4964989A (en) * 1986-12-23 1990-10-23 Pall Corporation Membranes with low protein adsorbability
US5084073A (en) * 1990-10-11 1992-01-28 Union Carbide Industrial Gases Technology Corporation Membrane drying process and system
US5641450A (en) * 1991-03-28 1997-06-24 Toray Industries, Inc. Process of making a module including a polysulphonic hollow fiber membrane
DE4217335C2 (de) * 1992-05-26 1996-01-18 Seitz Filter Werke Hydrophile Membran und Verfahren zu ihrer Herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9727934A1 *

Also Published As

Publication number Publication date
US6277483B1 (en) 2001-08-21
DE19603420C1 (de) 1997-05-22
WO1997027934A1 (fr) 1997-08-07

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