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WO1998035739A1 - Procede d'extraction de gaz dissous dans un liquide - Google Patents

Procede d'extraction de gaz dissous dans un liquide Download PDF

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Publication number
WO1998035739A1
WO1998035739A1 PCT/US1998/001972 US9801972W WO9835739A1 WO 1998035739 A1 WO1998035739 A1 WO 1998035739A1 US 9801972 W US9801972 W US 9801972W WO 9835739 A1 WO9835739 A1 WO 9835739A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
membrane
perfluoro
dimethyl
dioxole
Prior art date
Application number
PCT/US1998/001972
Other languages
English (en)
Inventor
Steven Sunshine
Original Assignee
Raychem Corporation
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 Raychem Corporation filed Critical Raychem Corporation
Publication of WO1998035739A1 publication Critical patent/WO1998035739A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0031—Degasification of liquids by filtration

Definitions

  • This invention relates to a method for extracting gases dissolved in a liquid.
  • the present invention provides a membrane-based method which is improved over prior art methods speed-wise. Accordingly, there is provided a method of extracting dissolved gas from a gas-containing liquid, comprising the steps of
  • Fig. 1 shows a preferred embodiment in which the membrane is a composite membrane.
  • Fig. 2 shows a mechanical support for the membrane.
  • Fig. 3 shows an apparatus for practicing this invention.
  • Figs. 4a and 4b show additional apparati for practicing this invention.
  • Amorphous polymers of perfluoro-2,2-dimethyl-l,3-dioxole have been used as permselective membranes for gas separation or enrichment processes, in which a component gas in a gas mixture is separated from or enriched with respect to the other component gases.
  • PFDD perfluoro-2,2-dimethyl-l,3-dioxole
  • the membrane need only be differentially permeable to the various component gases — it need not be impermeable to one or more of mixture components.
  • PFDD polymers have not been employed as the base material in permselective membranes for the separation of gases from a gas-containing liquid, an application which requires the membrane should be substantially impermeable to the liquid. Passage of the liquid through to the permeate chamber can interfere with the equipment used to transport or analyze the permeate gases or with the analytical method per se, for example preventing the use of infrared techniques. I have discovered that PFDD polymers unexpectedly offer an advantageous combination of high permeability to gases dissolved in a liquid and impermeability to the liquid.
  • PFDD polymer and "perfluoro-2,2-dimethyl-l,3- dioxole polymer” mean the homopolymer and copolymers of perfluoro-2,2-dimethy 1-1,3 - dioxole.
  • PFDD polymers suitable for this invention are disclosed in Squire, US 4,948,851 (1990); Squire, US 4,975,505 (1990); Squire, US 4,999,248 (1991); Squire, US 5,006,382 (1991); and Nemser et al, US 5,051,114 (1991); the disclosures of which are incorporated herein by reference.
  • PFDD is copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, perfluoromethyl vinyl ether, vinylidene fluoride, and chlorotrifluoroethylene with PFDD constituting between 65 and 99 mole % of the copolymer.
  • the PFDD polymer preferably has a glass transition temperature (Tg) between 140 and 240 °C.
  • Tg glass transition temperature
  • PFDD polymers are available under the tradename Teflon AF from E.I. Du Pont de Nemours and Company, Wilmington, Delaware, in grades such as 1600 and 2400, having T g 's of 160 and 240 °C, respectively.
  • the membrane may be an unsupported membrane of PFDD polymer, it may be desirable to minimize the thickness of the membrane to maximize the diffusion rate of the gases. Then, the membrane can beneficially be supported, for example on a porous support of, for example, vinylidene difluoride homopolymer or copolymer (collectively "PVDF polymer”), to form a composite membrane having improved ruggedness without sacrificing diffusion rates.
  • PVDF polymer vinylidene difluoride homopolymer or copolymer
  • Composite membrane 1 includes a thin layer 2 of PFDD polymer supported by a supporting material 3 made of PVDF polymer. Supporting material 3 is porous, having pores 4. In use, layer 2 should face the feed chamber, to avoid having the liquid filling up the void volume of support material 3.
  • layer 2 can be made very thin, as thin as 0.5-6 ⁇ m, by solvent casting of PFDD polymer onto supporting material 3. If coatings thicker than 0.5-6 ⁇ m are desired, multiple coatings may be applied. While multiple coating may undesirably thicken the PFDD polymer layer, it offers the advantage of safeguarding against pinhole defects, as might occur if only a single coating is used.
  • the permselective membrane permits the dissolved gas(es) in the gas-containing liquid to diffuse thereacross to the permeate chamber, while being substantially impermeable to the gas-containing liquid and retaining it in the feed chamber.
  • substantially impermeable it is meant that insufficient gas-containing liquid passes through to the permeate chamber to interfere with the functions of transporting the extracted gas, separating it into its constituent components, and or its analysis (with or without prior separation into constituent components).
  • Fig. 2 shows a membrane holder 10 adapted for supporting a circularly shaped membrane (not shown), comprising a circular perforated base 12 (e.g., a perforated metal plate or a wire mesh) having around its periphery a rubber edging 14.
  • a circular perforated base 12 e.g., a perforated metal plate or a wire mesh
  • the membrane is sandwiched between a pair of membrane holders 10, with edgings 14 gripping the edges of the membrane without damaging it.
  • Edgings 14 also provide a seal between the feed and permeate chambers and prevent liquid from leaking from one side to the other around the edges of the membrane.
  • the membrane need not necessarily be circular in shape, such shape being cited here only for purposes of illustration.
  • Separation cell 20 has a feed chamber 22 and a permeate chamber 24, separated from each other by a permselective membrane 26.
  • feed chamber 22 contains a liquid 29 containing dissolved therein one or more gases 30, gases 30 diffuse across membrane 26, but liquid 29 is retained.
  • feed chamber 22 be substantially filled with liquid 29, this is not essential; partial filling is permissible.
  • permeate chamber contains only gases 30.
  • the relative proportions of gases 30 on the permeate chamber (where there is more than one gas dissolved in liquid 29) will depend on their relative proportions dissolved in liquid 29 on the feed chamber and their respective distribution (Ostwald) coefficients.
  • Feed chamber 22 can be filled and emptied via inlets and outlets controlled by valves 28a and 28b. To prevent the buildup of depletion layers as the diffusion process takes place, it is preferable to provide some circulation of liquid 29.
  • Gases 30 on permeate chamber 24 can transported to a measurement apparatus via an outlet controlled by valve 28d.
  • a carrier gas can be introduced via an inlet controlled by valve 28c to facilitate transport.
  • Fig. 4a shows an alternative separation cell 31, in which the PFDD polymer membrane is in the form of a serpentine hollow tube 34.
  • the interior of tube 34 serves as the permeate chamber, while the volume of cell 31 external to tube 34 serves as feed chamber 32. It is to be understood that more than one tube 34 may be present, with only one shown here for simplicity.
  • Fig. 4b shows yet another alternative separation cell 41, in which the PFDD polymer membrane is in the form of a bundle of hollow fibers or tubes 44 (three shown). Again, the volume of cell 41 external to tubes 44 serves as feed chamber 42.
  • This invention is especially useful for the monitoring dissolved gases which accumulate in a power transformer's fluid as the transformer ages.
  • the oil in a transformer is typically either a hydrocarbon oil or a silicone oil. Faults in a transformer, such as a hot spot or an arc, cause localized deterioration of the oil and the generation of gases such as carbon monoxide, carbon dioxide, hydrogen, water vapor, methane, ethane, ethylene, and acetylene, or combinations thereof. The identity, concentration, and build-up rate of these gases is valuable for diagnosing the state of a transformer.
  • Teflon AF 1600 and Teflon AF 2400 are PFDD polymers while Teflon PTFE is a conventional tetrafluoroethylene polymer; all from E.I. Du Pont de Nemours and Company

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Ces gaz dissous dans un liquide, une huile de transformateur, par exemple, sont séparés dudit liquide au moyen d'une cellule de séparation pourvue d'une membrane permsélective faite d'un polymère perfluoro-2,2-diméthyl-1,3-dioxole.
PCT/US1998/001972 1997-02-14 1998-02-02 Procede d'extraction de gaz dissous dans un liquide WO1998035739A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80067697A 1997-02-14 1997-02-14
US08/800,676 1997-02-14

Publications (1)

Publication Number Publication Date
WO1998035739A1 true WO1998035739A1 (fr) 1998-08-20

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ID=25179059

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/001972 WO1998035739A1 (fr) 1997-02-14 1998-02-02 Procede d'extraction de gaz dissous dans un liquide

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Country Link
WO (1) WO1998035739A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1164185A3 (fr) * 2000-06-13 2002-11-27 Air Products And Chemicals, Inc. Procédé et appareil déstinés à réduire la formation de mousse pendant la fermentation
EP1568403A1 (fr) * 2004-02-25 2005-08-31 United Technologies Corporation Méthode de fabriquer une membrane non-poreuse
EP1782879A1 (fr) 2005-11-03 2007-05-09 United Technologies Corporation Sytème de désoxygénation d'essence avec une membrane multi-couche perméable à l'oxygène
WO2007093443A3 (fr) * 2006-02-17 2007-12-06 Boehringer Ingelheim Micropart Structure de membrane destinée à l'extraction de gaz
US7687110B2 (en) 2005-03-08 2010-03-30 Applied Microstructures, Inc. Method of in-line purification of CVD reactive precursor materials
RU2488089C1 (ru) * 2012-03-14 2013-07-20 Общество С Ограниченной Ответственностью Научно-Техническая Фирма "Бакс" Пробоотборник для отбора сероводорода из расплава серы

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073087A1 (fr) * 1981-08-20 1983-03-02 E.I. Du Pont De Nemours And Company Copolymères amorphes de perfluoro-2,2-diméthyl-1,3-dioxole
EP0376638A2 (fr) * 1988-12-29 1990-07-04 Japan Gore-Tex, Inc. Un tuyau pour la dégazéification des solvants
US4948851A (en) * 1981-08-20 1990-08-14 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
US4975505A (en) * 1981-08-20 1990-12-04 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
US4999248A (en) * 1981-08-20 1991-03-12 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
US5006382A (en) * 1981-08-20 1991-04-09 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
WO1992009353A1 (fr) * 1990-12-03 1992-06-11 W.L. Gore & Associates, Inc. Composites de copolymere de dioxole/tetrafluorethylene
EP0641594A1 (fr) * 1993-09-08 1995-03-08 W.L. Gore & Associates, Inc. Filtre oléophobe et hydrophobe perméable aux gaz

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073087A1 (fr) * 1981-08-20 1983-03-02 E.I. Du Pont De Nemours And Company Copolymères amorphes de perfluoro-2,2-diméthyl-1,3-dioxole
US4948851A (en) * 1981-08-20 1990-08-14 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
US4975505A (en) * 1981-08-20 1990-12-04 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
US4999248A (en) * 1981-08-20 1991-03-12 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
US5006382A (en) * 1981-08-20 1991-04-09 E. I. Du Pont De Nemours And Company Amorphous copolymers of perfluoro-2,2-dimethyl-1,3-dioxole
EP0376638A2 (fr) * 1988-12-29 1990-07-04 Japan Gore-Tex, Inc. Un tuyau pour la dégazéification des solvants
WO1992009353A1 (fr) * 1990-12-03 1992-06-11 W.L. Gore & Associates, Inc. Composites de copolymere de dioxole/tetrafluorethylene
EP0641594A1 (fr) * 1993-09-08 1995-03-08 W.L. Gore & Associates, Inc. Filtre oléophobe et hydrophobe perméable aux gaz

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1164185A3 (fr) * 2000-06-13 2002-11-27 Air Products And Chemicals, Inc. Procédé et appareil déstinés à réduire la formation de mousse pendant la fermentation
EP1568403A1 (fr) * 2004-02-25 2005-08-31 United Technologies Corporation Méthode de fabriquer une membrane non-poreuse
KR100696338B1 (ko) 2004-02-25 2007-03-21 유나이티드 테크놀로지스 코포레이션 비다공성 박막의 생산 방법
US8070859B2 (en) 2004-02-25 2011-12-06 Membrane Technology And Research, Inc. Method for producing a non-porous membrane
US7687110B2 (en) 2005-03-08 2010-03-30 Applied Microstructures, Inc. Method of in-line purification of CVD reactive precursor materials
EP1782879A1 (fr) 2005-11-03 2007-05-09 United Technologies Corporation Sytème de désoxygénation d'essence avec une membrane multi-couche perméable à l'oxygène
US7615104B2 (en) 2005-11-03 2009-11-10 United Technologies Corporation Fuel deoxygenation system with multi-layer oxygen permeable membrane
WO2007093443A3 (fr) * 2006-02-17 2007-12-06 Boehringer Ingelheim Micropart Structure de membrane destinée à l'extraction de gaz
JP2009526640A (ja) * 2006-02-17 2009-07-23 ベーリンガー インゲルハイム マイクロパーツ ゲゼルシャフト ミット ベシュレンクテル ハフツング ガス分離用の膜構造体
RU2488089C1 (ru) * 2012-03-14 2013-07-20 Общество С Ограниченной Ответственностью Научно-Техническая Фирма "Бакс" Пробоотборник для отбора сероводорода из расплава серы

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