WO2010020345A1 - Oxydation catalytique de chlorure d'hydrogène avec de l'oxygène dans un plasma non thermique - Google Patents

Oxydation catalytique de chlorure d'hydrogène avec de l'oxygène dans un plasma non thermique Download PDF

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WO2010020345A1
WO2010020345A1 PCT/EP2009/005683 EP2009005683W WO2010020345A1 WO 2010020345 A1 WO2010020345 A1 WO 2010020345A1 EP 2009005683 W EP2009005683 W EP 2009005683W WO 2010020345 A1 WO2010020345 A1 WO 2010020345A1
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plasma
reactor
oxidation
hcl
catalyst
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PCT/EP2009/005683
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German (de)
English (en)
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Eberhard Stelter
Frank-Dieter Kopinke
Ulf Roland
Robert Köhler
Frank Holzer
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Bayer Materialscience Ag
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/20—Improvements relating to chlorine production

Definitions

  • the invention relates to a process for the production of chlorine by catalytic oxidation of gaseous hydrogen chloride under the action of a non-thermal plasma.
  • the combined effect of catalyst and plasma results in higher levels of HCl conversion than either of the two activation methods taken alone.
  • By lowering the reaction temperature in the plasma reactor in comparison to the catalyzed Deacon reaction very high degrees of HCl conversion are possible without significant thermodynamic limitation.
  • the Deacon reaction can be carried out purely thermally at high temperatures (> 700 ° C) or catalyzed at lower temperatures (300 to 500 ° C).
  • Suitable catalysts are described, for example, in DE 1 567 788 A1.
  • Older methods use as the catalytically active component usually doped copper chloride (for example, Shell-Chlorine method, Dow-Hercules method), while more modern methods work with precious metals or their oxides and chlorides.
  • the Deacon reaction is exothermic with a standard reaction enthalpy of -57 kJ / mol chlorine. It is reversible. For thermodynamic reasons, low reaction temperatures and excess oxygen are desirable in order to shift the equilibrium position as far as possible in the direction of product formation. This is offset by the desire for the highest possible, technically usable reaction rates, which require temperatures above 300 0 C on the known catalysts. At these temperatures, the Deacon equilibrium is no longer completely on the product side. From the known thermodynamic data of the Deacon reaction can be calculated that at 350 0 C reaction temperature, 0.1 MPa gas pressure and a stoichiometric Eduktdream of four parts HCl to one part of oxygen, a maximum HCl conversion rate of 85% can be achieved.
  • SU A 1 801 943 describes a process for HCl oxidation with air in an electrical pulse discharge (10 to 40 kV peak voltage) at 20 to 30 ° C. With a residence time of up to 140 s in the discharge zone, HCl conversion rates up to 74% are achieved.
  • the patent does not contain information on the discharge arrangement used and the specific energy consumption. The inventors emphasize the absence of a catalyst as an essential feature of their process. From the embodiments of the invention it appears that the dew point of the water of reaction in the product mixture is exceeded. This inevitably leads to the formation of water films on the reactor walls, which ultimately lead to an unstable discharge behavior (sparkover). How the condensation of the water of reaction in the discharge reactor at 20 to 30 0 C can be avoided is not described.
  • EP 1914199 describes a process for the production of chlorine from a gaseous hydrogen chloride and oxygen-containing mixture under the action of ultraviolet radiation, at a wavelength in the range of 165 nm to 270 nm at a density of ultraviolet radiation of (10-40) 10 -4 W / cm 3 and a pressure of not more than 0.1 MPa.
  • the oxygen may be activated upon exposure to a current of accelerated electrons having an energy of 100 keV to 2 MeV.
  • the oxidation of the hydrogen chloride is carried out by the activated oxygen to form the target product.
  • WO2008002197 describes a method for the production of chlorine, in which a gaseous hydrogen chloride and oxygen mixture is transferred at a pressure of 1.1 to 5.0 bar under the action of electrical pulse discharge in a low-temperature plasma, in which hydrogen chloride is oxidized by oxygen. The oxidation product is separated after condensation of the water contained.
  • Van Drumpt et al. (1972) describe HCl oxidation in a modified Siemens tube at atmospheric pressure. It was possible to convert up to 6% of hydrogen chloride into chlorine. These are by far too low degrees of implementation for a sensible technical application.
  • EP1914199 describes a process for the production of chlorine from a gaseous hydrogen chloride and oxygen-containing mixture under the action of ultraviolet radiation, at a wavelength in the range from 165 nm to 270 nm at a density of ultraviolet radiation of (10-40) 10 -4 W / cm 3 and a pressure of not more than 0.1 MPa.
  • the oxygen may be activated upon exposure to a current of accelerated electrons having an energy of 100 keV to 2 MeV.
  • the oxidation of the hydrogen chloride is carried out by the activated oxygen to form the target product. It Almost quantitative degrees of implementation are asserted without there being any heating of the product mixture. It is not mentioned which energy expenditure is necessary for the excitation sources (UV or electrons) to achieve the stated degrees of conversion.
  • the main reaction path is via excited (individual) oxygen atoms, ozone is only mentioned as a by-product of the oxygen excitation.
  • WO2008002197 describes a method for the production of chlorine, in which a gaseous hydrogen chloride and oxygen mixture is transferred at a pressure of 1.1 to 5.0 bar under the action of electrical pulse discharge in a low-temperature plasma, in which hydrogen chloride is oxidized by oxygen. The oxidation product is separated after condensation of the water contained.
  • the document DE 10 2006 022 761 A1 describes an integrated process for the preparation of isocyanates from phosgene and at least one amine and oxidation of the resulting hydrogen chloride with oxygen to chlorine, wherein the chlorine is recycled to produce the phosgene.
  • processes for the production of chlorine by non-thermally activated reaction of hydrogen chloride with oxygen, in which from the resulting gas mixture in the reaction consisting at least of the target products of chlorine and water, unreacted hydrogen chloride and oxygen and optionally other minor components such as carbon dioxide and Nitrogen chlorine is removed and recycled into the phosgene production.
  • a particular disadvantage of the methods that operate using electron excitation is that stable operation of HCl oxidation is not possible with condensation of water.
  • the UV excitation is expected to be a continuous reduction in sales for the duration of the reaction.
  • the object of the present invention is therefore to provide a method for recycling hydrogen chloride to chlorine, which can be operated simply, safely and energy-efficiently.
  • very high degrees of hydrogen chloride conversion should be achieved, so as to simplify the work-up of the reaction products.
  • the invention relates to a process for the heterogeneously catalyzed oxidation of hydrogen chloride by means of oxygen-containing gases, characterized in that a gas mixture consisting at least of hydrogen chloride and oxygen flows through a suitable solid catalyst and simultaneously exposed to the action of a non-thermal plasma.
  • a method is used in which the non-thermal plasma is generated by silent electrical discharge.
  • the silent electric discharge is carried out in a barrier reactor with one or more current-limiting dielectric barriers.
  • the individual reactor tubes are designed, for example, as plasma reactors with a cylindrical discharge gap, similar to the Siemens tubes used for ozone generation.
  • the discharge gap is filled with a suitable catalyst in the form of a fixed bed and is continuously flowed through by the reaction mixture (hydrogen chloride, oxygen, chlorine, water vapor). Any number of these reactors can be connected in parallel to produce sufficient plant capacity.
  • the reaction mixture hydrogen chloride, oxygen, chlorine, water vapor.
  • the reaction temperature can be varied within a wide range. It should preferably be kept above the dew point of the product mixture at the reactor outlet (about 100 ° C.) in order to avoid condensate formation in the reactor.
  • a further preferred embodiment of the new method is therefore characterized in that the plasma-assisted HCl oxidation is carried out in a reactor having a tube with inner and outer electrodes.
  • a reactor having a tube with inner and outer electrodes.
  • Such a reactor is also referred to as a plasma reactor, wherein the electrodes are designed corrosion-protected, in particular with respect to the process gases are.
  • a barrier reactor is a plasma reactor in which the plasma is generated by a barrier discharge.
  • a further embodiment variant of the novel process is characterized in that the plasma-assisted HCl oxidation is carried out in a plurality of parallel-connected reactors in a tube bundle arrangement or parallel plate reactors.
  • the plasma-assisted HCl oxidation is carried out in particular at elevated pressure, preferably at a pressure of up to 25 bar, more preferably 5 to 25 bar.
  • the reaction temperature in the plasma-activated HCl oxidation can be set below about 300 0 C.
  • the HCl conversion is determined by the plasma-chemical activation of the reactants and their synergistic reaction on the catalyst.
  • the homogeneous plasma-activated HCl oxidation in the gas space of the catalyst bed contributes to the total sales.
  • the total conversion in the presence of the catalyst is always higher than that in the empty discharge tubes under the same external discharge conditions, ie the same applied high voltage.
  • reaction temperature of the HCl oxidation in the plasma in a range up to 300 0 C, preferably from 120 to 250 0 C, preferably 130 to 200 0 C is set.
  • a method is also preferred in which the plasma-assisted HCl oxidation is combined with a catalyzed HCl oxidation reaction and is carried out in a reaction space.
  • the reaction temperature of the combined plasma-supported and catalyzed HCl oxidation is set in a range of at least 300 ° C., preferably from 320 to 450 ° C., preferably 350 to 400 ° C.
  • thermodynamic conversion limits specified in the catalyzed process by using reactors connected in series, which operate on different activation principles.
  • a catalyzed process at high temperatures eg, 38O 0 C
  • a certain HCl conversion> 50% is achieved.
  • the product mixture leaving the process is released Temperatures below 300 0 C cooled and passed through a plasma reactor.
  • HCl conversion very high total HCl conversion levels can be achieved in the manner described, the catalyzed activation contributing the major part to the HCl conversion, while the plasma activation brings about the desired, very high overall conversion up to almost 100%.
  • the plasma-assisted HCl oxidation is combined with a catalyzed HCl oxidation reaction and is carried out in separate reaction spaces, wherein the plasma-assisted HCl oxidation is followed by the catalyzed HCl oxidation reaction.
  • a particularly preferred variant of the aforementioned method is characterized in that first the main portion of the HCl oxidation is achieved in particular up to a HCl conversion of at least 70%, preferably at least 80% in the catalyzed oxidation process, which is followed by the plasma-assisted HCl oxidation.
  • a tubular reactor with cylindrically symmetrical inner and outer electrodes is used. Between them there is at least one barrier (e.g., ceramic material) which prevents a direct breakdown of electrical discharge. There may also be multiple barriers, e.g. used in front of each electrode. Between both electrodes, a discharge gap (dielectric, plasma space) with a typical thickness of a few millimeters is formed, in which the catalyst is arranged in an optimum particle size as a packed bed. To generate the plasma, an alternating electrical voltage (for example 5 to 50 kV) is applied between the two electrodes.
  • alternating electrical voltage for example 5 to 50 kV
  • This high voltage can be applied as a low frequency sinusoidal voltage (e.g., 50 Hz) or as a short pulse duration pulsed voltage (e.g., in the micro or nanosecond range) and higher in frequency (e.g., in the kHz or MHz range).
  • the packed bed between the high-voltage electrodes is not only catalytically active, it can also significantly influence the discharge characteristics by its dielectric properties (plasma physical effect).
  • the applied high voltage in a range of 5 to 50 kV, preferably 20 to 30 kV o the active power density, in a range of 50 to 5000 J / l, preferably in the range 200 to 1000 J / l
  • the type of applied AC voltage either in sinusoidal form with a frequency of 50 or 60 Hz or as a pulsed high voltage with a pulse frequency in the range of 50 Hz to 50 kHz, preferably 1 to 5 kHz, and a pulse rise time of 5 to 5000 ns, preferably from 100 to 1000 ns
  • o the reduced field strength (measured in Townsend [Td]) should be adjusted in a range of 200 to 600 Td, preferably 350 to 500 Td.
  • the discharge gap should have a thickness of 1 to 50 mm, preferably 3 to 10 mm.
  • High Dielectric Constant Barrier Materials e.g. Ferroelectric ceramics, the generation of very high field strengths.
  • the thickness of the barriers is in the range of about 0.1 to 5 mm, preferably in the range between 0.5 and 2 mm.
  • a particular embodiment uses solids with ferroelectric properties (eg barium titanate) as constituents of the packed bed or as a catalyst support.
  • ferroelectric properties eg barium titanate
  • the electrical barrier or the electrical barriers are simultaneously used as a catalyst carrier.
  • a porous or rough barrier material is coated with the catalytically active components.
  • a particular advantage of this embodiment lies in the fact that compared to the flow through the catalyst bed a lower flow resistance. This allows smaller gap widths and thus higher electric field strengths in the plasma zone.
  • the silent electric discharge is carried out in a barrier reactor having one or more current-limiting dielectric barriers whose barrier or barriers simultaneously serve as carriers for the catalyst.
  • Such a method is particularly preferred when the silent electrical discharge in a barrier reactor with a ferroelectric barrier material, in particular based on
  • Barium titanate is performed.
  • other ferroelectrics can also be used.
  • heterogeneous catalysts for the plasma enhanced Deacon reaction a variety of solids have been found to be effective. Depending on the temperature range used, they preferably contain oxides, oxide chlorides or chlorides of the metals of Groups 1, 7 and 8 of the Periodic Table which are dispersed in finely divided form on porous support materials, e.g. Titanium dioxide, are applied.
  • Another effective catalyst consists of these catalytically active compounds on ferroelectric support materials, whereby several mechanisms of action - the chemical catalysis and a plasma-physical effect (the amplification of the plasma intensity) - can be advantageously combined.
  • the catalyst which is preferably used in the new process has as catalytic active components metals of the 1st, 7th or 8th subgroup of the Periodic Table of the Elements or oxides, oxide chlorides or chlorides of the metals of the 1st, 7th or 8th subgroup, or Mixtures of these metals or metal compounds.
  • the catalyst is particularly preferably selected from the series: ruthenium oxide, ruthenium chloride, ruthenium oxychloride or other ruthenium compounds on silica, alumina, titania, tin dioxide or zirconium dioxide as support.
  • the novel plasma-assisted HCl oxidation is particularly preferably used in combination with the catalyzed HCl oxidation with molecular oxygen which is also known as the Deacon process and which is operated in an upstream step or simultaneously.
  • hydrogen chloride is oxidized with oxygen in an exothermic equilibrium reaction to chlorine, whereby water vapor is obtained.
  • the reaction temperature is usually 150 to 500 0 C, the usual reaction pressure is 1 to 25 bar. Since it is an equilibrium reaction, it is expedient to work at the lowest possible temperatures at which the catalyst still has sufficient activity.
  • oxygen in excess of stoichiometric amounts of hydrogen chloride. For example, a two- to four-fold excess of oxygen is customary.
  • Suitable preferred catalysts for the Deacon process include ruthenium oxide, ruthenium chloride, ruthenium oxide chloride or other ruthenium compounds supported on silica, alumina, titania, tin dioxide or zirconia. Suitable catalysts can be obtained, for example, by applying ruthenium chloride to the support and then drying or drying and calcining. Suitable catalysts may, in addition to or instead of a ruthenium compound, also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium. Suitable catalysts may further contain chromium (III) oxide.
  • the catalyzed hydrogen chloride oxidation can either adiabatic or isothermal or approximately isothermal, discontinuous, but preferably continuously as flow or
  • Fixed bed process preferably as a fixed bed process, particularly preferably in tube bundle reactors of heterogeneous catalysts at a reactor temperature of 180 to 500 0 C, preferably 200 to
  • 1 to 25 bar 1000 to 25000 hPa
  • 1.2 to 20 bar more preferably 1.5 to 17 bar and in particular 2.0 to 15 bar be performed.
  • Typical reactors in which the catalyzed hydrogen chloride oxidation is carried out are fixed bed or fluidized bed reactors.
  • the catalyzed hydrogen chloride oxidation can preferably also be carried out in multiple stages.
  • Reactors with additional intermediate cooling can be used.
  • the hydrogen chloride can be added either completely together with the oxygen before the first reactor or distributed over the various reactors. This arrangement of individual reactors can also be combined in one apparatus.
  • a further preferred embodiment of a device suitable for the method consists in using a structured catalyst bed in which the catalyst activity increases in the flow direction.
  • Such structuring of the catalyst bed can be done by different impregnation of the catalyst support with active material or by different dilution of the catalyst with an inert material.
  • an inert material for example, rings, cylinders or balls of titanium dioxide, tin dioxide, zirconium dioxide or mixtures thereof, alumina, steatite, ceramic, glass, graphite or stainless steel can be used.
  • the inert material should preferably have similar external dimensions.
  • Suitable shaped catalyst bodies are shaped bodies of any shapes, preference being given to tablets, rings, cylinders, stars, carriage wheels or spheres, rings, cylinders or star strands being particularly preferred as the form.
  • Ruthenium compounds or copper compounds on support materials are particularly suitable as heterogeneous catalysts, preference being given to optionally doped ruthenium catalysts.
  • suitable carrier materials are silicon dioxide, graphite, rutile or anatase titanium dioxide, tin dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, preferably titanium dioxide, tin dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, particularly preferably ⁇ - or ⁇ -aluminum oxide or mixtures thereof ,
  • the copper or ruthenium-supported catalysts can be obtained, for example, by impregnation of the support material with aqueous solutions of CuCl 2 or RuCl 3 and optionally a promoter for doping, preferably in the form of their chlorides.
  • the shaping of the catalyst can take place after or preferably before the impregnation of the support material.
  • the catalysts are suitable as promoters alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, Rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, more preferably lanthanum and cerium, or mixtures thereof.
  • alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, Rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yt
  • the moldings can then be dried at a temperature of 100 to 400 0 C, preferably 100 to 300 0 C, for example, under a nitrogen, argon or air atmosphere and optionally calcined.
  • First C the shaped bodies are preferably dried and subsequently calcined at 200 to 400 0 C at 100 to 15O 0th
  • the aforementioned catalyst systems known for the Deacon process can also be used for the plasma-assisted HCl oxidation.
  • the conversion of hydrogen chloride in a single pass may preferably be limited to 15 to 90%, preferably 40 to 85%, particularly preferably 50 to 70%. Unreacted minor hydrogen chloride residues can be partially or completely recycled to the catalyzed hydrogen chloride oxidation after separation.
  • the volume ratio of Hydrogen chloride to oxygen at the reactor inlet is preferably 1: 1 to 20: 1, preferably 1: 1 to 8: 1, particularly preferably 1: 1 to 5: 1.
  • the separation step usually comprises several stages, namely the separation and optionally the recycling of small residues of unreacted hydrogen chloride from the product gas stream of hydrogen chloride oxidation, the drying of the resulting, essentially chlorine, oxygen and water-containing stream and the separation of chlorine from the dried Electricity.
  • the chlorine produced by the new process is further used in production processes for the production of polymers such as polyurethanes and PVC, which as a by-product provide the hydrogen chloride for the new oxidation process.
  • Another object of the invention is a barrier reactor with one or more current-limiting dielectric barriers, in particular for the oxidation of hydrogen chloride by means of oxygen-containing gases, characterized in that in the discharge gap of the barrier reactor catalyst is introduced as a fixed bed.
  • a barrier reactor characterized in that the reactor is designed as a tubular reactor with a tube having inner and outer electrodes, wherein in particular the electrodes are designed to be protected against corrosion by process gases.
  • barrier reactor in which the reactor is designed in the form of a tube bundle arrangement or several parallel plate reactors.
  • This tubular reactor consisted of a heatable outer tube and an inner tube. The wall thickness of outer and inner tube was about 1 mm.
  • the outer tube was steamed with a metal mirror.
  • the inner tube was cohesively filled by a copper tube.
  • the metal sheath functioning as an outer electrode was connected to the ground potential of a high voltage generator.
  • the copper inner tube was connected to the high voltage output of the generator. Between both electrodes a pulsed high voltage with variable amplitude and pulse frequency was applied.
  • AC pulses were applied with a peak voltage of 30 kV, a frequency of 600 Hz and a pulse duration of approximately 10 ⁇ s.
  • the gap between outer and inner glass tube (gap width 3 mm) was filled with rod-shaped catalyst (about 10 cm 3 , L xd (the rods) "2 mm x 1 mm, 1 wt .-% RuO 2 on TiO 2 ).
  • the reactor temperature was adjusted to 150 0 C. At the reactor exit was a cooled condensate separator.
  • the catalyst-filled annular gap was flowed through by 50 ml / min of a gas stream which consisted in equal parts of hydrogen chloride and oxygen. At the outlet of the reactor gas samples were taken and their chlorine content (absorption at 330 nm) was analyzed photometrically. When the high voltage was switched off, no significant chlorine content ( ⁇ 0.2% by volume) in the product gas could be measured. After switching on the high voltage and stabilizing the plasma, 20% by volume of chlorine in the product gas was measured. This concentration corresponds to a degree of HCl conversion of 63%.
  • Example 2 shows that even under the experimental conditions used, a homogeneous plasma leads to significant HCl oxidation.
  • the introduction of a catalyst significantly enhances this effect.
  • the catalyst without plasma is not active under the reaction conditions used (150 0 C).
  • Example 1 The experimental conditions described in Example 1 were changed so that the plasma reactor was operated at a temperature of 350 ° C. Under these conditions, the catalyzed process is already activated. When the plasma voltage was switched off, a chlorine concentration of 28.5% by volume was measured in the cooled product gas. This value corresponds to 80% HCl conversion. After switching on and stabilizing the plasma, the chlorine concentration increased to 34% by volume, which corresponds to an HCl conversion rate of about 90%.
  • the example shows that under the conditions of a catalyzed HCl oxidation, a significant increase in the chlorine yield by switching on the plasma is possible.
  • Example 1 The experimental setup described in Example 1 was extended by connecting two reactors of the same type in series.
  • the first reactor was operated under the experimental conditions described in Example 2 (350 ° C, without condensate) without plasma assistance.
  • the second reactor was operated under the conditions described in Example 1 (15O 0 C) with the product gas from reactor 1 as input gas. Both reactors were connected by a heated to 120 0 C PTFE tube.
  • reactor 2 was operated without plasma.
  • a chlorine concentration of 28.5% by volume was measured (corresponds to 80% HCl conversion).
  • the chlorine concentration increased to 38% by volume, which corresponds to an HCl conversion rate of about 97%.
  • the example shows that very high levels of HCl conversion can be achieved by connecting catalyzed and plasma-activated oxidation in series.
  • Example 1 The experimental setup described in Example 1 was modified such that the discharge gap, instead of rod-shaped catalyst (about 1% by weight of RuO 2 on TiO 2 ), with a fine-grained mixture of this catalyst having dielectric properties and barium titanate particles ferroelectric material which is catalytically inactive for the HCl oxidation was filled. Both components were mixed as sieved grain fraction (0.5 to 1 mm) in a mass ratio of 1: 1 and filled in the annular gap. Among the in Example 1 described experimentally measured 26 vol .-% chlorine in the cooled reaction gas. This corresponds to a degree of HCl conversion of 75%.
  • the example shows that a mixture of catalytically active dielectric and catalytically inactive ferroelectric particles has a positive overall effect on the plasma-activated oxidation of HCl.
  • Example 4 The experiment described in Example 4 was modified such that the annular gap of the reactor was filled solely with ferroelectric material which was used as carrier for a catalytically active component.
  • barium titanate particle fraction 0.5 to 1 mm
  • ruthenium acetate coated about 0.5 wt .-% Ru
  • HCl conversion rate approximately 45%.
  • the example shows that the special plasma-physical properties of ferroelectric materials can be exploited for plasma-activated HCl oxidation.
  • the inner electrode of the reactor described in Example 1 was modified in the following manner: The smooth glass tube functioning as an inner barrier was replaced by a tube of porous, ceramic material with an outer diameter of 12 mm and a wall thickness of 2 mm. The free gap width thereby reduced to about 1 mm.
  • the outer wall of the ceramic tube was wet-impregnated with ruthenium acetate (about 0.3 mg Ru per cm 2 of the geometric surface).
  • the barrier tube was installed in the reactor and the experimental conditions described in Example 1 were established. Without active plasma, no significant chlorine concentrations ( ⁇ 0.2% by volume) were measured in the product gas. After switching on and stabilizing the plasma, 11.8% by volume of chlorine was measured. This value corresponds to an HCl conversion rate of around 40%.
  • the example shows that a significant plasma effect can also be achieved with a catalyst layer on porous barrier material.

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Abstract

L'invention concerne un procédé pour la production de chlore par oxydation catalytique de chlorure d'hydrogène gazeux sous l'action d'un plasma non thermique.
PCT/EP2009/005683 2008-08-16 2009-08-06 Oxydation catalytique de chlorure d'hydrogène avec de l'oxygène dans un plasma non thermique WO2010020345A1 (fr)

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DE102008038032A DE102008038032A1 (de) 2008-08-16 2008-08-16 Katalytische Oxidation von Chlorwasserstoff mit Sauerstoff im nichtthermischen Plasma
DE102008038032.6 2008-08-16

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WO2017194537A1 (fr) * 2016-05-12 2017-11-16 Covestro Deutschland Ag Oxydation photocatalytique de chlorure d'hydrogène avec de l'oxygène
EP3421416A1 (fr) 2017-06-29 2019-01-02 Covestro Deutschland AG Oxydation photocatalytique de chlorure d'hydrogene à l'aide de monoxyde de carbone
EP3670444A1 (fr) 2018-12-18 2020-06-24 Covestro Deutschland AG Oxydation photocatalytique d'acide chlorhydrique à l'aide de l'oxygène

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DE102008063725A1 (de) 2008-12-18 2010-06-24 Bayer Materialscience Ag Katalytische Oxidation von Chlorwasserstoff mit Sauerstoff im nichtthermischen Plasma

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WO2017194537A1 (fr) * 2016-05-12 2017-11-16 Covestro Deutschland Ag Oxydation photocatalytique de chlorure d'hydrogène avec de l'oxygène
CN109071219A (zh) * 2016-05-12 2018-12-21 科思创德国股份有限公司 使用氧气的氯化氢光催化氧化
EP3421416A1 (fr) 2017-06-29 2019-01-02 Covestro Deutschland AG Oxydation photocatalytique de chlorure d'hydrogene à l'aide de monoxyde de carbone
EP3670444A1 (fr) 2018-12-18 2020-06-24 Covestro Deutschland AG Oxydation photocatalytique d'acide chlorhydrique à l'aide de l'oxygène
WO2020127022A1 (fr) 2018-12-18 2020-06-25 Covestro Intellectual Property Gmbh & Co. Kg Oxydation photocatalytique d'acide chlorhydrique avec de l'oxygène

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