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EP0788398A1 - Filter material and process for producing no 2-free gases - Google Patents

Filter material and process for producing no 2-free gases

Info

Publication number
EP0788398A1
EP0788398A1 EP95936489A EP95936489A EP0788398A1 EP 0788398 A1 EP0788398 A1 EP 0788398A1 EP 95936489 A EP95936489 A EP 95936489A EP 95936489 A EP95936489 A EP 95936489A EP 0788398 A1 EP0788398 A1 EP 0788398A1
Authority
EP
European Patent Office
Prior art keywords
filter
gases
liquids
filter material
free
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Withdrawn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
EP95936489A
Other languages
German (de)
French (fr)
Inventor
Andreas Schleicher
Georg Frank
Wolfgang Sixl
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.)
Ticona GmbH
Original Assignee
Hoechst AG
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
Priority claimed from DE4437985A external-priority patent/DE4437985A1/en
Priority claimed from DE4438529A external-priority patent/DE4438529A1/en
Application filed by Hoechst AG, Ticona GmbH filed Critical Hoechst AG
Publication of EP0788398A1 publication Critical patent/EP0788398A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • 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)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B23/00—Noble gases; Compounds thereof
    • C01B23/001—Purification or separation processes of noble gases
    • C01B23/0036—Physical processing only
    • C01B23/0042—Physical processing only by making use of membranes
    • C01B23/0047—Physical processing only by making use of membranes characterised by the membrane
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S55/00—Gas separation
    • Y10S55/35—Respirators and register filters
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent

Definitions

  • the invention relates to a filter material, a filter and a method for producing nitrogen dioxide-free gases and liquids.
  • NO 2 -free NO gas or NO gas mixtures are required in exhaust gas measurement technology for the calibration of measurement and analysis systems.
  • NO nitrogen monoxide
  • a converter is desirable here, which converts the NO 2 formed into NO shortly before the patient inhales without any other changes in the gas mixture, for example the humidity or the temperature. Compared to a NO 2 filter, this converter would have the advantage that the NO content that was originally set is not changed.
  • NO 2 The colorless nitrogen monoxide (NO) reacts rapidly with molecular oxygen to give brown nitrogen dioxide (NO 2 ).
  • NO 2 is therefore formed from NO.
  • NO 2 is therefore - due to the omnipresent oxygen - an inherent contamination of NO.
  • the NO 2 content must be very low due to the toxicity.
  • NO 2 can be removed from gases or liquids by contacting with a polyarylene ether.
  • a selective removal of NO 2 from NO or NO-containing media such as gases or liquids is possible using a polyarylene ether.
  • Polyarylene ethers are therefore suitable as filter material for NO 2 . This is surprising since the polyarylene ethers differ greatly in structure from the polyarylene sulfides and contain no sulfur groups.
  • the invention relates to a filter material for removing NO 2 from gases and liquids, which contains a polyarylene ether.
  • Another object of the invention is a filter for removing NO 2 from gases and liquids, which contains a polyarylene ether.
  • the invention also relates to a method for producing NO 2 -free Gases or liquids, the gas or liquid to be cleaned being brought into contact with a material which contains a polyarylene ether.
  • NO x is used as a collective term for NO, NO 2 and N 2 O 4 .
  • N 2 O 4 is removed from gases and liquids using polyarylene ether.
  • the filter material, the filter and the method according to the invention are also suitable for removing NO 2 from gases or liquids containing NO.
  • a polyarylene ether is a polymer that contains at least one arylene ether unit (-AO-; A stands for arylene).
  • An arylene denotes an aromatic unit with two binding sites, eg -C ⁇ H 4 -.
  • Mono- or polynuclear aromatics can form an arylene unit, such as benzene, pyridine, naphthalene, phenanthrene, anthracene. Substituted arylene units are preferred.
  • Arylene substituents are, for example, C T -C T ⁇ -Alky such as -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H, -C (CH 3 ) 3 , -CH 2 - CH (CH 3 ) 2 , -C 2 H 4 -CH (CH 3 ) 2 or -CH 2 -C (CH 3 ) 3 .
  • Suitable polyarylene ethers are described in the as yet unpublished European patent application with the file number 951 12259.7, filing date August 4, 1995, entitled "Filter material and process for removing ozone from gases and liquids", to which reference is made.
  • the preferred polyarylene ether is poly- [2,6-dimethylphenylene oxide].
  • the polyarylene ether can also be blended with one or more other polymers.
  • the polyarylene ether can also be a block copolymer or a blend which contains at least one polyarylene ether.
  • Suitable blends are, for example, polyarylene ether blends which contain polystyrene homopolymer and / or polystyrene copolymer and / or polyamide and / or polyolefin.
  • polyarylene ethers examples include "Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A21, B. Elvers (Ed.), VCH, Weinheim-Basel, Cambridge-New York 1992, keyword 'Poly (Phenylene Oxides ) ', Page 605-614 ", to which reference is made.
  • Polyarylene ethers and polyarylene ether-containing polymers are referred to below as polymer.
  • the polymer can be used, for example, as a powder, granules, fibers, nonwoven, fabric, films and / or moldings.
  • the powders have commercially available particle sizes, and granules can also be used. It is important here that the gas or liquid to be treated can be passed through the powder, for example in the form of a fixed bed, without interference. If the polymer is used as a fiber, these 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.
  • the polymer can generally be used as an unblended material. However, it is also possible to add fillers, such as chalk, talc, clay, mica, and / or fibrous reinforcing agents, such as glass and carbon fibers, whiskers, and further additives and processing aids, for example lubricants. Release agents, antioxidants, UV stabilizers.
  • fillers such as chalk, talc, clay, mica, and / or fibrous reinforcing agents, such as glass and carbon fibers, whiskers, and further additives and processing aids, for example lubricants. Release agents, antioxidants, UV stabilizers.
  • Coatings of carrier materials with the polymer can be obtained by applying solutions of the polymer (solvents e.g. toluene, chloroform) to the carrier material. Impregnations are e.g. produced by soaking an absorbent carrier material.
  • solvents e.g. toluene, chloroform
  • Impregnations are e.g. produced 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.
  • Substances can also be applied to the polymer, for example metals, in particular noble metals and transition metals, or metal oxides such as transition metal oxides.
  • the metals or metal oxides can be applied to the polymer, for example by impregnation, which are then present, for example, in the form of small clusters.
  • 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 between minus 10 to 200 ° C, preferably between 0 and 180 ° C.
  • the required contact time of the medium to be cleaned with the filter material depends, among other things, on the flow rate, the residence time, the surface of the filter material, the geometry of the filter and the temperature.
  • the time of contact of the substituted polyarylene ether with the medium to be cleaned ranges between 0.001 seconds and 10 minutes, preferably between 0.01 seconds and 1 minute. The times can also be exceeded.
  • the size of the specific surface area of the polymer has a significant impact on the filter effect of the polymer.
  • the greater the specific surface area of the polymer the greater the filtering effect of the polymer.
  • a large specific surface area and porous structures of the polymer, a balanced ratio of micropores and macropores proving to be favorable, are particularly advantageous for a filtering effect.
  • the filter effect of the polymer is also influenced by the crystallinity or the size of the amorphous part of the polymer. A high amorphous content in the polymer generally favors the filter effect of the polymer.
  • the removal of nitrogen dioxide from gases or liquids by contact with a polyarylene ether can be based on chemical action, catalytic action and / or physical interaction.
  • the polyarylene ether reacts with the nitrogen dioxide and undergoes oxidation.
  • the alkyl group is oxidized in the case of alkyl-substituted polyarylene ethers. This occurs particularly easily in the benzyl position, that is to say on the carbon atom of the alkyl group of an arylene unit which is closest to an aromatic nucleus.
  • the removal of NO 2 can be used for gas streams and liquids containing NO x .
  • the method for NO 2 removal works, for example, in the case of gases with an NO content between 60% by volume and 1 ppb, preferably 50% by volume and 10 ppb and particularly preferably between 40% by volume and 50 ppb.
  • the separable NO 2 content is between 50% and 1 ppb, preferably 20% by volume and 10 ppb and particularly preferably between 10% by volume and 10 ppb.
  • the ratio between NO and NO 2 in the gases or liquids to be treated can be between 1000,000: 1 and 1: 1,000,000, preferably between 10,000: 1 and 1: 10,000 and particularly preferably between 1,000: 1 and 1: 1,000.
  • the filter can e.g. in the form of a powder bed, a fleece, a fleece-powder mixture, a grid or honeycomb structure.
  • the powder can also be incorporated into nonwovens made of other materials.
  • the filter material, the filter and the method for NO 2 removal are suitable, for example, for producing NO 2 -free NO gas or NO 2 -free NO-containing gas for test gases and especially for applications of NO in medical technology, for example in patients with severe pulmonary symptoms can be reduced by adding NO to the air we breathe to reduce the high blood pressure in the pulmonary circulation.
  • IRDS Infant Respiratory Distress Syndrome
  • ARDS Adult Respiratory Distress Syndrome
  • applications in the field of cardiosurgery are also conceivable, for intensive ventilation of patients with NO, in order to lower the high blood pressure in the pulmonary circulation. What is important for these applications is the exact setting of the NO content as well as the minimization up to the elimination of the NO 2 content.
  • the method and the filter for NO 2 removal can be used at several points in a ventilation system in medical technology.
  • the filter can be installed immediately behind the pressure reducing valve to the To minimize the proportion of NO 2 which has arisen or remained during the production of the NO / nitrogen gas mixture used.
  • gas mixtures can be purified which contain NO in a concentration between 1 ppb and 100,000 ppm in nitrogen, preferably 1 ppm to 10,000 ppm.
  • the volume flow of the NO / nitrogen gas mixture can be between 0.001 and 1000 l / min, preferably 0.01 and 250 l / min.
  • the gas containing NO and the added air can be combined in front of or in the filter, so that a NO 2 -free gas mixture is inhaled.
  • the filter can then consist, for example, of a breathing mask, in the supply air flow of which the polymer-containing filter is inserted.
  • nitrogen monoxide When the polymer comes into contact with nitrogen dioxide, nitrogen monoxide is partially formed. The filter effect of the polymer against nitrogen monoxide is negligible. Nevertheless, nitrogen monoxide can also be removed quantitatively if at least one oxidative inorganic or organic compound is added to the polymer or filter material, which has a redox potential of at least 0.96 V against standard hydrogen electrode (SHE), e.g. chlorine lime, sodium hypochlorite, vanadium pentoxide or dichlorodicyanoquinone. These oxidants convert the NO to NO 2 .
  • SHE standard hydrogen electrode
  • the invention therefore furthermore relates to a filter material and a filter for removing NO and NO 2 from gases and liquids, the filter material or the filter containing a polyarylene ether and an oxidizing agent with a redox potential of at least 0.96 V SHE.
  • the invention also relates to a process for the production of NO-free and NO 2 -free gases or liquids, characterized in that the gas or the liquid to be cleaned is mixed with an oxidizing agent with a redox potential of at least 0.96 V SHE and a Contacting material containing a polyarylene ether.
  • the filter material, the filter and the method for removing NO and / or NO 2 can be used with all nitrogen oxide-containing gases and liquids. They can be used, for example, in filter masks, in air conditioning systems, in automobiles (e.g. air filters, exhaust filters), to remove the nitrogen oxides generated during combustion (e.g. flue gas cleaning), and also to remove and neutralize nitrogen oxides in liquids.
  • Polyarylene ethers can also be used as a suspension or solution to remove NO and / or NO 2 from gases.
  • polyarylene ether suspensions can consist of finely divided polyarylene ether in water.
  • Solutions of polyarylene ether can be prepared, for example, with aromatic solvents such as toluene or non-aromatic solvents such as chloroform. A gas to be cleaned is passed through the liquid to remove nitrogen oxides.
  • NO and / or NO 2 can be removed from a liquid, for example, by suspending the polymer in the liquid (stirring method) or by passing it through a column packed with the polymer (column method).
  • a gas mixture of 100 ppm NO 2 was mixed in a gas mixing system consisting of flow controllers (type 1259C) and the associated control device (type 247C, both from MKS Instruments, 81829 Kunststoff, Federal Republic of Germany) by diluting a commercial test gas mixture (538 pp NO 2 in synthetic air, Messer Griesheim GmbH, Sondergaswerk, 47009 Duisburg, Federal Republic of Germany) with nitrogen and passed at room temperature (25 ° C) over a filter cartridge, abbreviated with poly-para [2,6 dimethyl-phenylene oxide] PPO, in finely ground granulate form (average particle diameter D 50 : approx. 50 m) was filled.
  • the absorption path is characterized by the following parameters:
  • Inner diameter of the filter cartridge 2 cm used mass of PPO: 15 g
  • the gas was passed through the filter cartridge to analyze the NO and
  • NO 2 content in a NO / NO 2 chemoluminescence measuring device (type CLD 700 El Ht, Eco
  • the NO 2 concentration remained below the MAK value of 5 ppm for 18 hours.
  • Example 1 (measuring range 0-1000 ppm) passed through a filter cartridge and analyzed.
  • the absorption path is characterized by the following parameters:
  • Inner diameter of the filter cartridge 2 cm used mass of PPO: 5 g
  • the filter was gassed until the let-through NO 2 concentration was approx. 80% of the inlet concentration.
  • the filter capacity calculated from this was 18% (percent by weight) based on NO 2 .
  • Example 3 With a gas mixture with 500 ppm NO 2 in helium, produced as in Example 1 (but with a test gas mixture with 600 ppm NO 2 in helium; measuring range 0-1000 ppm), the NO 2 concentration remained 20 minutes below the detection limit. After 16 hours 40 ppm were measured, ie after this time the filter has an efficiency of over 90%.
  • Example 4 A gas mixture of 500 ppm NO 2 in synthetic air was passed as in Example 1 at room temperature (25 ° C.) over a filter cartridge, which was granulated with a polyarylene ether (Blendex XHPP 820, GE Plastics, USA) (average particle diameter approx. 500-800 ⁇ m) was filled.
  • the absorption path is characterized by the following parameters:
  • Inner diameter of the filter cartridge 1 cm used mass of PPO: 5 g

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Biomedical Technology (AREA)
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  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Polyarylene ethers are used as filter material for removing NO2 from gases and liquids. NO can also be removed in the presence of an oxidizing agent with a redox potential of at least 0.96 V SHE. The filter material is used in producing NO2-free gases, for example in the field of medicine.

Description

Besc reibung Description
Filtermaterial und Verfahren zur Herstellung von NO2-freien Gasen oder FlüssigkeitenFilter material and process for the production of NO 2 -free gases or liquids
Gegenstand der Erfindung ist ein Filtermaterial, ein Filter und ein Verfahren zur Herstellung von stickstoffdioxidfreien Gasen und Flüssigkeiten.The invention relates to a filter material, a filter and a method for producing nitrogen dioxide-free gases and liquids.
DE 43 28 450 A1 beschreibt ein Filtermaterial und ein Verfahren zur Entfernung von Stickoxiden aus Gasen und Flüssigkeiten. Polyarylensulfide werden als polymeres Filtermaterial für Stickstoffdioxid (NO2) eingesetzt. Bei der Reaktion von NO2 mit Polyarylensulfid werden die Schwefelgruppen oxidiert und dabei NO2 zu NO reduziert.DE 43 28 450 A1 describes a filter material and a method for removing nitrogen oxides from gases and liquids. Polyarylene sulfides are used as a polymer filter material for nitrogen dioxide (NO 2 ). When NO 2 reacts with polyarylene sulfide, the sulfur groups are oxidized and NO 2 is reduced to NO.
NO2-freies NO-Gas oder NO-Gasgemische werden in der Abgasmeßtechnik zur Kalibrierung von Meß- und Analysesystemen benötigt.NO 2 -free NO gas or NO gas mixtures 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. Wichtig hierbei ist sowohl die exakte Einstellung des NO-Gehaltes, als auch die Minimierung bis hin zur Eliminierung des NO2-Gehaltes. Dieses Problem tritt in der oben genannten Anwendung verstärkt auf, da hier NO mit Luftsauerstoff bei Temperaturen um 40 °C und bei hoher Luftfeuchtigkeit gemischt und über Wegstrecken von ca. 3 - 6 m geleitet werden. Dabei wird ein Teil des NO zu NO2 konvertiert werden. Dies führt zu einer Erhöhung des NO2-Gehalts im Gas, was schädlich für den Patienten ist und zu einer Reduktion des NO-Gehalt um das gebildete NO2. Wünschenswert ist hier ein Konverter, der das gebildete NO2 kurz vor dem Einatmen durch den Patienten ohne sonstige Veränderungen des Gasgemisches, z.B. der Feuchtigkeit oder der Temperatur wieder in NO umwandelt. Gegenüber einem NO2-Filter hätte dieser Konverter den Vorteil, daß der NO-Gehalt, der ursprünglich eingestellt wurde nicht verändert wird.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. What is important here is the exact setting of the NO content, as well as the minimization up to the elimination of the NO 2 content. This problem occurs more frequently in the above-mentioned application, since here NO is mixed with atmospheric oxygen at temperatures around 40 ° C and at high atmospheric humidity and passed over distances of approx. 3 - 6 m. Part of the NO will be converted to NO 2 . This leads to an increase in the NO 2 content in the gas what is harmful to the patient and leads to a reduction in the NO content by the NO 2 formed . A converter is desirable here, which converts the NO 2 formed into NO shortly before the patient inhales without any other changes in the gas mixture, for example the humidity or the temperature. Compared to a NO 2 filter, this converter would have the advantage that the NO content that was originally set is not changed.
Das farblose Stickstoffmonoxid (NO) reagiert mit molekularem Sauerstoff rasch zu braunem Stickstoffdioxid (NO2). In Gegenwart von Luft oder bei Luftzutritt wird daher NO2 aus NO gebildet. NO2 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 NO2 sehr gering sein.The colorless nitrogen monoxide (NO) reacts rapidly with molecular oxygen to give brown nitrogen dioxide (NO 2 ). In the presence of air or in the presence of air, NO 2 is therefore formed from NO. NO 2 is therefore - due to the omnipresent oxygen - an inherent contamination of NO. Particularly in the case of medical use of NO, the NO 2 content must be very low due to the toxicity.
Es wurde gefunden, daß eine Entfernung von NO2 aus Gasen oder Flüssigkeiten durch Kontaktierung mit einem Polyarylenether möglich ist. Darüberhinaus ist eine selektive Entfernung von NO2 aus NO oder NO-haltigen Medien wie Gasen oder Flüssigkeiten mit Hilfe eines Polyarylenether möglich. Polyarylenether eignen sich daher als Filtermaterial für NO2. Dies ist überraschend, da sich die Polyarylenether von den Polyarylensulfiden strukturell stark unterscheiden und keine Schwefelgruppen enthalten.It has been found that NO 2 can be removed from gases or liquids by contacting with a polyarylene ether. In addition, a selective removal of NO 2 from NO or NO-containing media such as gases or liquids is possible using a polyarylene ether. Polyarylene ethers are therefore suitable as filter material for NO 2 . This is surprising since the polyarylene ethers differ greatly in structure from the polyarylene sulfides and contain no sulfur groups.
Die Erfindung betrifft ein Filtermaterial zur Entfernung von NO2 aus Gasen und Flüssigkeiten, das einen Polyarylenether enthält.The invention relates to a filter material for removing NO 2 from gases and liquids, which contains a polyarylene ether.
Weiterer Gegenstand der Erfindung ist ein Filter zur Entfernung von NO2 aus Gasen und Flüssigkeiten, das einen Polyarylenether enthält.Another object of the invention is a filter for removing NO 2 from gases and liquids, which contains a polyarylene ether.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung von NO2-freien Gasen oder Flüssigkeiten, wobei das zu reinigende Gas oder die zu reinigende Flüssigkeit mit einem Material in Kontakt gebracht wird, das einen Polyarylenether enthält.The invention also relates to a method for producing NO 2 -free Gases or liquids, the gas or liquid to be cleaned being brought into contact with a material which contains a polyarylene ether.
NOx wird als Sammelbegriff für NO, NO2 und N2O4 verwendet.NO x is used as a collective term for NO, NO 2 and N 2 O 4 .
NO2 und N2O4 stehen im chemischen Gleichgewicht. N2O4 wird durch Polyarylenether aus Gasen und Flüssigkeiten entfernt.NO 2 and N 2 O 4 are in chemical equilibrium. N 2 O 4 is removed from gases and liquids using polyarylene ether.
Die Ausdrücke "frei von NO2" und "quantitative Entfernung von NO2" bedeuten, daß der Gehalt von NO2 in einem Medium kleiner als 1 ppm ist.The terms "free of NO 2 " and "quantitative removal of NO 2 " mean that the content of NO 2 in a medium is less than 1 ppm.
Das Filtermaterial, das Filter und das Verfahren gemäß der Erfindung eignen sich auch zur Entfernung von NO2 aus NO enthaltenden Gasen oder Flüssigkeiten.The filter material, the filter and the method according to the invention are also suitable for removing NO 2 from gases or liquids containing NO.
Ein Polyarylenether ist ein Polymer, das mindestens eine Arylenether-Einheit (-A-O-; A steht für Arylen) enthält. Ein Arylen bezeichnet eine aromatische Einheit mit zwei Bindungsstellen, z.B. -CΘH4-. Ein- oder mehrkernige Aromaten können eine Aryleneinheit bilden, wie Benzol, Pyridin, Naphthalin, Phenanthren, Anthracen. Bevorzugt sind substituierte Aryleneinheiten. Arylen-Substituenten sind beispielsweise CT-CTβ-Alky wie -CH3, -C2H5, -C3H7, -C4H9, -C5H , -C(CH3)3 , -CH2- CH(CH3)2, -C2H4-CH(CH3)2 oder -CH2-C(CH3)3. Geeignete Polyarylenether sind beschrieben in der noch unveröffentlichten europäischen Patentanmeldung mit dem Aktenzeichen 951 12259.7, Anmeldetag 04.08.1995, mit dem Titel "Filtermaterial und Verfahren zur Entfernung von Ozon aus Gasen und Flüssigkeiten", worauf Bezug genommen wird.A polyarylene ether is a polymer that contains at least one arylene ether unit (-AO-; A stands for arylene). An arylene denotes an aromatic unit with two binding sites, eg -C Θ H 4 -. Mono- or polynuclear aromatics can form an arylene unit, such as benzene, pyridine, naphthalene, phenanthrene, anthracene. Substituted arylene units are preferred. Arylene substituents are, for example, C T -C Tβ -Alky such as -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H, -C (CH 3 ) 3 , -CH 2 - CH (CH 3 ) 2 , -C 2 H 4 -CH (CH 3 ) 2 or -CH 2 -C (CH 3 ) 3 . Suitable polyarylene ethers are described in the as yet unpublished European patent application with the file number 951 12259.7, filing date August 4, 1995, entitled "Filter material and process for removing ozone from gases and liquids", to which reference is made.
Bevorzugter Polyarylenether ist Poly-[2,6-dimethyl-phenylenoxid]. Der Polyarylenether kann auch mit einem oder mehreren anderen Polymeren verschnitten sein.The preferred polyarylene ether is poly- [2,6-dimethylphenylene oxide]. The polyarylene ether can also be blended with one or more other polymers.
Der Polyarylenether kann auch ein Blockcopolymer oder ein Blend, der mindestens einen Polyarylenether enthält, sein. Geeignete Blends sind beispielsweise Polyarylenether-Blends, die Polystyrol-Homopolymer und/oder Polystyrol- Copolymer und/oder Polyamid und/oder Polyolefin enthalten.The polyarylene ether can also be a block copolymer or a blend which contains at least one polyarylene ether. Suitable blends are, for example, polyarylene ether blends which contain polystyrene homopolymer and / or polystyrene copolymer and / or polyamide and / or polyolefin.
Beispiele für Polyarylenether und deren Herstellung sind in "Ullmann 's Encyclopedia of Industrial Chemistry, 5. Auflage, Volume A21 , B. Elvers (Ed.), VCH, Weinheim-Basel, Cambridge-New York 1992, Stichwort 'Poly (Phenylene Oxides)', Seite 605-614" aufgeführt, worauf Bezug genommen wird.Examples of polyarylene ethers and their preparation can be found in "Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A21, B. Elvers (Ed.), VCH, Weinheim-Basel, Cambridge-New York 1992, keyword 'Poly (Phenylene Oxides ) ', Page 605-614 ", to which reference is made.
Polyarylenether und Polyarylenether-haltige Polymere werden im folgenden als Polymer bezeichnet.Polyarylene ethers and polyarylene ether-containing polymers are referred to below as polymer.
Das Polymer kann zum Beispiel als Pulver, Granulate, Fasern, Vlies, Gewebe, Folien und/oder Formkörper verwendet werden. Die Pulver besitzen handelsübliche Teilchengrößen, wobei auch Granulate verwendbar sind. Wichtig hierbei ist es, daß das zu behandelnde Gas oder die Flüssigkeit durch das Pulver, beispielsweise in Form eines Festbettes ohne Störung durchgeleitet werden kann. Wird das Polymer als Faser verwendet, werden diese als Stapelfasern, Nadelfilz, "non woven" Material, Kardenband oder Gewebe eingesetzt. Auch Folien oder Folienschnipsel können in geeigneter Form Verwendung finden.The polymer can be used, for example, as a powder, granules, fibers, nonwoven, fabric, films and / or moldings. The powders have commercially available particle sizes, and granules can also be used. It is important here that the gas or liquid to be treated can be passed through the powder, for example in the form of a fixed bed, without interference. If the polymer is used as a fiber, these 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.
Das Polymer kann im allgemeinen als unverschnittenes Material eingesetzt werden. Möglich ist aber auch der Zusatz von Füllstoffen, wie Kreide, Talk, Ton, Glimmer, und/oder faserförmige Verstärkungsmittel, wie Glas- und Kohlenstoffasern, Whiskers, sowie weitere Zusatzstoffe und Verarbeitungshilfsmittel, z.B. Gleitmittel, Trennmittel, Antioxidantien, UV-Stabilisatoren, enthalten.The polymer can generally be used as an unblended material. However, it is also possible to add fillers, such as chalk, talc, clay, mica, and / or fibrous reinforcing agents, such as glass and carbon fibers, whiskers, and further additives and processing aids, for example lubricants. Release agents, antioxidants, UV stabilizers.
Beschichtungen von Trägermaterialien mit dem Polymer können durch Auftragen von Lösungen des Polymers (Lösemittel z.B. Toluol, Chloroform) auf das Trägermaterial erhalten werden. Imprägnierungen werden z.B. durch Tränken eines saugfähigen Trägermaterials hergestellt. Als Trägermaterial werden im allgemeinen anorganische Stoffe wie Glas, Kieselgel, Aluminiumoxid, Sand, keramische Massen, Metall und organische Stoffe wie Kunststoffe eingesetzt.Coatings of carrier materials with the polymer can be obtained by applying solutions of the polymer (solvents e.g. toluene, chloroform) to the carrier material. Impregnations are e.g. produced 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.
Dem Polymer können auch Stoffe aufgebracht werden, zum Beispiel Metalle, insbesondere Edelmetalle und Übergangsmetalle, oder Metalloxide wie Übergangsmetalloxide. Die Metalle oder Metalloxide können beispielsweise durch Aufimprägnieren auf das Polymer aufgebracht werden, die dann zum Beispiel in Form kleiner Cluster vorliegen.Substances can also be applied to the polymer, for example metals, in particular noble metals and transition metals, or metal oxides such as transition metal oxides. The metals or metal oxides can be applied to the polymer, for example by impregnation, which are then present, for example, in the form of small clusters.
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 zwischen minus 10 bis 200° C, vorzugsweise zwischen 0 und 180° 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 between minus 10 to 200 ° C, preferably between 0 and 180 ° C.
Die erforderliche Kontaktzeit des zu reinigenden Mediums mit dem Filtermaterial ist unter anderem abhängig von der Strömungsgeschwindigkeit, der Verweilzeit, der Oberfläche des Filtermaterials, der Geometrie des Filters und der Temperatur. Im allgemeinen liegt die Zeit des Kontaktes des substituierte Polyarylenethers mit dem zu reinigenden Medium im Bereich zwischen 0,001 Sekunden und 10 Minuten, vorzugsweise zwischen 0,01 Sekunden und 1 Minute. Die Zeiten können aber auch überschritten werden.The required contact time of the medium to be cleaned with the filter material depends, among other things, on the flow rate, the residence time, the surface of the filter material, the geometry of the filter and the temperature. In general, the time of contact of the substituted polyarylene ether with the medium to be cleaned ranges between 0.001 seconds and 10 minutes, preferably between 0.01 seconds and 1 minute. The times can also be exceeded.
Die Größe der spezifischen Oberfläche des Polymers hat einen bedeutenden Einfluß auf die Filterwirkung des Polymers. Im allgemeinen ist die Filterwirkung des Polymers um so größer je größer die spezifische Oberfläche des Polymers ist. Eine große spezifische Oberfläche und poröse Strukturen des Polymers, wobei ein abgestimmtes Verhältnis von Mikro- und Makroporen sich als günstig erweist, sind für eine Fiiterwirkung besonders vorteilhaft. Die Filterwirkung des Polymers wird auch von der Kristallinität beziehungsweise von der Größe des amorphen Anteils des Polymers beeinflußt. Ein hoher amorpher Anteil im Polymer begünstigt im allgemeinen die Filterwirkung des Polymers.The size of the specific surface area of the polymer has a significant impact on the filter effect of the polymer. In general, the greater the specific surface area of the polymer, the greater the filtering effect of the polymer. A large specific surface area and porous structures of the polymer, a balanced ratio of micropores and macropores proving to be favorable, are particularly advantageous for a filtering effect. The filter effect of the polymer is also influenced by the crystallinity or the size of the amorphous part of the polymer. A high amorphous content in the polymer generally favors the filter effect of the polymer.
Die Entfernung von Stickstoffdioxid aus Gasen oder Flüssigkeiten durch Kontakt mit einem Polyarylenether kann auf chemischer Wirkung, katalytischer Wirkung und/oder physikalischer Wechselwirkung beruhen. Bei der chemischen Wirkung reagiert das Polyarylenether mit dem Stickstoffdioxid und erfährt dabei eine Oxidation. Bei alkylsubstituierten Polyarylenethern wird die Alkylgruppe oxidiert. Dies erfolgt besonders leicht in der Benzyl-Position, das heißt an dem einem aromatischen Kern nächstgelegenen Kohlenstoffatom der Alkylgruppe einer Arylen- Einheit.The removal of nitrogen dioxide from gases or liquids by contact with a polyarylene ether can be based on chemical action, catalytic action and / or physical interaction. In the chemical action, the polyarylene ether reacts with the nitrogen dioxide and undergoes oxidation. The alkyl group is oxidized in the case of alkyl-substituted polyarylene ethers. This occurs particularly easily in the benzyl position, that is to say on the carbon atom of the alkyl group of an arylene unit which is closest to an aromatic nucleus.
Bei der Entfernung von NO2 aus Gasen oder Flüssigkeiten werden aus dem Polymer keine flüchtigen Produkte gebildet.No volatile products are formed from the polymer when NO 2 is removed from gases or liquids.
Die Entfernung von NO2 kann bei NOx-haltigen Gasströmen und Flüssigkeiten angewendet werden. Das Verfahren zur NO2-Entfernung arbeitet z.B. bei Gasen mit einem NO-Gehalt zwischen 60 Vol.-% und 1 ppb, vorzugsweise 50 Vol.-% und 10 ppb und besonders bevorzugt zwischen 40 Voi.-% und 50 ppb. Der abtrennbare NO2-Gehalt liegt zwischen 50 % und 1 ppb, vorzugsweise 20 Vol.-% und 10 ppb und besonders bevorzugt zwischen 10 Vol.-% und 10 ppb. Das Verhältnis zwischen NO und NO2 in den zu behandelnden Gasen oder Flüssigkeiten kann dabei zwischen 1000 000 : 1 und 1 : 1 000 000, vorzugsweise zwischen 10 000 : 1 und 1 :10000 und besonders bevorzugt zwischen 1 000 : 1 und 1 : 1 000 liegen.The removal of NO 2 can be used for gas streams and liquids containing NO x . The method for NO 2 removal works, for example, in the case of gases with an NO content between 60% by volume and 1 ppb, preferably 50% by volume and 10 ppb and particularly preferably between 40% by volume and 50 ppb. The separable NO 2 content is between 50% and 1 ppb, preferably 20% by volume and 10 ppb and particularly preferably between 10% by volume and 10 ppb. The ratio between NO and NO 2 in the gases or liquids to be treated can be between 1000,000: 1 and 1: 1,000,000, preferably between 10,000: 1 and 1: 10,000 and particularly preferably between 1,000: 1 and 1: 1,000.
Das Filter kann das Polymer 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 e.g. in the form of a powder bed, a fleece, a fleece-powder mixture, a grid or honeycomb structure. The powder can also be incorporated into nonwovens made of other materials.
Das Filtermaterial, das Filter und das Verfahren zur NO2-Entfernung eignet sich beispielsweise zur Herstellung von NO2-freiem NO-Gas oder NO2-freien NO- haltigem Gas für Prüfgase und besonders für Anwendungen von NO in der Medizintechnik z.B. bei Patienten mit schweren pulmonalen Krankheitsbildern kann durch Zudosierung von NO zur Atemluft der Bluthochdruck im Lungenkreislauf gesenkt werden. Dies gilt sowohl für IRDS (Infant Respiratory Distress Syndrome) als auch für ARDS (Adult Respiratory Distress Syndrome)-Patienten. Denkbar sind aber auch Anwendungen im Bereich der Cardiochirurgie, zur Intensivbeatmung der Patienten mit NO, um den Bluthochdruck im pulmonalen Kreislauf zu senken. Wichtig für diese Anwendungen ist sowohl die exakte Einstellung des NO- Gehaltes, als auch die Minimierung bis hin zur Eliminierung des NO2-Gehaltes.The filter material, the filter and the method for NO 2 removal are suitable, for example, for producing NO 2 -free NO gas or NO 2 -free NO-containing gas for test gases and especially for applications of NO in medical technology, for example in patients with severe pulmonary symptoms can be reduced by adding NO to the air we breathe to reduce the high blood pressure in the pulmonary circulation. This applies to both IRDS (Infant Respiratory Distress Syndrome) and ARDS (Adult Respiratory Distress Syndrome) patients. However, applications in the field of cardiosurgery are also conceivable, for intensive ventilation of patients with NO, in order to lower the high blood pressure in the pulmonary circulation. What is important for these applications is the exact setting of the NO content as well as the minimization up to the elimination of the NO 2 content.
Wegen der Schädlichkeit von NO2 für den Menschen ist die Bildung von NO2 aus NO und Sauerstoff bei medizinischen NO- Anwendungen, wo Mischungen von NO und Sauerstoff bei erhöhter Temperatur (z. B. 40° C) und als feuchtes Gas eingesetzt werden, ein großes Problem. Der Einsatz des erfindungsgemäßen Verfahrens oder Filters zur NO2-Entfernung kann dieses Problem beseitigen. Zwischen Filter und Lunge entstehendes NO2 kann nicht mehr entfernt werden. Der Weg zwischen Filter und Lunge sollte daher möglichst gering sein.Because of the harmfulness of NO 2 to humans, the formation of NO 2 from NO and oxygen in medical NO applications, where mixtures of NO and oxygen are used at elevated temperature (for example 40 ° C.) and as a moist gas, a big problem. The use of the method or filter according to the invention for NO 2 removal can eliminate this problem. NO 2 generated between the filter and the lungs can no longer be removed. The path between the filter and the lungs should therefore be as short as possible.
Das Verfahren und das Filter zur NO2-Entfernung können an mehreren Stellen in einem Beatmungssystem in der Medizintechnik zur Anwendung kommen. Das Filter kann unmittelbar hinter dem Druckreduzierventeil angebracht werden, um den Anteil an NO2, der bei der Herstellung der eingesetzten NO/Stickstoff-Gasmischung entstanden oder übriggebleiben ist, zu minimieren. Mit diesem hier beschriebenen Verfahren können Gasmischungen gereinigt werden, die NO in einer Konzentration zwischen 1 ppb und 100 000 ppm in Stickstoff, vorzugsweise 1 ppm bis 10 000 ppm enthalten. Der Volumenstrom des NO / Stickstoff-Gasgemisches kann dabei zwischen 0.001 und 1000 l/min vorzugsweise 0.01 und 250 l/min liegen.The method and the filter for NO 2 removal can be used at several points in a ventilation system in medical technology. The filter can be installed immediately behind the pressure reducing valve to the To minimize the proportion of NO 2 which has arisen or remained during the production of the NO / nitrogen gas mixture used. With the method described here, gas mixtures can be purified which contain NO in a concentration between 1 ppb and 100,000 ppm in nitrogen, preferably 1 ppm to 10,000 ppm. The volume flow of the NO / nitrogen gas mixture can be between 0.001 and 1000 l / min, preferably 0.01 and 250 l / min.
Bei einer Behandlung mit einer NO-Aufnahme über die Lunge kann das NO-haltige Gas und die zugesetzte Luft vor oder im Filter vereinigt werden und damit erreicht werden, daß ein NO2-freies Gasgemisch eingeatmet wird. Das Filter kann dann z.B. aus einer Atemmaske bestehen, in deren Zuluftstrom das Polymer enthaltene Filter eingesetzt ist.In the case of treatment with an NO uptake via the lungs, the gas containing NO and the added air can be combined in front of or in the filter, so that a NO 2 -free gas mixture is inhaled. The filter can then consist, for example, of a breathing mask, in the supply air flow of which the polymer-containing filter is inserted.
Bei dem Kontakt des Polymers mit Stickstoffdioxid entsteht teilweise Stickstoffmonoxid. Die Filterwirkung des Polymers gegenüber Stickstoffmonoxid ist vernachlässigbar gering. Dennoch läßt sich auch Stickstoffmonoxid quantitativ entfernen, wenn dem Polymer oder Filtermaterial mindestens eine oxidativ wirkende anorganische bzw. organische Verbindung zugesetzt wird, die ein Redoxpotential von mindestens 0,96 V gegen Standardwasserstoffelektrode (SHE) aufweist, z.B. Chlorkalk, Natriumhypochlorit, Vanadinpentoxid oder Dichlordicyanochinon. Diese Oxidationsmittel überführen das NO in NO2. Durch Verwendung eines geeigneten Oxidationsmittels in Kombination mit einem Polyarylenether sind das Filtermaterial, das Filter und das Verfahren auch zur Entfernung von NO aus Gasen und Flüssigkeiten geeignet.When the polymer comes into contact with nitrogen dioxide, nitrogen monoxide is partially formed. The filter effect of the polymer against nitrogen monoxide is negligible. Nevertheless, nitrogen monoxide can also be removed quantitatively if at least one oxidative inorganic or organic compound is added to the polymer or filter material, which has a redox potential of at least 0.96 V against standard hydrogen electrode (SHE), e.g. chlorine lime, sodium hypochlorite, vanadium pentoxide or dichlorodicyanoquinone. These oxidants convert the NO to NO 2 . By using a suitable oxidizing agent in combination with a polyarylene ether, the filter material, the filter and the method are also suitable for removing NO from gases and liquids.
Ein weiterer Gegenstand der Erfindung ist daher ein Filtermaterial und ein Filter zur Entfernung von NO und NO2 aus Gasen und Flüssigkeiten, wobei das Filtermaterial oder das Filter einen Polyarylenether und ein Oxidationsmittel mit einem Redoxpotential von mindestens 0,96 V SHE enthält. Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung von NO-freien und NO2-freien Gasen oder Flüssigkeiten, dadurch gekennzeichnetz, daß das zu reinigende Gas oder die zu reinigende Flüssigkeit mit einem Oxidationsmittel mit einem Redoxpotential von mindestens 0,96 V SHE und einem Material in Kontakt gebracht wird, das einen Polyarylenether enthält.The invention therefore furthermore relates to a filter material and a filter for removing NO and NO 2 from gases and liquids, the filter material or the filter containing a polyarylene ether and an oxidizing agent with a redox potential of at least 0.96 V SHE. The invention also relates to a process for the production of NO-free and NO 2 -free gases or liquids, characterized in that the gas or the liquid to be cleaned is mixed with an oxidizing agent with a redox potential of at least 0.96 V SHE and a Contacting material containing a polyarylene ether.
Das Filtermaterial, das Filter und das Verfahren zur Entfernung von NO und/oder NO2 können bei allen stickoxidhaltigen Gasen und Flüssigkeiten angewendet werden. Sie können beispielsweise Anwendung finden in Filtermasken, in Klimaanlagen, in Automobilen (z.B. Luftfilter, Abgasfilter), zur Entfernung der bei der Verbrennung entstandenen Stickoxide (z.B. Rauchgasreinigung), ferner zur Entfernung und Unschädlichmachung von Stickoxiden in Flüssigkeiten.The filter material, the filter and the method for removing NO and / or NO 2 can be used with all nitrogen oxide-containing gases and liquids. They can be used, for example, in filter masks, in air conditioning systems, in automobiles (e.g. air filters, exhaust filters), to remove the nitrogen oxides generated during combustion (e.g. flue gas cleaning), and also to remove and neutralize nitrogen oxides in liquids.
Polyarylenether können zur Entfernung von NO und/oder NO2 aus Gasen auch als Suspension oder Lösung eingesetzt werden. Beispielsweise können Polyarylenether-Suspensionen aus feinverteiltem Polyarylenether in Wasser bestehen. Lösungen von Polyarylenether sind beispielweise mit aromatischen Lösemitteln wie Toluol oder nichtaromatischen Lösemitteln wie Chloroform herstellbar. Zur Entfernung von Stickoxiden wird ein zu reinigendes Gas durch die Flüssigkeit geleitet.Polyarylene ethers can also be used as a suspension or solution to remove NO and / or NO 2 from gases. For example, polyarylene ether suspensions can consist of finely divided polyarylene ether in water. Solutions of polyarylene ether can be prepared, for example, with aromatic solvents such as toluene or non-aromatic solvents such as chloroform. A gas to be cleaned is passed through the liquid to remove nitrogen oxides.
Die Entfernung von NO und/oder NO2 aus einer Flüssigkeit kann zum Beispiel dadurch erfolgen, daß das Polymer in der Flüssigkeit suspendiert (Ausrührverfahren) oder durch eine mit dem Polymer gepackte Säule (Säulenverfahren) geleitet wird.NO and / or NO 2 can be removed from a liquid, for example, by suspending the polymer in the liquid (stirring method) or by passing it through a column packed with the polymer (column method).
Vorteilhaft für die Entfernung von NO2 oder NO aus einem Gas oder einer Flüssigkeit ist die Verwendung von einem Filtermaterial mit großer Oberfläche, zum Beispiel ein poröses Pulver oder eine poröse Faser. BeispieleIt is advantageous to remove NO 2 or NO from a gas or a liquid by using a filter material with a large surface area, for example a porous powder or a porous fiber. Examples
1 ) Ein Gasgemisch von 100 ppm NO2 wurde in einem Gasmischsystem, bestehend aus Flow-Controllern (Typ 1259C) und dem zugehörigen Kontrollgerät (Typ 247C, beide von MKS Instruments, 81829 München, Bundesrepublik Deutschland), durch Verdünnung eines kommerziellen Prüfgasgemisches (538 pp NO2 in synthetischer Luft, Messer Griesheim GmbH, Sondergaswerk, 47009 Duisburg, Bundesrepublik Deutschland) mit Stickstoff hergestellt und bei Zimmertemperatur (25° C) über eine Filterpatrone geleitet, die mit Poly-para[2,6 dimethyl-phenylenoxid], abgekürzt PPO, in feingemahlener Granulatform (mittlerer Teilchendurchmesser D50 : ca. 50 m) gefüllt war. Die Absorptionsstrecke ist durch folgende Parameter gekennzeichnet:1) A gas mixture of 100 ppm NO 2 was mixed in a gas mixing system consisting of flow controllers (type 1259C) and the associated control device (type 247C, both from MKS Instruments, 81829 Munich, Federal Republic of Germany) by diluting a commercial test gas mixture (538 pp NO 2 in synthetic air, Messer Griesheim GmbH, Sondergaswerk, 47009 Duisburg, Federal Republic of Germany) with nitrogen and passed at room temperature (25 ° C) over a filter cartridge, abbreviated with poly-para [2,6 dimethyl-phenylene oxide] PPO, in finely ground granulate form (average particle diameter D 50 : approx. 50 m) was filled. The absorption path is characterized by the following parameters:
Innendurchmesser der Filterpatrone: 2 cm eingesetzte Masse von PPO : 15 gInner diameter of the filter cartridge: 2 cm used mass of PPO: 15 g
Schütthöhe von PPO: 9 cmDumping height of PPO: 9 cm
Gas-Durchsatz: 25 l/hGas throughput: 25 l / h
Gas-Strömungsgeschwindigkeit: 2.2 cm/sGas flow rate: 2.2 cm / s
Das Gas wurde nach Durchgang durch die Filterpatrone zur Analyse des NO undThe gas was passed through the filter cartridge to analyze the NO and
NO2 Gehalts in ein NO/NO2-Chemolumineszenzmeßgerät (Typ CLD 700 El Ht, EcoNO 2 content in a NO / NO 2 chemoluminescence measuring device (type CLD 700 El Ht, Eco
Physics AG, Durnten, Schweiz; minimale Nachweisgrenze 0.1 ppm, Linearität ± 1Physics AG, Durnten, Switzerland; minimum detection limit 0.1 ppm, linearity ± 1
% vom Vollausschlag), mit der Meßbereichseinstellung% of full scale), with the measuring range setting
0-100 ppm, geleitet.0-100 ppm.
Die Filterwirkung auf NO2 tritt sofort ein. Im Zeitraum von 2 Stunden lag die NO2-The filter effect on NO 2 occurs immediately. In a period of 2 hours, the NO 2 -
Konzentration unterhalb der Nachweisgrenze von 1 ppm. Für weitereConcentration below the detection limit of 1 ppm. For further
18 Stunden blieb die NO2-Konzentration unterhalb des MAK-Wertes von 5 ppm.The NO 2 concentration remained below the MAK value of 5 ppm for 18 hours.
2) Ein Gasgemisch von 500 ppm NO2 in synthetischer Luft wurde wie in2) A gas mixture of 500 ppm NO 2 in synthetic air was as in
Beispiel 1 (Meßbereich 0-1 000 ppm) über eine Filterpatrone geleitet und analysiert. Die Absorptionsstrecke ist durch folgende Parameter gekennzeichnet:Example 1 (measuring range 0-1000 ppm) passed through a filter cartridge and analyzed. The absorption path is characterized by the following parameters:
Innendurchmesser der Filterpatrone: 2 cm eingesetzte Masse von PPO: 5 gInner diameter of the filter cartridge: 2 cm used mass of PPO: 5 g
Schütthöhe von PPO: 3 cmDumping height of PPO: 3 cm
Gas-Durchsatz: 48 l/hGas throughput: 48 l / h
Gas-Strömungsgeschwindigkeit: 4.25 cm/sGas flow rate: 4.25 cm / s
Der Filter wurde solange begast, bis die durchgelassene NO2-Konzentration ca. 80 % der Eingangskonzentration betrug. Die hieraus errechnete Filterkapazität betrug 18% (Gewichtsprozent) bezogen auf NO2.The filter was gassed until the let-through NO 2 concentration was approx. 80% of the inlet concentration. The filter capacity calculated from this was 18% (percent by weight) based on NO 2 .
3) Bei einem Gasgemisch mit 500 ppm NO2 in Helium, hergestellt wie in Beispiel 1 (jedoch mit einem Prüfgasgemisch mit 600 ppm NO2 in Helium; Meßbereich 0-1000 ppm), blieb die NO2-Konzentration 20 Minuten unterhalb der Nachweisgrenze. Nach 16 Stunden wurden 40 ppm gemessen, d.h. der Filter hat nach dieser Zeit einen Wirkungsgrad von noch über 90 %.3) With a gas mixture with 500 ppm NO 2 in helium, produced as in Example 1 (but with a test gas mixture with 600 ppm NO 2 in helium; measuring range 0-1000 ppm), the NO 2 concentration remained 20 minutes below the detection limit. After 16 hours 40 ppm were measured, ie after this time the filter has an efficiency of over 90%.
4) Ein Gasgemisch von 500 ppm NO2 in synthetischer Luft wurde wie in Beispiel 1 bei Zimmertemperatur (25° C) über eine Filterpatrone geleitet, die mit einem Polyarylenether (Blendex XHPP 820, GE Plastics, USA) in Granulatform (mittlerer Teilchendurchmesser ca. 500-800 μm) gefüllt war. Die Absorptionsstrecke ist durch folgende Parameter gekennzeichnet:4) A gas mixture of 500 ppm NO 2 in synthetic air was passed as in Example 1 at room temperature (25 ° C.) over a filter cartridge, which was granulated with a polyarylene ether (Blendex XHPP 820, GE Plastics, USA) (average particle diameter approx. 500-800 μm) was filled. The absorption path is characterized by the following parameters:
Innendurchmesser der Filterpatrone: 1 cm eingesetzte Masse von PPO: 5 gInner diameter of the filter cartridge: 1 cm used mass of PPO: 5 g
Schütthöhe von PPO: 4,5 cmDumping height of PPO: 4.5 cm
Gas-Durchsatz: 48 l/hGas throughput: 48 l / h
Gas-Strömungsgeschwindigkeit: 4.25 cm/s Direkt zu Beginn des Experiments blieb die NO2-Konzentration für 5 Minuten unterhalb der Nachweisgrenze. Nach 3 Stunden wurden 75 ppm NO2 vom Filter durchgelassen (Meßbereich 0-1 000 ppm). Gas flow rate: 4.25 cm / s Right at the start of the experiment, the NO 2 concentration remained below the detection limit for 5 minutes. After 3 hours, 75 ppm NO 2 was let through by the filter (measuring range 0-1000 ppm).

Claims

Patentansprüche: Claims:
1. Filtermaterial zur Entfernung von NO2 aus Gasen und Flüssigkeiten, das einen Polyarylenether enthält.1. Filter material for the removal of NO 2 from gases and liquids, which contains a polyarylene ether.
2. Filter zur Entfernung von NO2 aus Gasen und Flüssigkeiten, das einen Polyarylenether enthält.2. Filter for removing NO 2 from gases and liquids, which contains a polyarylene ether.
3. Verfahren zur Herstellung von NO2-freien Gasen oder Flüssigkeiten, dadurch gekennzeichnetz, daß das zu reinigende Gas oder die zu reinigende Flüssigkeit mit einem Material in Kontakt gebracht wird, das einen Polyarylenether enthält.3. Process for the production of NO 2 -free gases or liquids, characterized in that the gas to be cleaned or the liquid to be cleaned is brought into contact with a material which contains a polyarylene ether.
4. Filtermaterial zur Entfernung von NO und NO2 aus Gasen und Flüssigkeiten, dadurch gekennzeichnet, daß das Filtermaterial einen Polyarylenether und ein Oxidationsmittel mit einem Redoxpotential von mindestens 0,96 V SHE enthält.4. Filter material for removing NO and NO 2 from gases and liquids, characterized in that the filter material contains a polyarylene ether and an oxidizing agent with a redox potential of at least 0.96 V SHE.
5. Filter zur Entfernung von NO und NO2 aus Gasen und Flüssigkeiten, dadurch gekennzeichnet, daß das Filter einen Polyarylenether und ein Oxidationsmittel mit einem Redoxpotential von mindestens 0,96 V SHE enthält.5. Filter for removing NO and NO 2 from gases and liquids, characterized in that the filter contains a polyarylene ether and an oxidizing agent with a redox potential of at least 0.96 V SHE.
6. Filtermaterial nach Anspruch 1 oder 4, Filter nach Anspruch 2 oder 5 oder Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der Polyarylenether Poly-[2,6-dimethyl-phenylenoxid] ist.6. Filter material according to claim 1 or 4, filter according to claim 2 or 5 or method according to claim 3, characterized in that the polyarylene ether is poly- [2,6-dimethyl-phenylene oxide].
7. Verwendung eines Filtermaterials nach Anspruch 1 oder eines Filters nach Anspruch 2 zur Erzeugung von NO2-freien Prüfgasen. 7. Use of a filter material according to claim 1 or a filter according to claim 2 for the generation of NO 2 -free test gases.
8. Verwendung eines Filtermaterials nach Anspruch 1 oder eines Filters nach Anspruch 2 zur Erzeugung von NO2-freiem NO-Gas oder NO2-freien NO- Gasgemischen.8. Use of a filter material according to claim 1 or a filter according to claim 2 for the production of NO 2 -free NO gas or NO 2 -free NO gas mixtures.
9. Verwendung eines Filtermaterials nach Anspruch 1 oder eines Filters nach Anspruch 2 als Atemschutzfilter.9. Use of a filter material according to claim 1 or a filter according to claim 2 as a respiratory protection filter.
10. Verwendung eines Filtermaterials nach Anspruch 1 oder eines Filters nach Anspruch 2 zur Erzeugung von NO2-freien Stickstoffmonoxid-Stickstoff-Luft- Gemischen für medizinische Applikationen.10. Use of a filter material according to claim 1 or a filter according to claim 2 for the production of NO 2 -free nitrogen monoxide-nitrogen-air mixtures for medical applications.
1 1 . Verwendung eines Filtermaterials nach Anspruch 1 oder eines Filters nach Anspruch 2 zur Erzeugung von NO2-freien Stickstoffmonoxid-Stickstoff-Luft- Gemischen zur Behandlung von IRDS, ARDS, Lungenversagen, Migräne, Asthma, persistierende pulmonale Hypertonie basierend auf Linksherzinsuffizienz oder zur Verbesserung der Lungenfunktion.1 1. Use of a filter material according to claim 1 or a filter according to claim 2 for the production of NO 2 -free nitrogen monoxide nitrogen air mixtures for the treatment of IRDS, ARDS, lung failure, migraines, asthma, persistent pulmonary hypertension based on left heart failure or to improve lung function .
12. Verfahren zur Herstellung von NO-freien und NO2-freien Gasen oder Flüssigkeiten, dadurch gekennzeichnetz, daß das zu reinigende Gas oder die zu reinigende Flüssigkeit mit einem Oxidationsmittel mit einem Redoxpotential von mindestens 0,96 V SHE und einem Material in Kontakt gebracht wird, das einen Polyarylenether enthält. 12. A process for the production of NO-free and NO 2 -free gases or liquids, characterized in that the gas or liquid to be cleaned is brought into contact with an oxidizing agent with a redox potential of at least 0.96 V SHE and a material that contains a polyarylene ether.
EP95936489A 1994-10-25 1995-10-13 Filter material and process for producing no 2-free gases Withdrawn EP0788398A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4437985A DE4437985A1 (en) 1994-10-25 1994-10-25 Polyarylene ethers are used in the prodn. of respiratory filters and to remove nitrogen dioxide from gas mixtures
DE4437985 1994-10-25
DE4438529 1994-11-01
DE4438529A DE4438529A1 (en) 1994-11-01 1994-11-01 Polyarylene ethers are used in the prodn. of respiratory filters and to remove nitrogen dioxide from gas mixtures
PCT/EP1995/004036 WO1996012551A1 (en) 1994-10-25 1995-10-13 Filter material and process for producing no2-free gases

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EP (1) EP0788398A1 (en)
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US5846297A (en) 1998-12-08
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