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EP0765289A1 - Process and filter for producing no 2?-free nitrogen monoxide with sulphurous polymers - Google Patents

Process and filter for producing no 2?-free nitrogen monoxide with sulphurous polymers

Info

Publication number
EP0765289A1
EP0765289A1 EP95922470A EP95922470A EP0765289A1 EP 0765289 A1 EP0765289 A1 EP 0765289A1 EP 95922470 A EP95922470 A EP 95922470A EP 95922470 A EP95922470 A EP 95922470A EP 0765289 A1 EP0765289 A1 EP 0765289A1
Authority
EP
European Patent Office
Prior art keywords
filter
free
sulfur
gas
containing polymer
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Withdrawn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
EP95922470A
Other languages
German (de)
French (fr)
Inventor
Jörg von Eysmondt
Andreas Schleicher
Georg Frank
Manfred Eschwey
Hanns Stresius
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.)
Messer Griesheim GmbH
Ticona GmbH
Original Assignee
Hoechst AG
Messer Griesheim GmbH
Ticona 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 Hoechst AG, Messer Griesheim GmbH, Ticona GmbH filed Critical Hoechst AG
Publication of EP0765289A1 publication Critical patent/EP0765289A1/en
Withdrawn legal-status Critical Current

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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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P11/00—Drugs for disorders of the respiratory system
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24—Nitric oxide (NO)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • 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
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4533—Gas separation or purification devices adapted for specific applications for medical purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4541—Gas separation or purification devices adapted for specific applications for portable use, e.g. gas masks
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention relates to a method for producing nitrogen dioxide-free gases and liquids and a filter for the selective removal of nitrogen dioxide from gases and liquids.
  • Nitrogen monoxide gas or nitrogen monoxide gas mixtures which are free of nitrogen dioxide are required in exhaust gas measurement technology for the calibration of measurement and analysis systems.
  • NO nitrogen monoxide
  • N0 2 brown nitrogen dioxide
  • N0 2 The colorless nitrogen monoxide (NO) reacts quickly with molecular oxygen to give brown nitrogen dioxide (N0 2 ).
  • NO 2 is therefore formed from NO.
  • N0 2 is therefore - due to the omnipresent oxygen - an inherent contamination of NO.
  • the content of N0 2 must be very low due to the toxicity. Efforts have therefore not been lacking to selectively absorb the NO 2 once formed or to convert it to NO.
  • N0 2 dissolves very well in concentrated inorganic acids such as HN0 3 or H 2 S0 4 . NO can therefore be cleaned very well with the aid of a gas scrubber using the abovementioned acids (A. Golloch, inorganic chemical preparations, Walter de Gruyter Verlag 1985, pp. 232 f.).
  • the disadvantage here is the relatively high level of safety and procedural complexity.
  • the task was to find a simple method and a filter for the selective removal of NO 2 from NO x -containing gases or liquids.
  • the invention therefore relates to a process for the production of NO-containing gases or liquids which are free of NO 2 , a NO x -containing gas or a NO x -containing liquid being brought into contact with a material which contains a sulfur-containing polymer, N0 2 is preferably removed from an NO-containing gas mixture.
  • free of NO 2 means that the content of NO in a medium is less than 1 ppm.
  • NO x is used as a collective term for the nitrogen oxides NO, N0 2 and N 2 0 and also includes mixtures of these oxides.
  • Polymers containing sulfur are, for example, linear or branched polyaryl systems (average molecular weight, Mw: 4000-200000) with the repeating unit of the formula I, which contain at least one thioether group,
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , W, X, Y and Z are independently the same or different.
  • the indices n, m, i, j, k, I, o and p are integers from 0 to 4, the sum of which must be at least 2.
  • Ar 1 , Ar 2 Ar 3 and Ar 4 in formula (I) stand for simple or directly via para, meta or ortho-linked aryl systems with 6 to 18 carbon atoms.
  • W, X, Y and Z represent linking groups selected from -S0 2 -, -S-, -SO-, -0-, -CO-, -C0 2 -, alkyl or alkylidene groups with 1 -6 carbon atoms and -NR 1 groups, where R 1 stands for alkyl or alkylene groups with 1-6 C atoms.
  • the aryl systems of the formula (I) can additionally, independently of one another, in accordance with their chemical structure, one or more common functional groups, for example alkyl radicals, halogens, sulfonic acid, amino, nitro, cyano, hydroxy or Contain carboxy groups.
  • Block copolymers of units of the formula (I) can also be used.
  • Preferred sulfur-containing polymers are polyarylenes with repeating units of the formulas (II-VI), the syntheses of which, for. B. in Chimia 28 (9), 567:
  • Particularly preferred sulfur-containing polymers are polyphenylene sulfides (PPS) with the repeating unit of the formula (VIII), the production process for. B. is described in the patents US 3,919, 177, US 4,038,262 and US 4,282,347.
  • PPS of the formula (VIII) can also have a 1,2 and / or a 1,3 linkage on the aromatic nucleus up to a proportion of 50 mole percent.
  • PPS is understood to mean both the linear and the cross-linked material.
  • the PPS of the formula (VIII) can independently of one another have 1 to 4 functional units per aryl unit Contain groups, for example alkyl radicals, halogens, sulfonic acid, hydroxyl, amino, nitro, cyano or carboxy groups.
  • polyarylene thioethers according to the invention are used, polyarylene thioethers having an average molecular weight of 4,000 to 200,000, preferably 10,000 to 150,000, in particular 25,000 to 100,000, are generally suitable (determined by gel permeation chromatography).
  • the sulfur-containing polymers can be used as powder, fiber, nonwoven, fabric, film, sintered material, molded body or as a coating or impregnation of carrier materials. Moldings with a particularly large surface area can be produced by suitable processes, e.g. with lattice or honeycomb structure.
  • the powders have e.g. commercially available particle sizes, whereby granules can also be used. It is important here that the gas or liquid to be treated can be passed through the polymer material, for example in the form of a powder fixed bed, without interference. If the polymers are used as fibers, they are used as staple fibers, needle felt, "non-woven" material, card sliver or fabric. Films or film snippets can also be used in a suitable form.
  • Coatings of support materials with a sulfur-containing polymer such as polyphenylene sulfide can be obtained by applying solutions of the sulfur-containing polymer to the support material. Impregnations are produced, for example, by soaking an absorbent carrier material.
  • inorganic substances such as glass, silica gel, aluminum oxide, sand, ceramic materials, metal and organic substances such as plastics are used as the carrier material.
  • Metals, in particular noble metals and transition metals, or metal oxides such as transition metal oxides, for example by impregnation, which are then present, for example, in the form of small clusters, can also be applied to the sulfur-containing polymers.
  • the process according to the invention can be carried out at any temperature which is below the softening point of the polymers used.
  • the application temperatures are in the range of minus 30 to + 240 ° C, preferably minus 25 to + 220 ° C.
  • Nitrogen dioxide is generally removed quantitatively, the reaction times being dependent on the flow rate, the surface of the cleaning material, the geometry of the absorber and the temperature.
  • the time of contact of the sulfur-containing polymer with the medium to be cleaned is in the range from 0.001 seconds to 10 minutes, preferably 0.01 seconds to 5 minutes. The times can also be exceeded.
  • the sulfur-containing polymer e.g. Polyarylene thioether
  • customary fillers such as chalk, talc, clay, mica, and / or fibrous reinforcing agents, such as glass and / or carbon fibers, whiskers, and other customary additives and processing aids, e.g. Lubricants, release agents, antioxidants, UV stabilizers.
  • the method according to the invention can be used for gas streams and liquids containing NO x .
  • the process works with a gas, for example NO content in the range from 60 vol.% To 1 ppb, preferably 50 vol.% To 10 ppb and in particular 40 vol.% To 50 ppb.
  • the separable N0 2 content is in the range from 50 vol.% To 1 ppb, preferably 20 vol.% To 10 ppb and in particular from 10 vol.% To 10 ppb.
  • the ratio between NO and N0 in the gases or liquids to be treated can be from 1,000,000: 1 to 1: 1,000,000, preferably from 10,000: 1 to 1: 10,000 and in particular from 1,000: 1 to 1: 1000.
  • the removal of NO 2 can be effected, for example, by using a filter which contains a sulfur-containing polymer.
  • the removal of N0 from liquids or gases can also be done, for example, by whirling up a powder that contains sulfur-containing polymer. This can be a stirring of a powder in a liquid.
  • the process for removing NO 2 from liquids or gases can be carried out in a batch or column process, as in other conventional adsorption processes for purifying gases or liquids, or in the case of separation processes which are based on an adsorption process.
  • Another object of the invention is a filter for removing N0 from NO x -containing gases or NO x -containing liquids containing a sulfur-containing polymer.
  • the filter can also be operated in combination with other filter materials, such as dust filters.
  • the filter which contains a sulfur-containing polymer, can contain the filter material, for example in the form of a powder bed, a fleece, a fleece-powder mixture, a lattice or honeycomb structure.
  • the powder can also be incorporated into nonwovens made of other materials.
  • the method and the filter are particularly suitable for the production of NO test gases, for example a raw NO gas which is contaminated with NO 2 and contains a high NO concentration, is passed through the filter and cleaned in the process and then to the desired level Concentration is diluted with an oxygen-free gas.
  • NO test gases for example a raw NO gas which is contaminated with NO 2 and contains a high NO concentration
  • Concentration is diluted with an oxygen-free gas.
  • the dilution and filtering steps can also be performed in parallel or in reverse order.
  • the method and the filter according to the invention can be used in medical technology.
  • the NO-containing gas and the added air can be combined in front of or in the filter and it can thereby be achieved that an N0 2 -free gas mixture is inhaled.
  • the filter can consist, for example, of a breathing mask, in the supply air flow of which the filter containing the sulfur-containing polymer is inserted.
  • IRDS Infant Respiratory Distress Syndrome
  • Lung failure migraines
  • persistent pulmonary hypertension based on left heart failure or to improve lung function can be used.
  • a so-called NO raw gas consisting of approx. 20 vol.% NO in nitrogen, which was contaminated with 795 ppm N0 2 due to the production process, was passed through a filter cartridge which was filled with polyphenylene sulfide (Mw: 30,000, melting point Tm: 288 * C) in granular form (average particle diameter approx. 1 mm).
  • the absorption path is characterized by the following parameters:
  • the gas was at the outlet of the absorber bed using an FTIR spectrophotometer (manufacturer: Perkin-Elmer, Ueberlingen, Federal Republic of Germany) and a NO / N0 2 chemoluminescence measuring device (type CSI 1600, Columbia Scientific Instruments, Austin, Texas, USA) to N0 2 - and NO content examined.
  • the N0 concentration was below the detection limit of 100 ppb over the entire period of 4 hours over which the measurement was made.
  • a gas mixture of 158 ppm NO 2 in nitrogen was passed through a filter cartridge as in Example 1.
  • the N0 content of the gas mixture was determined by IR spectroscopy immediately at the outlet of the filter.
  • the N0 2 concentration was below the detection limit.
  • Example 3 Analogous to Example 1, a capacity was determined for the filter mentioned in Example 1 using a gas mixture of 1% by volume of NO 2 and 99% by volume of nitrogen. The gas mixture was passed through the filter until the N0 content of the gas after the filter rose above an N0 2 content of 1 ppm. The amount of gas that flowed through the filter until the set limit of the N0 2 content was reached was defined as the absorption capacity of the filter. At a temperature of 22 ° C there was an absorption capacity of approx. 2% by weight of the filter mass.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pulmonology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Epidemiology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Gas Separation By Absorption (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Filtering Materials (AREA)
  • Treating Waste Gases (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

A process and filter for producing NO2-free nitrogen monoxide are based on putting a NO2-containing gas or liquid in contact with a material that contains a sulphurous polymer, for example polyarylene thioether, in particular polyphenylene sulphide. The process or filter are suitable for generating NO2-free nitrogen monoxide-nitrogen-air mixtures for medical applications.

Description

Verfahren und Filter zur Herstellung von N0 -freiem Stickstoffmonoxid mit schwefelhaltigen PolymerenProcess and filter for the production of N0 -free nitrogen monoxide with sulfur-containing polymers
Die Erfindung betrifft ein Verfahren zur Herstellung von stickstoffdioxidfreien Gasen und Flüssigkeiten und ein Filter zur selektiven Entfernung von Stickstoffdioxid aus Gasen und Flüssigkeiten.The invention relates to a method for producing nitrogen dioxide-free gases and liquids and a filter for the selective removal of nitrogen dioxide from gases and liquids.
Stickstoffmonoxid-Gas oder Stickstoffmonoxid-Gasgemische, die frei von Stickstoffdioxid sind, werden in der Abgasmeßtechnik zur Kalibrierung von Meß- und Analysesystemen benötigt.Nitrogen monoxide gas or nitrogen monoxide gas mixtures which are free of nitrogen dioxide are required in exhaust gas measurement technology for the calibration of measurement and analysis systems.
In jüngster Zeit hat der medizinische Einsatz von Stickstoffmonoxid (NO) besondere Bedeutung erlangt. Bei Patienten mit schweren pulmonalen Krankheitsbildern kann durch Zudosierung von NO zur Atemluft der Bluthochdruck im Lungenkreislauf gesenkt werden. Verbunden mit der bronchodilatorischen Wirkung von NO kommt es zu einer verbesserten Belüftung diverser Lungenabschnitte und damit auch zu einem verbesserten Gasaustausch.The medical use of nitrogen monoxide (NO) has recently become particularly important. In patients with severe pulmonary symptoms, the addition of NO to the air we breathe can reduce the high blood pressure in the pulmonary circulation. Combined with the bronchodilatory effect of NO, there is an improved ventilation of various lung sections and thus an improved gas exchange.
Das farblose Stickstoffmonoxid (NO) reagiert mit molekularem Sauerstoff rasch zu braunem Stickstoffdioxid (N02). In Gegenwart von Luft oder bei Luftzutritt wird daher N02 aus NO gebildet. N02 ist deshalb - aufgrund des allgegenwärtigen Sauerstoffs - eine inhärente Verunreinigung von NO. Besonders bei einer medizinischen Verwendung von NO muß aufgrund der Giftigkeit der Gehalt von N02 sehr gering sein. Es hat deshalb nicht an Bemühungen gefehlt, das einmal gebildete N02 selektiv zu absorbieren bzw. zu NO zu konvertieren. Die katalytische Umwandlung des N02 zu NO in Gegenwart von Sauerstoff nach:The colorless nitrogen monoxide (NO) reacts quickly with molecular oxygen to give brown nitrogen dioxide (N0 2 ). In the presence of air or in the presence of air, NO 2 is therefore formed from NO. N0 2 is therefore - due to the omnipresent oxygen - an inherent contamination of NO. Especially with a medical use of NO, the content of N0 2 must be very low due to the toxicity. Efforts have therefore not been lacking to selectively absorb the NO 2 once formed or to convert it to NO. The catalytic conversion of N0 2 to NO in the presence of oxygen after:
2 N 02 ^ 2 N O + 02 2 N 0 2 ^ 2 NO + 0 2
am Cu-, Mo- oder Ni-Kontakt bei Temperaturen von > 220 *C ist möglich. Diese Methode wird angewandt bei der separaten Erfassung von NO und N02 nach dem Chemolumineszensverfahren (siehe Bedienungs- und Wartungsanleitung für das NOx-Meßgerät CSI 1600 der Columbia Scientific Industries, Austin Texas, 1980). Nachteilig bei diesem Verfahren ist die notwendige hohe Temperatur und die Möglichkeit der Rekombination von NO + 02 zu N02 nach dem Abkühlen des Gas¬ stromes.at the Cu, Mo or Ni contact at temperatures of> 220 * C is possible. This method is used for the separate detection of NO and NO 2 by the chemiluminescence method (see operating and maintenance instructions for the NO x measuring device CSI 1600 from Columbia Scientific Industries, Austin Texas, 1980). A disadvantage of this method is the high temperature required and the possibility of recombining NO + 0 2 to N0 2 after the gas stream has cooled.
Es ist weiterhin bekannt, daß sich N02 sehr gut in konzentrierten anorganischen Säuren wie HN03 oder H2S04 löst. Man kann deshalb NO sehr gut mit Hilfe einer Gaswäsche durch die obengenannten Säuren reinigen (A. Golloch, Anorganisch¬ chemische Präparate, Walter de Gruyter Verlag 1985, S. 232 f.). Nachteilig hierbei ist der verhältnismäßig hohe sicherheits- und verfahrenstechnische Aufwand.It is also known that N0 2 dissolves very well in concentrated inorganic acids such as HN0 3 or H 2 S0 4 . NO can therefore be cleaned very well with the aid of a gas scrubber using the abovementioned acids (A. Golloch, inorganic chemical preparations, Walter de Gruyter Verlag 1985, pp. 232 f.). The disadvantage here is the relatively high level of safety and procedural complexity.
Weitere Methoden sind die fraktionierte Kondensation und Destillation zur Entfernung des N02 aus NO. Eine zusammenfassende Darstellung der Reinigungsverfahren für NO findet man in: G. Brauer, Handbuch der präparativen anorganischen Chemie, Bd. 1 , S.470f., 3. Auflage (1975), Verlag F. Enke.Other methods are fractional condensation and distillation to remove the NO 2 from NO. A summary of the cleaning processes for NO can be found in: G. Brauer, Handbuch der preparative inorganic Chemie, Vol. 1, pp. 470f., 3rd edition (1975), Verlag F. Enke.
Die Aufgabe bestand darin, ein einfaches Verfahren und ein Filter zur selektiven Entfernung von N02 aus NOx-haltigen Gasen oder Flüssigkeiten zu finden.The task was to find a simple method and a filter for the selective removal of NO 2 from NO x -containing gases or liquids.
Es zeigte sich, daß eine selektive Entfernung von N02 aus NO oder NO-haltigen Medien wie Gasen oder Flüssigkeiten durch Kontaktierung mit einem schwefelhaltigen Polymer, bevorzugt Polyarylenthioether, insbesondere Polyphenylensulfid, sehr effizient durchführbar ist. Die Erfindung betrifft daher ein Verfahren zur Herstellung von NO enthaltenden Gasen oder Flüssigkeiten, die frei von N02 sind, wobei ein NOx-haltiges Gas oder eine NOx-haltige Flüssigkeit mit einem Material in Kontakt gebracht werden, das ein schwefelhaltiges Polymer enthält, vorzugsweise wird N02 aus einem NO-haltigen Gasgemisch entfernt .It was found that a selective removal of NO 2 from NO or NO-containing media such as gases or liquids by contacting with a sulfur-containing polymer, preferably polyarylene thioether, in particular polyphenylene sulfide, can be carried out very efficiently. The invention therefore relates to a process for the production of NO-containing gases or liquids which are free of NO 2 , a NO x -containing gas or a NO x -containing liquid being brought into contact with a material which contains a sulfur-containing polymer, N0 2 is preferably removed from an NO-containing gas mixture.
Der Ausdruck "frei von N02" bedeutet, daß der Gehalt von N0 in einem Medium kleiner als 1 ppm ist.The expression "free of NO 2 " means that the content of NO in a medium is less than 1 ppm.
NOx wird als Sammelbegriff für die Stickstoffoxide NO, N02 und N20 verwendet und bezieht auch Mischungen dieser Oxide ein.NO x is used as a collective term for the nitrogen oxides NO, N0 2 and N 2 0 and also includes mixtures of these oxides.
Schwefelhaltige Polymere sind beispielsweise lineare oder verzweigte Polyarylsysteme (mittleres Molekulargewicht, Mw: 4000-200000) mit der Wiederholungseinheit der Formel I, die mindestens eine Thioethergruppe enthalten,Polymers containing sulfur are, for example, linear or branched polyaryl systems (average molecular weight, Mw: 4000-200000) with the repeating unit of the formula I, which contain at least one thioether group,
-[(Ar1 )n-X]m-[(Ar2)i-Y]j-[(Ar3)k-Z]l-[(Ar4)0-W]p- (I)- [(Ar 1 ) n -X] m - [(Ar 2 ) i -Y] j - [(Ar 3 ) k -Z] l - [(Ar 4 ) 0 -W] p - (I)
wobei Ar1 , Ar2, Ar3, Ar4, W, X, Y und Z unabhängig voneinander gleich oder verschieden sind. Die Indizes n, m, i, j, k, I, o und p sind ganze Zahlen von 0 bis 4 wobei ihre Summe mindestens 2 ergeben muß. Ar1 , Ar2 Ar3 und Ar4 stehen in der Formel (I) für einfache oder direkt über para-, meta- oder orthoverknüpfte Arylsysteme mit 6 bis 18 C-Atomen. W, X, Y und Z stellen Verknüpfungsgruppen dar, ausgewählt aus -S02-, -S-, -SO-, -0-, -CO-, -C02-, Alkyl- oder Alkylidengruppen mit 1 -6 C-Atomen und -NR1-Gruppen, wobei R1 für Alkyl- oder Alkyiden-Gruppen mit 1-6 C-Atomen steht. Die Arylsysteme der Formel (I) können im Sinne der Erfindung entsprechend ihrer chemischen Struktur noch zusätzlich unabhängig voneinander ein oder mehrere gängige funktionelle Gruppen, z.B. Alkylreste, Halogene, Sulfonsäure-, Amino-, Nitro-, Cyano-, Hydroxy- oder Carboxygruppen enthalten. Ferner sind auch Blockcopolymere aus Einheiten der Formel (I) einsetzbar.where Ar 1 , Ar 2 , Ar 3 , Ar 4 , W, X, Y and Z are independently the same or different. The indices n, m, i, j, k, I, o and p are integers from 0 to 4, the sum of which must be at least 2. Ar 1 , Ar 2 Ar 3 and Ar 4 in formula (I) stand for simple or directly via para, meta or ortho-linked aryl systems with 6 to 18 carbon atoms. W, X, Y and Z represent linking groups selected from -S0 2 -, -S-, -SO-, -0-, -CO-, -C0 2 -, alkyl or alkylidene groups with 1 -6 carbon atoms and -NR 1 groups, where R 1 stands for alkyl or alkylene groups with 1-6 C atoms. According to the invention, the aryl systems of the formula (I) can additionally, independently of one another, in accordance with their chemical structure, one or more common functional groups, for example alkyl radicals, halogens, sulfonic acid, amino, nitro, cyano, hydroxy or Contain carboxy groups. Block copolymers of units of the formula (I) can also be used.
Die Wechselwirkung der schwefelhaltigen Polymere wie Polyarylenthioether mit NO ist gegenüber der Wechselwirkung mit N02 vernachlässigbar gering, daher ist eine Abtrennung von N02 aus einem NOx-haltigen Gasstrom möglich.The interaction of the sulfur-containing polymers such as polyarylene thioether with NO is negligible compared to the interaction with N0 2 , so it is possible to separate N0 2 from a NO x- containing gas stream.
Bevorzugte schwefelhaltige Polymere sind Polyarylene mit Wiederholungseinheiten der Formeln (ll-VI), deren Synthesen z. B. in Chimia 28(9), 567 beschrieben sind:Preferred sulfur-containing polymers are polyarylenes with repeating units of the formulas (II-VI), the syntheses of which, for. B. in Chimia 28 (9), 567:
sowie Polyarylenthioether mit wiederkehrenden Einheiten der Formel (VII), die z.B. in US-A-4,016, 145 beschrieben sind.as well as polyarylene thioethers with repeating units of formula (VII), e.g. in US-A-4,016, 145.
Besonders bevorzugte schwefelhaltige Polymere sind Polyphenylensulfide (PPS) mit der wiederkehrenden Einheit der Formel (VIII), deren Herstellungsprozess z. B. in den Patentschriften US 3,919, 177, US 4,038,262 und US 4,282,347 beschrieben ist.Particularly preferred sulfur-containing polymers are polyphenylene sulfides (PPS) with the repeating unit of the formula (VIII), the production process for. B. is described in the patents US 3,919, 177, US 4,038,262 and US 4,282,347.
PPS der Formel (VIII) kann auch bis zu einem Anteil von 50 Molprozent eine 1 ,2- und/oder eine 1 ,3-Verknüpfung am aromatischen Kern aufweisen. Unter PPS ist sowohl das lineare als auch das vernetzte Material zu verstehen. Ferner kann das PPS der Formel (VIII) pro Aryleinheit unabhängig voneinander 1 bis 4 funktioneile Gruppen enthalten, z.B. Alkylreste, Halogene, Sulfonsäure-, Hydroxy-, Amino-, Nitro-, Cyano- oder Carboxygruppen.PPS of the formula (VIII) can also have a 1,2 and / or a 1,3 linkage on the aromatic nucleus up to a proportion of 50 mole percent. PPS is understood to mean both the linear and the cross-linked material. Furthermore, the PPS of the formula (VIII) can independently of one another have 1 to 4 functional units per aryl unit Contain groups, for example alkyl radicals, halogens, sulfonic acid, hydroxyl, amino, nitro, cyano or carboxy groups.
Werden Polyarylenthioether gemäß der Erfindung eingesetzt, so sind im allgemeinen Polyarylenthioether geeignet, die ein mittleres Molekulargewicht von 4000 bis 200000, vorzugsweise 10000 bis 150000, insbesondere 25000 bis 100000, aufweisen (bestimmt durch Gelpermeationschromatographie).If polyarylene thioethers according to the invention are used, polyarylene thioethers having an average molecular weight of 4,000 to 200,000, preferably 10,000 to 150,000, in particular 25,000 to 100,000, are generally suitable (determined by gel permeation chromatography).
Die schwefelhaltigen Polymere können als Pulver, Faser, Vlies, Gewebe, Folie, gesintertes Material, Formkörper oder als Beschichtung oder Imprägnierung von Trägermaterialien eingesetzt werden. Durch geeignete Verfahren lassen sich Formkörper mit besonders großer Oberfläche herstellen, z.B. mit Gitter- oder Wabenstruktur. Die Pulver besitzen z.B. handelsübliche Teilchengrößen, wobei auch Granulate verwendbar sind. Wichtig hierbei ist es, daß das zu behandelnde Gas oder die Flüssigkeit durch das Polymermaterial, beispielsweise in Form eines Pulver-Festbettes, ohne Störung durchgeleitet werden kann. Werden die Polymere als Fasern verwendet, werden diese als Stapelfasern, Nadelfilz, "non woven" Material, Kardenband oder Gewebe eingesetzt. Auch Folien oder Folienschnipsel können in geeigneter Form Verwendung finden.The sulfur-containing polymers can be used as powder, fiber, nonwoven, fabric, film, sintered material, molded body or as a coating or impregnation of carrier materials. Moldings with a particularly large surface area can be produced by suitable processes, e.g. with lattice or honeycomb structure. The powders have e.g. commercially available particle sizes, whereby granules can also be used. It is important here that the gas or liquid to be treated can be passed through the polymer material, for example in the form of a powder fixed bed, without interference. If the polymers are used as fibers, they are used as staple fibers, needle felt, "non-woven" material, card sliver or fabric. Films or film snippets can also be used in a suitable form.
Beschichtungen von Trägermaterialien mit schwefelhaltigem Polymer wie Polyphenylensulfid können durch Auftragen von Lösungen des schwefelhaltigen Polymers auf das Trägermaterial erhalten werden. Imprägnierungen werden z.B. durch Tränken eines saugfähigen Tr.ägermaterials hergestellt. Als Trägermaterial werden im allgemeinen anorganische Stoffe wie Glas, Kieselgel, Aluminiumoxid, Sand, keramische Massen, Metall und organische Stoffe wie Kunststoffe eingesetzt. Auf die schwefelhaltigen Polymere können auch z.B. Metalle, insbesondere Edelmetalle und Übergangsmetalle, oder Metalloxide wie Übergangsmetalloxide, beispielsweise durch Aufimprägnieren aufgebracht werden, die dann z.B. in Form kleiner Cluster vorliegen.Coatings of support materials with a sulfur-containing polymer such as polyphenylene sulfide can be obtained by applying solutions of the sulfur-containing polymer to the support material. Impregnations are produced, for example, by soaking an absorbent carrier material. In general, inorganic substances such as glass, silica gel, aluminum oxide, sand, ceramic materials, metal and organic substances such as plastics are used as the carrier material. Metals, in particular noble metals and transition metals, or metal oxides such as transition metal oxides, for example by impregnation, which are then present, for example, in the form of small clusters, can also be applied to the sulfur-containing polymers.
Das Verfahren gemäß der Erfindung kann bei jeder Temperatur, die unterhalb des Erweichungspunktes der verwendeten Polymere liegt, durchgeführt werden. Im allgemeinen liegen die Anwendungtemperaturen im Bereich minus 30 bis + 240 ° C, vorzugsweise minus 25 bis + 220 ° C.The process according to the invention can be carried out at any temperature which is below the softening point of the polymers used. In general, the application temperatures are in the range of minus 30 to + 240 ° C, preferably minus 25 to + 220 ° C.
Die Entfernung von Stickstoffdioxid erfolgt im allgemeinen quantitativ, wobei die Reaktionszeiten von der Strömungsgeschwindigkeit, der Oberfläche des Reinigungsmaterials, der Geometrie des Absorbers und der Temperatur abhängig sind. Im allgemeinen liegt die Zeit des Kontaktes des schwefelhaltigen Polymers mit dem zu reinigenden Medium im Bereich von 0,001 Sekunden bis 10 Minuten, vorzugsweise 0,01 Sekunden bis 5 Minuten. Die Zeiten können aber auch überschritten werden.Nitrogen dioxide is generally removed quantitatively, the reaction times being dependent on the flow rate, the surface of the cleaning material, the geometry of the absorber and the temperature. In general, the time of contact of the sulfur-containing polymer with the medium to be cleaned is in the range from 0.001 seconds to 10 minutes, preferably 0.01 seconds to 5 minutes. The times can also be exceeded.
Bei der Entfernung von N02 aus NOx-haltigem Gas oder NOx-haltiger Flüssigkeit werden aus dem Polymer keine flüchtigen Produkte gebildet.When N0 2 is removed from NO x -containing gas or NO x -containing liquid, no volatile products are formed from the polymer.
Das schwefelhaltige Polymer, z.B. Polyarylenthioether, kann im allgemeinen als unverschnittenes Material eingesetzt werden. Möglich ist aber auch der Zusatz von üblichen Füllstoffen, wie Kreide, Talk, Ton, Glimmer, und/oder faserförmigen Verstärkungsmitteln, wie Glas- und/oder Kohlenstoffasern, Whiskers, sowie weiteren üblichen Zusatzstoffen und Verarbeitungshilfmitteln, z.B. Gleitmittel, Trennmittel, Antioxidantien, UV-Stabilisatoren.The sulfur-containing polymer, e.g. Polyarylene thioether, can generally be used as an unblended material. However, it is also possible to add customary fillers, such as chalk, talc, clay, mica, and / or fibrous reinforcing agents, such as glass and / or carbon fibers, whiskers, and other customary additives and processing aids, e.g. Lubricants, release agents, antioxidants, UV stabilizers.
Das Verfahren gemäß der Erfindung kann bei NOx-haltigen Gasströmen und Flüssigkeiten angewendet werden. Das Verfahren arbeitet z.B. bei Gasen mit einem NO-Gehalt im Bereich von 60 Vol.-% bis 1 ppb, vorzugsweise 50 Vol.-% bis 10 ppb und insbesondere 40 Vol.-% bis 50 ppb. Der abtrennbare N02-Gehalt liegt im Bereich von 50 Vol.-% bis 1 ppb, vorzugsweise 20 Vol.-% bis 10 ppb und insbesondere von 10 Vol.-% bis 10 ppb. Das Verhältnis zwischen NO und N0 in den zu behandelnden Gasen oder Flüssigkeiten kann dabei von 1000000 : 1 bis 1 : 1000000, vorzugsweise von 10000 : 1 bis 1 : 10000 und insbesondere von 1000 : 1 bis 1 : 1000 liegen.The method according to the invention can be used for gas streams and liquids containing NO x . The process works with a gas, for example NO content in the range from 60 vol.% To 1 ppb, preferably 50 vol.% To 10 ppb and in particular 40 vol.% To 50 ppb. The separable N0 2 content is in the range from 50 vol.% To 1 ppb, preferably 20 vol.% To 10 ppb and in particular from 10 vol.% To 10 ppb. The ratio between NO and N0 in the gases or liquids to be treated can be from 1,000,000: 1 to 1: 1,000,000, preferably from 10,000: 1 to 1: 10,000 and in particular from 1,000: 1 to 1: 1000.
In dem Verfahren gemäß der Erfindung kann die Entfernung von N02 z.B. durch Einsatz eines Filters, das ein schwefelhaltiges Polymer enthält, bewirkt werden. Die Entfernung von N0 aus Flüssigkeiten oder Gasen kann beispielsweise auch durch Aufwirbeln eines Pulvers, das schwefelhaltiges Polymer enthält, erfolgen. Dies kann ein Ausrühren von einem Pulver in einer Flüssigkeit sein. Das Verfahren zur Entfernung von N02 aus Flüssigkeiten oder Gasen kann wie bei anderen üblichen Adsorptionsverfahren zur Reinigung von Gasen oder Flüssigkeiten oder wie bei Trennverfahren, die auf einem Adsorptionsvorgang beruhen, in einem Batch- oder Säulenverfahren durchgeführt werden.In the method according to the invention, the removal of NO 2 can be effected, for example, by using a filter which contains a sulfur-containing polymer. The removal of N0 from liquids or gases can also be done, for example, by whirling up a powder that contains sulfur-containing polymer. This can be a stirring of a powder in a liquid. The process for removing NO 2 from liquids or gases can be carried out in a batch or column process, as in other conventional adsorption processes for purifying gases or liquids, or in the case of separation processes which are based on an adsorption process.
Ein weiterer Gegenstand der Erfindung ist ein Filter zur Entfernung von N0 aus NOx-haltigen Gasen oder NOx-haltigen Flüssigkeiten, das ein schwefelhaltiges Polymer enthält.Another object of the invention is a filter for removing N0 from NO x -containing gases or NO x -containing liquids containing a sulfur-containing polymer.
Die Angaben zum schwefelhaltigen Polymer, die im Zusammenhang mit dem Verfahren gemäß der Erfindung gemacht wurden, gelten für das Filter entsprechend.The information on the sulfur-containing polymer, which was made in connection with the method according to the invention, applies accordingly to the filter.
Das Filter kann auch in Kombination mit anderen Filtermaterialien, z.B. Staubfiltern, betrieben werden. Das Filter, das ein schwefelhaltiges Polymer enthält, kann das Filtermaterial z.B. in Form von einem Pulver-Schüttbett, einem Vlies, einer Vlies-Pulver-Mischung, einer Gitter- oder Wabenstruktur enthalten. Das Pulver kann aber auch in Vliese aus anderen Werkstoffen eingearbeitet werden.The filter can also be operated in combination with other filter materials, such as dust filters. The filter, which contains a sulfur-containing polymer, can contain the filter material, for example in the form of a powder bed, a fleece, a fleece-powder mixture, a lattice or honeycomb structure. The powder can also be incorporated into nonwovens made of other materials.
Das Verfahren und das Filter sind besonders geeignet für die Herstellung von NO- Prüfgasen, wobei z.B. ein NO-Rohgas, das mit N02 verunreinigt ist und eine hohe NO-Konzentration enthält, durch das Filter geleitet und dabei gereinigt wird und anschließend auf die gewünschte Konzentration mit einem sauerstofffreien Gas verdünnt wird. Die Schritte der Verdünnung und der Filterung können auch parallel oder in umgekehrter Reihenfolge durchgeführt werden.The method and the filter are particularly suitable for the production of NO test gases, for example a raw NO gas which is contaminated with NO 2 and contains a high NO concentration, is passed through the filter and cleaned in the process and then to the desired level Concentration is diluted with an oxygen-free gas. The dilution and filtering steps can also be performed in parallel or in reverse order.
Weiter können das Verfahren und das Filter gemäß der Erfindung Anwendung in der Medizintechnik finden. So kann beispielsweise bei einer Behandlung mit einer NO-Aufnahme über die Lunge das NO-haltige Gas und die zugesetzte Luft vor oder im Filter vereinigt und damit erreicht werden, daß ein N02-freies Gasgemisch ein¬ geatmet wird. Das Filter kann zum Beispiel aus einer Atemmaske bestehen, in deren Zuluftstrom das das schwefelhaltige Polymer enthaltende Filter eingesetzt ist.Furthermore, the method and the filter according to the invention can be used in medical technology. For example, in the case of a treatment with an NO intake via the lungs, the NO-containing gas and the added air can be combined in front of or in the filter and it can thereby be achieved that an N0 2 -free gas mixture is inhaled. The filter can consist, for example, of a breathing mask, in the supply air flow of which the filter containing the sulfur-containing polymer is inserted.
Das Filter gemäß der Erfindung kann zur Erzeugung von N02-freien Stickstoffmonoxid-Stickstoff-Luft-Gemischen für die Behandlung von IRDS (IRDS = Infant Respiratory Distress Syndrome), ARDS ( = Acute Respiratory Distress Syndrome, auch = Adult Respiratory Distress Syndrome), Lungenversagen, Migräne, persistierende pulmonale Hypertonie basierend auf Linksherzinsuffizienz oder zur Verbesserung der Lungenfunktion eingesetzt werden.The filter according to the invention can be used to generate N0 2 -free nitrogen monoxide-nitrogen-air mixtures for the treatment of IRDS (IRDS = Infant Respiratory Distress Syndrome), ARDS (= Acute Respiratory Distress Syndrome, also = Adult Respiratory Distress Syndrome), Lung failure, migraines, persistent pulmonary hypertension based on left heart failure or to improve lung function can be used.
Beispiele:Examples:
1 .) Ein sogennantes NO-Rohgas, bestehend aus ca. 20 Vol.-% NO in Stickstoff, das herstellungsbedingt mit 795 ppm N02 verunreinigt war, wurde über eine Filterpatrone geleitet, die mit Poylphenylensulfid (Mw: 30 000, Schmelzpunkt Tm: 288 * C) in Granulatform (mittlerer Teilchendurchmesser ca. 1 mm) gefüllt war. Die Absorptionsstrecke ist durch folgende Parameter gekennzeichnet:1.) A so-called NO raw gas, consisting of approx. 20 vol.% NO in nitrogen, which was contaminated with 795 ppm N0 2 due to the production process, was passed through a filter cartridge which was filled with polyphenylene sulfide (Mw: 30,000, melting point Tm: 288 * C) in granular form (average particle diameter approx. 1 mm). The absorption path is characterized by the following parameters:
Innendurchmesser: 2,5cmInner diameter: 2.5 cm
Schütthöhe: 32,5 cmDumping height: 32.5 cm
Masse: 100,5 gWeight: 100.5 g
Durchsatz: 100 l/hFlow: 100 l / h
Das Gas wurde am Ausgang des Absorberbettes mittels eines FTIR- Spektralphotometers (Hersteller: Perkin-Elmer, Überlingen, Bundesrepublik Deutschland) und eines NO/N02-Chemolumineszensmeßgerätes (Typ CSI 1600, Columbia Scientific Instruments, Austin, Texas, USA) auf N02- und NO-Gehalt untersucht. Im gesamten Zeitraum von 4 Stunden, über den gemessen wurde, lag die N0 -Konzentration unterhalb der Nachweisgrenze von 100 ppb.The gas was at the outlet of the absorber bed using an FTIR spectrophotometer (manufacturer: Perkin-Elmer, Ueberlingen, Federal Republic of Germany) and a NO / N0 2 chemoluminescence measuring device (type CSI 1600, Columbia Scientific Instruments, Austin, Texas, USA) to N0 2 - and NO content examined. The N0 concentration was below the detection limit of 100 ppb over the entire period of 4 hours over which the measurement was made.
2.) Ein Gasgemisch von 158 ppm N02 in Stickstoff wurde wie in Beispiel 1 über eine Filterpatrone geleitet. Unmittelbar am Ausgang des Filters wurde IR- spektroskopisch der N0 -Gehalt des Gasgemisches bestimmt. Die N02- Konzentration lag unterhalb der Nachweisgrenze.2.) A gas mixture of 158 ppm NO 2 in nitrogen was passed through a filter cartridge as in Example 1. The N0 content of the gas mixture was determined by IR spectroscopy immediately at the outlet of the filter. The N0 2 concentration was below the detection limit.
3.) Analog Beispiel 1 wurde eine Kapazitätsbestimmung für das in Beispiel 1 genannte Filter mittels eines Gasgemisches aus 1 Vol.-% N02 und 99 Vol.-% Stickstoff durchgeführt. Das Gasgemisch wurde durch das Filter geleitet, bis der N0 -Gehalt des Gases nach dem Filter über einen N02-Gehalt von 1 ppm anstieg. Die Gasmenge, die das Filter durchströmte bis der gesetzte Grenzwert des N02- Gehaltes erreicht wurde, wurde als Aufnahmekapazität des Filters definiert. Bei einer Temperatur von 22° C ergab sich eine Aufnahmekapazität von ca. 2 Gew.-% der Filtermasse. 3.) Analogous to Example 1, a capacity was determined for the filter mentioned in Example 1 using a gas mixture of 1% by volume of NO 2 and 99% by volume of nitrogen. The gas mixture was passed through the filter until the N0 content of the gas after the filter rose above an N0 2 content of 1 ppm. The amount of gas that flowed through the filter until the set limit of the N0 2 content was reached was defined as the absorption capacity of the filter. At a temperature of 22 ° C there was an absorption capacity of approx. 2% by weight of the filter mass.

Claims

Patentansprüche Claims
1 . Verfahren zur Herstellung von NO enthaltenden Gasen oder Flüssigkeiten, die frei von N02 sind, dadurch gekennzeichnet, daß ein NOx-haltiges Gas oder eine NOx-haltige Flüssigkeit mit einem Material in Kontakt gebracht werden, das ein schwefelhaltiges Polymer enthält.1 . A process for the preparation of NO-containing gases or liquids which are free of NO 2 , characterized in that a NO x -containing gas or a NO x -containing liquid are brought into contact with a material which contains a sulfur-containing polymer.
2. Filter zur Entfernung von N02 aus NOx-haltigen Gasen oder NOx-haltigen Flüssigkeiten, dadurch gekennzeichnet, daß es ein schwefelhaltiges Polymer enthält.2. Filter for removing N0 2 from NO x -containing gases or NO x -containing liquids, characterized in that it contains a sulfur-containing polymer.
3. Verfahren nach Anspruch 1 oder Filter nach Anspruch 2, dadurch gekennzeichnet, daß das schwefelhaltige Polymer ein Polyarylenthioether ist.3. The method according to claim 1 or filter according to claim 2, characterized in that the sulfur-containing polymer is a polyarylene thioether.
4. Verfahren nach Anspruch 1 oder 3 oder Filter nach Anspruch 2 oder 3, dadurch gekennzeichnet, daß das schwefelhaltige Polymer Polyphenylensulfid ist.4. The method according to claim 1 or 3 or filter according to claim 2 or 3, characterized in that the sulfur-containing polymer is polyphenylene sulfide.
5. Verfahren nach einem oder mehreren der Ansprüche 1 , 3, 4, dadurch ge¬ kennzeichnet, daß N02-freies NO-Gas oder N02-freie NO-Gasgemische erzeugt werden.5. The method according to one or more of claims 1, 3, 4, characterized ge indicates that N0 2 -free NO gas or N0 2 -free NO gas mixtures are generated.
6. Verfahren nach einem oder mehreren der Ansprüche 1 , 3, 4, 5 oder Filter nach Anspruch 2 bis 4, dadurch gekennzeichnet, daß das schwefelhaltige Polymer als Pulver, Faser, Vlies, Gewebe, Folie, Folienteile, gesintertes Material, Formkörper, Kombination zweier oder mehrerer der genannten Ausführungsformen oder als Beschichtung oder Imprägnierung von Trägermaterialien eingesetzt wird. 6. The method according to one or more of claims 1, 3, 4, 5 or filter according to claim 2 to 4, characterized in that the sulfur-containing polymer as a powder, fiber, nonwoven, fabric, film, film parts, sintered material, molded body, combination two or more of the above-mentioned embodiments or as a coating or impregnation of carrier materials.
7. Verfahren nach einem oder mehreren der Ansprüche 1 , 3 bis 6 oder Filter nach Anspruch 2 bis 4 oder 6, dadurch gekennzeichnet, daß das schwefelhaltige Polymer ein mittleres Molekulargewicht-im Bereich von 4000 bis 200000 Atomgewichtseinheiten hat.7. The method according to one or more of claims 1, 3 to 6 or filter according to claim 2 to 4 or 6, characterized in that the sulfur-containing polymer has an average molecular weight in the range from 4000 to 200,000 atomic weight units.
8. Verfahren nach einem oder mehreren der Ansprüche 1 , 3 bis 7, dadurch gekennzeichnet, daß die Entfernung des Stickstoffdioxides bei Temperaturen von minus 30 bis + 240 * C, vorzugsweise minus 25 bis + 220"C, erfolgt.8. The method according to one or more of claims 1, 3 to 7, characterized in that the removal of the nitrogen dioxide is carried out at temperatures from minus 30 to + 240 * C, preferably minus 25 to + 220 "C.
9. Verwendung eines Filters nach Anspruch 2 als Atemschutzfilter.9. Use of a filter according to claim 2 as a respiratory protection filter.
10. Verwendung eines Filters nach Anspruch 2 zur Erzeugung von N02-freiem NO-Gas oder N02-freien NO-Gasgemischen, insbesondere zur Erzeugung von N02- freien Prüfgasen.10. Use of a filter according to claim 2 for the production of N0 2 -free NO gas or N0 2 -free NO gas mixtures, in particular for the production of N0 2 - free test gases.
1 1 . Verwendung eines Filters nach Anspruch 2 zur Erzeugung von N02-freien Stickstoffmonoxid-Stickstoff-Luft-Gemischen für medizinische Applikationen.1 1. Use of a filter according to claim 2 for the production of N0 2 -free nitrogen monoxide-nitrogen-air mixtures for medical applications.
12. Verwendung eines Filters nach Anspruch 2 zur Erzeugung von N02-freien Stickstoffmonoxid-Stickstoff-Luft-Gemischen zur Behandlung von IRDS, ARDS, Lungenversagen, Migräne, Asthma, persistierende pulmonale Hypertonie basierend auf Linksherzinsuffizienz oder zur Verbesserung der Lungenfunktion. 12. Use of a filter according to claim 2 for the production of N0 2 -free nitrogen monoxide-nitrogen-air mixtures for the treatment of IRDS, ARDS, lung failure, migraine, asthma, persistent pulmonary hypertension based on left heart failure or to improve lung function.
EP95922470A 1994-06-07 1995-05-22 Process and filter for producing no 2?-free nitrogen monoxide with sulphurous polymers Withdrawn EP0765289A1 (en)

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TW309445B (en) 1997-07-01
HU219383B (en) 2001-03-28
JPH10505315A (en) 1998-05-26
CA2192069A1 (en) 1995-12-14
HU9603354D0 (en) 1997-02-28
KR970703275A (en) 1997-07-03
AU2735495A (en) 1996-01-04
CN1150413A (en) 1997-05-21
NO965220L (en) 1996-12-06
PL317485A1 (en) 1997-04-14
HUT75290A (en) 1997-05-28
CZ357996A3 (en) 1997-05-14
NO965220D0 (en) 1996-12-06
BR9507943A (en) 1997-09-02
FI964887A0 (en) 1996-12-05
FI964887A (en) 1996-12-05
WO1995033682A1 (en) 1995-12-14
DE4419860A1 (en) 1995-12-14

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