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WO1998005414A1 - Membrane composite comportant un revetement de copolymeres sequences polyether-polyester, destinee a la separation de gaz polaires contenus dans des melanges gazeux - Google Patents

Membrane composite comportant un revetement de copolymeres sequences polyether-polyester, destinee a la separation de gaz polaires contenus dans des melanges gazeux Download PDF

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Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
composite membrane
membrane according
blocks
water vapor
separation
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.)
Ceased
Application number
PCT/DE1997/001618
Other languages
German (de)
English (en)
Inventor
Klaus-Viktor Peinemann
Yanwei Cen
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
Priority to EP97935495A priority Critical patent/EP0946271A1/fr
Publication of WO1998005414A1 publication Critical patent/WO1998005414A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • 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
    • 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
    • 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.

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

Membrane composite constituée d'une membrane support microporeuse et d'une couche de séparation appliquée sur ladite membrane support. Cette membrane composite se caractérise en ce que la couche de séparation est réalisée à partir d'un copolyéther-ester séquencé et présente une épaisseur ≤ 3 νm. Cette membrane composite permet de séparer sélectivement des gaz polaires (vapeur d'eau, hydrogène sulfuré) contenus dans des mélanges gazeux, et peut être utilisée par exemple pour sécher du gaz naturel avant son introduction dans un réseau central de distribution.
PCT/DE1997/001618 1996-08-07 1997-07-30 Membrane composite comportant un revetement de copolymeres sequences polyether-polyester, destinee a la separation de gaz polaires contenus dans des melanges gazeux Ceased WO1998005414A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97935495A EP0946271A1 (fr) 1996-08-07 1997-07-30 Membrane composite comportant un revetement de copolymeres sequences polyether-polyester, destinee a la separation de gaz polaires contenus dans des melanges gazeux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19631841A DE19631841C2 (de) 1996-08-07 1996-08-07 Kompositmembran mit einer Beschichtung aus Polyether-Polyester-Block-Copolymeren zur Abtrennung von polaren Gasen aus Gasgemischen
DE19631841.6 1996-08-07

Publications (1)

Publication Number Publication Date
WO1998005414A1 true WO1998005414A1 (fr) 1998-02-12

Family

ID=7802002

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1997/001618 Ceased WO1998005414A1 (fr) 1996-08-07 1997-07-30 Membrane composite comportant un revetement de copolymeres sequences polyether-polyester, destinee a la separation de gaz polaires contenus dans des melanges gazeux

Country Status (3)

Country Link
EP (1) EP0946271A1 (fr)
DE (1) DE19631841C2 (fr)
WO (1) WO1998005414A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2488089C1 (ru) * 2012-03-14 2013-07-20 Общество С Ограниченной Ответственностью Научно-Техническая Фирма "Бакс" Пробоотборник для отбора сероводорода из расплава серы

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10101295A1 (de) * 2001-01-12 2002-07-18 Linde Ag Verfahren zum Verlüssigen eines Kohlenwasserstoffreichen Stromes
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)

* Cited by examiner, † Cited by third party
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 (fr) * 1972-11-14 1974-07-16
EP0111360A1 (fr) * 1982-12-02 1984-06-20 Akzo N.V. Produit stratifié flexible
EP0315981A2 (fr) * 1987-11-12 1989-05-17 Nitto Denko Corporation Procédé de séparation de méthane utilisant des membranes perméables
WO1989006158A1 (fr) * 1987-12-31 1989-07-13 Membrane Technology & Research, Inc. Procede de separation d'hydrocarbures superieurs a partir de flux de gaz naturel ou produit
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 (fr) * 1994-03-11 1995-09-14 Akzo Nobel Nv Dispositif permettant de separer des melanges de substances ou de purifier des substances par pervaporation
DE4432482A1 (de) * 1994-09-13 1996-03-14 Akzo Nobel Nv Vorrichtung zur Trocknung gasförmiger Medien

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS594417A (ja) * 1982-07-01 1984-01-11 Teijin Ltd 乾燥用品
JPH04227827A (ja) * 1987-07-20 1992-08-17 Mitsubishi Rayon Co Ltd 多孔質中空繊維状膜の製造方法及び多孔質中空繊維状膜
DE4306276A1 (de) * 1992-10-07 1994-04-14 Wolff Walsrode Ag Wasserdampfdurchlässige, atmungsaktive Folien sowie deren Verwendung
US5628179A (en) * 1993-11-04 1997-05-13 General Electric Co. Steam attemperation circuit for a combined cycle steam cooled gas turbine

Patent Citations (8)

* Cited by examiner, † Cited by third party
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 (fr) * 1972-11-14 1974-07-16
EP0111360A1 (fr) * 1982-12-02 1984-06-20 Akzo N.V. Produit stratifié flexible
EP0315981A2 (fr) * 1987-11-12 1989-05-17 Nitto Denko Corporation Procédé de séparation de méthane utilisant des membranes perméables
WO1989006158A1 (fr) * 1987-12-31 1989-07-13 Membrane Technology & Research, Inc. Procede de separation d'hydrocarbures superieurs a partir de flux de gaz naturel ou produit
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 (fr) * 1994-03-11 1995-09-14 Akzo Nobel Nv Dispositif permettant de separer des melanges de substances ou de purifier des substances par pervaporation
DE4432482A1 (de) * 1994-09-13 1996-03-14 Akzo Nobel Nv Vorrichtung zur Trocknung gasförmiger Medien

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
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 *
MULDER M.: "Basic Principles of Membrane Technology", 1990, KLUWER, DORDRECHT, NL, XP002048510, 200820 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2488089C1 (ru) * 2012-03-14 2013-07-20 Общество С Ограниченной Ответственностью Научно-Техническая Фирма "Бакс" Пробоотборник для отбора сероводорода из расплава серы

Also Published As

Publication number Publication date
DE19631841C2 (de) 1998-11-05
EP0946271A1 (fr) 1999-10-06
DE19631841A1 (de) 1998-02-12

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