WO2023025716A1 - Procédé et dispositif pour éliminer l'oxygène résiduel de gaz inertes par synthèse de nanoparticules métalliques - Google Patents

Procédé et dispositif pour éliminer l'oxygène résiduel de gaz inertes par synthèse de nanoparticules métalliques Download PDF

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Publication number
WO2023025716A1
WO2023025716A1 PCT/EP2022/073308 EP2022073308W WO2023025716A1 WO 2023025716 A1 WO2023025716 A1 WO 2023025716A1 EP 2022073308 W EP2022073308 W EP 2022073308W WO 2023025716 A1 WO2023025716 A1 WO 2023025716A1
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WO
WIPO (PCT)
Prior art keywords
inert gas
residual oxygen
electrodes
nanoparticles
ppm
Prior art date
Application number
PCT/EP2022/073308
Other languages
German (de)
English (en)
Inventor
Vinzent OLSZOK
Malte BIERWIRTH
Alfred P. Weber
Original Assignee
Technische Universität Clausthal
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 Technische Universität Clausthal filed Critical Technische Universität Clausthal
Priority to EP22768693.8A priority Critical patent/EP4392164A1/fr
Publication of WO2023025716A1 publication Critical patent/WO2023025716A1/fr

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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
    • B01D53/32—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 electrical effects other than those provided for in group B01D61/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818—Employing electrical discharges or the generation of a plasma

Definitions

  • Patent application file number not yet assigned
  • the invention relates to a method and a device for removing residual oxygen from an inert gas.
  • oxide layers on their surface within a short time at room temperature in air. This oxide formation is disruptive for various processes, for example in semiconductor production. Such oxide layers can also be a hindrance when processing metals.
  • UHV ultra-high vacuum
  • UHV systems are expensive to purchase and operate.
  • the implementation of processes in UHV systems is time-consuming because the formation of an ultra-high vacuum requires a long pumping time that increases with falling residual pressure.
  • materials with a low vapor pressure, for example cannot be processed in an ultra-high vacuum.
  • oxygen scavengers For example, titanium chips are heated in ultra-high vacuum systems in order to stimulate the formation of titanium oxide, as a result of which the oxygen partial pressure drops.
  • Another known way of removing residual oxygen from an inert gas is to pass the inert gas through a sodium-potassium alloy that is liquid at room temperature and reacts with the residual oxygen.
  • this alloy of alkali metals is highly reactive and should be handled with great care from a safety point of view.
  • DE 44 26 081 B4 discloses a gas cleaning device for cleaning gases contaminated with pollutants, with a housing having an inlet opening and an exhaust gas opening and with a fan having at least one fan blade located between them and a device for generating a glow discharge between a housing inner wall and the fan blade .
  • the device includes a magnetic layer on the outside of the housing and electrodes on the inside surface of the housing and at least on the fan blade tip.
  • the inner wall of the housing and/or the fan blade are provided with a catalytically active metal layer which is selected from platinum, palladium, ruthenium and rhodium.
  • a cathode and an anode opposed to each other Upstream of the gas purification device, there are provided a cathode and an anode opposed to each other, and a deoxidizing element formed of zinc or indium and interposed between the anode and the cathode on the cathode side.
  • Exhaust gas is not directly introduced into the gas purification device but is first introduced into the deoxidizing element.
  • the oxygen contained in the exhaust gas comes into contact with zinc or indium or a site from which oxygen has been removed by sputtering zinc oxide (or indium oxide), thereby selectively trapping or removing the oxygen. absorbed and removed from the exhaust gas.
  • the oxygen-free exhaust gas is then fed to the gas cleaning device, where the gas is cleaned.
  • the invention is based on the object of demonstrating a method and a device for removing residual oxygen from an inert gas which are highly effective but do not require the use of highly reactive substances and also do not contaminate the inert gas with highly reactive substances.
  • a voltage is applied between two electrodes adjacent to the inert gas, which causes a direct gas discharge in the inert gas.
  • the direct gas discharge removes metal from at least one of the electrodes, forming nanoparticles in the inert gas.
  • the nanoparticles oxidize spontaneously, consuming the residual oxygen.
  • both of these electrodes also consist of metal, which is removed as a result of the gas discharge and forms nanoparticles in the inert gas, which then oxidize using the residual oxygen.
  • the other of the electrodes can be formed from a rather inert metal, which is removed to a lesser extent and also forms less reactive nanoparticles than the metal of the at least one of the electrodes.
  • the at least one of the two electrodes can be formed at least predominantly from aluminum or iron. This can also apply to the other of the two electrodes.
  • the other of the two electrodes can consist of a material, such as tungsten, which is not removed or is removed to a lesser extent as a result of the direct gas discharge. Tests have shown that the tendency of iron and aluminum nanoparticles to oxidize is completely sufficient to reduce the residual oxygen content in inert gases to well below 10'9 ppm. It can be assumed that other metals such as copper, magnesium and titanium are also suitable for the formation of nanoparticles in the method according to the invention, which oxidize spontaneously while consuming the residual oxygen in the inert gas.
  • Magnesium has an outstanding effect that can be used in particular for argon and other noble gases as inert gases. However, magnesium has no long-term stability under nitrogen due to nitride formation on electrode surfaces.
  • metal is to be removed from the at least one electrode in a significantly more than stoichiometric amount in order to form a sufficient number of nanoparticles with a sufficiently large reactive surface area to remove the residual oxygen from the inert gas to the desired extent.
  • 4 mol to 100 mol, preferably 8 mol to 40 mol, of the metal can be removed per 1 mol molecule of residual oxygen.
  • metal in the order of 1 pg can be removed in order to form the nanoparticles from it.
  • the oxidized nanoparticles are inert. Nevertheless, it is usually useful to filter the oxidized nanoparticles from the inert gas. This can easily be achieved with a series connection of particle filters with increasing degrees of separation.
  • the series connection of two 99.5% particle filters and one 99.999% particle filter has proven itself to essentially completely remove the oxidized nanoparticles from the inert gas without the 99.999% particle filter having to be changed frequently because it becomes contaminated with the filtered nanoparticles added.
  • the residual oxygen content can even be reduced to below 1 ⁇ 10′ 14 ppm. Concrete a residual oxygen content of 3.5 ⁇ 10′15 ppm was achieved when the process according to the invention was carried out twice.
  • a device for removing residual oxygen from inert gas according to the method according to the invention has a reaction space between a gas inlet and a gas outlet, two electrodes adjoining the reaction space and a voltage source.
  • the voltage source is designed to apply a voltage between the electrodes, which causes a direct gas discharge into the reaction space filled with inert gas, metal being removed from at least one of the electrodes by the direct gas discharge, forming nanoparticles in the inert gas. These nanoparticles oxidize spontaneously, consuming the residual oxygen.
  • the at least one of the electrodes can be formed at least predominantly from aluminum or iron or another of the metals copper, magnesium and titanium.
  • an oxygen probe for example a lambda probe
  • a controller of the device can then be designed to control the voltage source depending on the signal from the oxygen probe in such a way that so much material is removed that the residual oxygen content in the inert gas is reduced to 1 x 10' 10 ppm, preferably 1 x 10' 11 ppm, more preferably to 1 x 10' 12 ppm and most preferably to 1 x 10' 13 ppm.
  • the controller can also control a device that determines the flow of the inert gas through the reaction space, for example a valve between a pressure vessel for the inert gas and the gas inlet into the reaction space.
  • two or even more devices according to the invention can be connected in series, so that the inert gas flows through their reaction chambers one after the other.
  • a filter device which is designed to filter the oxidized nanoparticles from the inert gas, is preferably arranged downstream of the reaction space.
  • the filter device can have a series connection of particle filters with increasing degrees of separation, as has already been explained in connection with the method according to the invention.
  • a Changing the particle filter is only seldom necessary during operation of the device according to the invention because the particle filters only clog very slowly if their degree of separation is designed appropriately due to the small absolute number of nanoparticles formed and correspondingly to be filtered off with the particle filters.
  • the oxidation of the nanoparticles by the residual oxygen in the inert gas also takes place in the filter, i. H. as long as the nanoparticles are in contact with the inert gas.
  • Fig. 1 is a schematic representation of a device according to the invention.
  • FIG. 2 is a plot of a residual oxygen content in an inert gas versus time after the device according to FIG. 1 has been switched on until after the device has been switched off again.
  • the device 1 shown schematically in FIG. 1 has a reaction chamber 2 between a gas inlet 3 and a gas outlet 4, which are indicated by arrows.
  • Two metal electrodes 5 and 6 are arranged in the reaction chamber 2 and are connected to a voltage source 7 .
  • the voltage source 7 is shown as a DC voltage source; alternatively, the voltage source 7 can be designed as an alternating voltage source and/or as a pulsed voltage source.
  • the voltage source 7 applies a high voltage between the electrodes 5 and 6 which exceeds the breakdown voltage of an inert gas 8 arranged in the reaction space 2 . This results in a direct gas discharge 9 between the electrodes 5 and 6, which is visible as a spark gap 10 between the electrodes.
  • the current from the voltage source 7 charges a capacitor 11 connected across the gap between the electrodes 5 and 6 between the outputs of the voltage source 7 .
  • This increases the voltage across the capacitor 11, which is applied to the electrodes 5 and 6 is present.
  • the breakdown voltage which is linearly dependent on the distance between the electrodes 5 and 6, is reached, a rapid gas discharge 9 occurs between the electrodes 5 and 6.
  • the electrical energy stored in the capacitor 11 is released in the form of a spark. Accordingly, the gas discharge 9 does not take place continuously, but in the form of individual sparks with a frequency of the order of 1 Hz to a few kHz, often from 10 to 100 Hz. This frequency increases with the strength of the current from the voltage source 7 charging the capacitor 11 .
  • a larger capacitance of the capacitor 1 which is in a typical order of magnitude of a few to a few 10 nF, leads to higher energies of the individual sparks and thus to higher rates of removal of the metal from the electrodes 5 and 6.
  • the gas discharge 9 leads to a removal of metal from the electrodes 5 and 6, from which nanoparticles 12 form within the inert gas 8 in the reaction chamber 2.
  • a filter device 13 for filtering off the nanoparticles 12 from the inert gas 8 is arranged in front of the gas outlet 4 of the reaction chamber 2 . In concrete terms, this can involve a series connection of two 99.5% particle filters 14 and 15 and a 99.999% particle filter 16 .
  • the residual oxygen in the inert gas can also react with the nanoparticles 12 in the filter device 13 .
  • the residual oxygen in the inert gas exiting through the gas outlet 4 is detected using an oxygen probe 17 .
  • a controller 19 controls the voltage source 7 as a function of the signal 18 from the oxygen probe 17 .
  • FIG. 2 documents the time course of the oxygen concentration in nitrogen in ppm measured with the oxygen probe 17 according to FIG. 1 after the device 1 according to FIG. 1 was switched on and later switched off again.
  • the residual oxygen content drops quickly to 1 ⁇ 10′1 ppm after the gas discharge 9 has started.
  • the residual oxygen content is further reduced to about 1 ⁇ 10 -11 ppm.
  • the residual oxygen content rises again to about 1 ppm, which corresponds to the supplied nitrogen gas of purity 5.0.
  • the residual oxygen content could be reduced to 1 ⁇ 10-13 ppm.
  • two devices 1 connected in series a residual oxygen content of 3.5 ⁇ 10′15 ppm was even achieved.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

Pour éliminer l'oxygène résiduel d'un gaz inerte (8), une tension est appliquée entre deux électrodes adjacentes au gaz inerte (8), cette tension provoquant une décharge gazeuse (9) directe dans le gaz inerte (8). Consécutivement à la décharge gazeuse (9), du métal est enlevé par au moins l'une des électrodes (5, 6). Le métal forme des nanoparticules (12) dans le gaz inerte (8) qui s'oxydent spontanément par consommation de l'oxygène résiduel.
PCT/EP2022/073308 2021-08-24 2022-08-22 Procédé et dispositif pour éliminer l'oxygène résiduel de gaz inertes par synthèse de nanoparticules métalliques WO2023025716A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22768693.8A EP4392164A1 (fr) 2021-08-24 2022-08-22 Procédé et dispositif pour éliminer l'oxygène résiduel de gaz inertes par synthèse de nanoparticules métalliques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021121928.0 2021-08-24
DE102021121928.0A DE102021121928A1 (de) 2021-08-24 2021-08-24 Verfahren und Vorrichtung zum Entfernen von Restsauerstoff aus Inertgasen mittels Synthese von Metallnanopartikeln

Publications (1)

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WO2023025716A1 true WO2023025716A1 (fr) 2023-03-02

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PCT/EP2022/073308 WO2023025716A1 (fr) 2021-08-24 2022-08-22 Procédé et dispositif pour éliminer l'oxygène résiduel de gaz inertes par synthèse de nanoparticules métalliques

Country Status (3)

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EP (1) EP4392164A1 (fr)
DE (1) DE102021121928A1 (fr)
WO (1) WO2023025716A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4426081B4 (de) 1993-07-23 2006-06-08 Hokushin Industries, Inc., Yokohama Gasreinigungsvorrichtung
CN111617714A (zh) * 2020-05-27 2020-09-04 常州大学 一种催化反应装置及催化剂带电研究用仪器和使用方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4426081B4 (de) 1993-07-23 2006-06-08 Hokushin Industries, Inc., Yokohama Gasreinigungsvorrichtung
CN111617714A (zh) * 2020-05-27 2020-09-04 常州大学 一种催化反应装置及催化剂带电研究用仪器和使用方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A. RAI ET AL.: "Understanding the mechanism of aluminium nanoparticle oxidation", COMBUSTION THEORY AND MODELLING, vol. 10, no. 5, October 2006 (2006-10-01), pages 843 - 859, XP055556563, Retrieved from the Internet <URL:http://dx.doi.org/10.1080/13647830600800686> DOI: 10.1080/13647830600800686
A. RAI ET AL: "Understanding the mechanism of aluminium nanoparticle oxidation", COMBUSTION THEORY AND MODELLING, vol. 10, no. 5, 21 December 2010 (2010-12-21), GB, pages 843 - 859, XP055556563, ISSN: 1364-7830, DOI: 10.1080/13647830600800686 *
DAHLE S ET AL: "Gas purification by the plasma-oxidation of a rotating sacrificial electrode", PLASMA SOURCES SCIENCE AND TECHNOLOGY, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL, GB, vol. 24, no. 3, 2 June 2015 (2015-06-02), pages 35021, XP020285578, ISSN: 0963-0252, [retrieved on 20150602], DOI: 10.1088/0963-0252/24/3/035021 *
EISENNANOPARTIKEL W. KARIM ET AL.: "Size-dependent redox behavior of iron observed by in-situ single nanoparticle spectro-microscopy on well-defined model systems", SCIENTIFIC REPORTS, vol. 6, 6 January 2016 (2016-01-06), pages 18818

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Publication number Publication date
EP4392164A1 (fr) 2024-07-03
DE102021121928A1 (de) 2023-03-02

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