WO1995028626A1 - Systeme d'extraction de gaz contenus dans des liquides avec detection consecutive et utilisation dudit systeme - Google Patents

Systeme d'extraction de gaz contenus dans des liquides avec detection consecutive et utilisation dudit systeme Download PDF

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Publication number
WO1995028626A1
WO1995028626A1 PCT/DE1995/000495 DE9500495W WO9528626A1 WO 1995028626 A1 WO1995028626 A1 WO 1995028626A1 DE 9500495 W DE9500495 W DE 9500495W WO 9528626 A1 WO9528626 A1 WO 9528626A1
Authority
WO
WIPO (PCT)
Prior art keywords
permeation
gas
foils
gases
space
Prior art date
Application number
PCT/DE1995/000495
Other languages
German (de)
English (en)
Inventor
Alfred MÜHLWITZ
Hans-Jochen Rindfleisch
Fred Schaffarzik
Original Assignee
Medium - Sensor 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
Priority claimed from DE19944413197 external-priority patent/DE4413197A1/de
Application filed by Medium - Sensor Gmbh filed Critical Medium - Sensor Gmbh
Priority to AU22539/95A priority Critical patent/AU2253995A/en
Priority to DE19580326T priority patent/DE19580326D2/de
Publication of WO1995028626A1 publication Critical patent/WO1995028626A1/fr

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; viscous liquids; paints; inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
    • G01N33/2841—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel gas in oil, e.g. hydrogen in insulating oil
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0011—Sample conditioning
    • G01N33/0016—Sample conditioning by regulating a physical variable, e.g. pressure, temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

Definitions

  • the extraction of gases contained in liquids is used in many fields of technology. However, the preferred area of application is analysis for the qualitative and quantitative detection of the extracted gases.
  • the gases contained in the liquid can allow conclusions to be drawn about their condition. In the presence of certain gases, disturbances or environmental pollution can be signaled.
  • DE 28 04 367 AI describes a method and a device for removing and analyzing a gas carried in a liquid volume.
  • the liquid is circulated using the density at different temperatures.
  • the oil taken from a transformer housing is cooled by a temperature of 80 to 85 C in a tube with cooling plates designed as a cooling device by 10 to 20 ° C and then returned to the housing.
  • a gas separation cell is arranged, which consists of a porous carrier tube and a semipermeable membrane.
  • the gas that accumulates in the cell is transported into the gas detector / analyzer unit with the aid of a carrier gas.
  • a carrier gas and on the other hand, the restriction of gas detection to gases with a low molecular weight, for example hydrogen, carbon monoxide and carbon dioxide.
  • the detection of the gas concentrations in the liquid can also be achieved in known ways in that it is not the permeation gas flow of the respective gas component but its concentration in the gas space that is determined after the partial pressure equilibrium has been set.
  • the time that the compensation process takes also depends on the membrane area, the membrane thickness and the volume of the gas space with respect to the membrane area and thickness, but in the inverse ratio to the permeation gas flow. This means that in practical cases this time with a disk-shaped membrane and a measuring cell arranged behind it cannot be reduced to below the values available for recording damage-relevant processes. This means that the speed of the gas measurement is too low in comparison to the speed of the concentration changes in the transformer oil in order to be able to detect damage processes at an early stage.
  • the invention is based on the problem of effectively carrying out a quasi-continuous and rapid extraction of gases of high solubility and low concentration from liquids with the aid of permeation technology, in order to recognize damage development or disturbance within a few hours in an immediately subsequent analysis and to signalize.
  • the distance between two permeation foils, which are connected to one another in a gas-tight manner is inversely proportional in size to the thickness of the permeation foils.
  • the distance should preferably be less than 400 ⁇ m with a permeation film thickness of 10 ⁇ m.
  • the distance between the permeation foils must be able to be reversibly reduced to at least 50% of its initial value by the action of a force.
  • At least one tubular or tubular discharge leads to the measuring cell. If a support layer is arranged in the gas space, it can be advantageous for the diversion to continue in the form of a channel into the support layer. Spacers made of pressure-resistant and gas-conducting material can also ensure the necessary maintenance of the distance.
  • edges of the permeation foils are connected using known techniques. It may be advantageous to metallize these edges beforehand.
  • Either mechanical or physical means can be used to discharge the gas collected in the gas space by permeation.
  • the gas separated from the liquid by permeation is displaced from the space between the two gas-permeable foils, an internal pressure gradient building up towards the outlets and thus a rapid outflow of the gas from the gap-shaped gas space is achieved.
  • the time for the removal of the gas is determined solely by the speed at which the displacement front which arises as a result of the progressive reduction in volume moves toward the diversions which are under normal pressure.
  • the resulting internal pressure leads to an expansion of the gap-shaped gas space due to the elastic expansion of the permeation foils, whereby the flow resistance is reduced and the rapid removal of the gas additionally is supported.
  • the removal of the gas can also be accelerated according to the invention in that a pressure is built up in the liquid container, which acts on the permeation foils and compresses the gas-conducting support layer in the gas space.
  • the device according to the invention is particularly suitable for monitoring water or waste water for gases which cause damage in the context of environmental protection and for timely detection of disturbances in oil-filled high-voltage devices, in particular transformers.
  • the device can be arranged inside the medium to be examined or outside in a circuit.
  • the device is enclosed by a pressure-resistant container 15, which is connected via the inlet 22 and the outlet 23 to the liquid 4 to be examined, so that the liquid 4 completely fills the container 15.
  • FIG. 2 shows a very similar device.
  • the permeation foils 1 are coated with a gas-permeable layer made of permanently magnetic material 7, the opposite layers being magnetized in opposite directions to one another. As a result, the permeation foils 1 are kept at a distance.
  • the gas-permeable layer made of permanent magnetic material 7 can also be replaced by a protective grid 16. This is said to cause undesired balloon-like inflation of the permeation films 1 Prevent during permeation.
  • a hydraulic container 13 can also be used.
  • the permeation foils 1 are surrounded by a gas-permeable metallization layer, which represents the counterelectrode 12.
  • the capacitor plates serving as the electrode 11 are arranged in a cylinder shape around the permeation films 1.
  • spacer strips 14 are provided.
  • a direct voltage of 10 KV is applied to the electrode 11.
  • the counter electrode 12 is grounded.
  • the permeation films 1 are kept at a distance, so that a support layer 6 is omitted.
  • FIG. 4 shows a further variant of the device according to the invention.
  • strip-shaped spacers 8 made of pressure-resistant and gas-conducting material, which run towards the outlet 3, are arranged within the elastic, gas-conducting support layer 6, which simultaneously function as channels.
  • Section A - A shows a section through the permeation films 1 before the permeable gas is discharged. Section A ,. - A_, after that.
  • the device according to the invention is embodied in the form of a band in accordance with FIG. 5 and is attached to a hub 24 with its side facing away from the diversion 3, is additionally fixed by a pressure roller 25 and is held taut by a spring 26.
  • the left picture in FIG. 5 shows a side view, on the right a front view is shown.
  • FIG. 1 The structure of the device is shown in Figure 1.
  • pump 17 By means of pump 17 there is a constant flow through the container 15 with the liquid 4 to be examined.
  • valve 18 To carry out of the first measuring cycle, valve 18 is closed and valve 20 is opened.
  • the valve 19 in the drain line 23 is closed, as a result of which the pump 17 builds up a pressure in the container 15, which acts on the permeation films 1, compresses the gas-conducting support layer 6 and the gas located in the gas space 2 between the permeation films 1 into the measuring cell 9 presses where the detection is performed.
  • valve 20 is closed and valve 18 is opened.
  • valve 19 By subsequently opening the valve 19, the pressure prevailing in the container 15 is reduced, the gas-conducting support layer 6 erecting itself when the valve 18 is still open and outside air which is under normal pressure is sucked into the gas space 2 between the permeation films 1.
  • the next measuring cycle begins when the partial pressure equilibrium with the surrounding liquid 4 has been established again in the gas space 2 between the two permeation foils 1.
  • the liquid 4 to be examined is pumped into the container 15 by the pump 17. Both a continuous and a cyclical mode of operation are possible.
  • the valves 18, 20 and 21 are closed.
  • valve 19 is open, otherwise closed.
  • valve 20 is opened, as a result of which the permeable gas is led to the measuring cell 9 under the application of pressure and is detected there.
  • the pressure can be applied by mechanical means, shown in other examples, or with compressed air.
  • the permeation foils 1 are located in a hydraulic container 13, which is arranged outside the liquid 4 to be examined.
  • the valves 18, 19, 20 and 21 are initially closed.
  • a defined volume, for example 35 cm, is now removed from the hydraulic container 13 via valve 21. It can be advantageous to install a capillary in the discharge line 3, which ensures pressure equalization with the outside atmosphere during the process. After reaching the partial pressure equilibrium, the mene amount of liquid 4 supplied again or there is a complete exchange and refill.
  • the permeable gas is discharged and detected in the measuring cell 9.
  • the gas space 2 of permeation foils 1 according to FIG. 3 arranged between capacitor plates can be emptied after the partial pressure equilibrium has been reached by switching off the current.
  • This principle does not require a support layer 6 in the gas space 2.
  • the permeation foils 1 provided with bar-shaped spacers 8 and a support layer 6 are located in a closed container 15.
  • the volume in the gas space 2 is reduced, with the channels formed by the spacers 8 and those in the edge zones of the spacers 8 resulting gusset 10 is followed by the removal of the displaced gas.
  • the permeable gas is discharged from the gas space 2 exclusively by mechanical means.
  • the elastic support layer 6 is pressed together with the valve 20 and the valve 18 open, whereby the gas is pressed into the measuring cell 9.
  • the support layer 6 straightens up again, whereby air which is under normal pressure is sucked into the support layer 6 of the gas space 2 when the valve 18 is open and the valve 20 is closed.
  • Valve 18 is then closed.
  • the next measuring cycle begins with the opening of the valve 20 and the winding of the permeation foils 1 onto the hub 24.
  • the gas can be expelled from the support layer 6 are supported by a pressure roller 25.
  • the invention can be used commercially in all fields in which gases dissolved in liquids are extracted and then examined qualitatively or quantitatively. The results obtained allow conclusions to be drawn about the state of the liquid.
  • a preferred area of application is environmental protection when monitoring water or waste water.
  • the invention enables the operating state of oil-filled high-voltage devices to be monitored, in which damage processes are to be expected and which must be recognized in good time.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Pathology (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

Des liquides de différente nature, par exemple des eaux, des eaux usées ou des huiles isolantes pour transformateurs, peuvent présenter des concentrations différentes de gaz dissous, qui constituent une source d'accidents considérable ou entraînent des manifestations perturbatrices. L'invention vise à permettre une extraction quasi-continue et rapide de ces gaz, selon la technique de perméation, afin de détecter ou de signaler immédiatement ou à temps, l'émergence d'une défaillance ou d'une manifestation perturbatrice, par une détection effectuée immédiatement à la suite de l'extraction. Selon l'invention, l'extraction s'effectue à l'aide d'un dispositif qui comprend deux films de perméation (1) reliés l'un à l'autre, de manière étanche aux gaz, par leurs bords et au moins une conduite de sortie (3) qui est tubulaire ou se présente sous forme de flexible. Afin que l'écart entre les films de perméation (1) qui constituent le compartiment du gaz (2) soit maintenu, on peut disposer une couche de soutien (6) ou maintenir ledit écart par des moyens physiques, par exemple magnétiquement ou électrostatiquement. L'écart est inversement proportionnel à l'épaisseur des films de perméation (1) et peut être ramené, élastiquement, de manière réversible, à au moins 50 % de sa valeur initiale, sous l'action d'une force. Les gaz collectés sont expulsés sous l'action de pressions les plus diverses, une détection consécutive étant effectuée dans une cellule de mesure (9).
PCT/DE1995/000495 1994-04-14 1995-04-10 Systeme d'extraction de gaz contenus dans des liquides avec detection consecutive et utilisation dudit systeme WO1995028626A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU22539/95A AU2253995A (en) 1994-04-14 1995-04-10 Device for extracting the gases in liquids with subsequent detection, and its use
DE19580326T DE19580326D2 (de) 1994-04-14 1995-04-10 Vorrichtung zur Extraktion mit anschließendem Nachweis der in Flüssigkeiten enthaltenen Gase und deren Verwendung

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4413197.6 1994-04-14
DE19944413197 DE4413197A1 (de) 1994-04-14 1994-04-14 Vorrichtung zur Extraktion mit anschließendem Nachweis der in Flüssigkeiten enthaltenen Gase und deren Verwendung
DE19513331A DE19513331A1 (de) 1994-04-14 1995-04-03 Vorrichtung zur Extraktion mit anschließendem Nachweis der in Flüssigkeiten enthaltenen Gase
DE19513331.5 1995-04-03

Publications (1)

Publication Number Publication Date
WO1995028626A1 true WO1995028626A1 (fr) 1995-10-26

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Country Status (3)

Country Link
AU (1) AU2253995A (fr)
DE (1) DE19580326D2 (fr)
WO (1) WO1995028626A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5749942A (en) * 1997-02-14 1998-05-12 Raychem Corporation Apparatus for extracting a gas from a liquid and delivering the gas to a collection station
US6037592A (en) * 1997-02-14 2000-03-14 Underground Systems, Inc. System for measuring gases dissolved in a liquid
CN111108381A (zh) * 2017-08-04 2020-05-05 丹麦蓝单元公司 二氧化碳和/或硫化氢检测系统和方法及其应用
AT523841B1 (de) * 2020-10-19 2021-12-15 Omicron Electronics Gmbh Vorrichtung und Verfahren zum Entgasen einer Einrichtung und entsprechendes Prüfsystem zur Gasanalyse

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4112737A (en) * 1977-04-27 1978-09-12 Morgan Schaffer Corporation Transformer fault detection
DE3205229A1 (de) * 1982-02-13 1983-08-25 Sartorius GmbH, 3400 Göttingen Wegwerf-filter
DE3433179A1 (de) * 1984-09-10 1986-03-20 INTERATOM GmbH, 5060 Bergisch Gladbach Verfahren und vorrichtung zum quantitativen nachweis von wasserstoffisotopen in einem medium
US4890478A (en) * 1987-09-11 1990-01-02 Westinghouse Electric Corp. Gas-in-oil monitoring apparatus and method
EP0448973A1 (fr) * 1990-02-27 1991-10-02 Toray Industries, Inc. Module à membrane enroulée en spirale et perméable aux gaz ainsi qu'appareil et procédé pour son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4112737A (en) * 1977-04-27 1978-09-12 Morgan Schaffer Corporation Transformer fault detection
DE3205229A1 (de) * 1982-02-13 1983-08-25 Sartorius GmbH, 3400 Göttingen Wegwerf-filter
DE3433179A1 (de) * 1984-09-10 1986-03-20 INTERATOM GmbH, 5060 Bergisch Gladbach Verfahren und vorrichtung zum quantitativen nachweis von wasserstoffisotopen in einem medium
US4890478A (en) * 1987-09-11 1990-01-02 Westinghouse Electric Corp. Gas-in-oil monitoring apparatus and method
EP0448973A1 (fr) * 1990-02-27 1991-10-02 Toray Industries, Inc. Module à membrane enroulée en spirale et perméable aux gaz ainsi qu'appareil et procédé pour son utilisation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5749942A (en) * 1997-02-14 1998-05-12 Raychem Corporation Apparatus for extracting a gas from a liquid and delivering the gas to a collection station
US6037592A (en) * 1997-02-14 2000-03-14 Underground Systems, Inc. System for measuring gases dissolved in a liquid
CN111108381A (zh) * 2017-08-04 2020-05-05 丹麦蓝单元公司 二氧化碳和/或硫化氢检测系统和方法及其应用
US11609204B2 (en) 2017-08-04 2023-03-21 Blue Unit A/S Carbon dioxide and/or hydrogen sulphide detection system and method and use thereof
AT523841B1 (de) * 2020-10-19 2021-12-15 Omicron Electronics Gmbh Vorrichtung und Verfahren zum Entgasen einer Einrichtung und entsprechendes Prüfsystem zur Gasanalyse
AT523841A4 (de) * 2020-10-19 2021-12-15 Omicron Electronics Gmbh Vorrichtung und Verfahren zum Entgasen einer Einrichtung und entsprechendes Prüfsystem zur Gasanalyse

Also Published As

Publication number Publication date
AU2253995A (en) 1995-11-10
DE19580326D2 (de) 1997-07-31

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