EP3624939A1 - Procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, contaminé - Google Patents

Procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, contaminé

Info

Publication number
EP3624939A1
EP3624939A1 EP18726095.5A EP18726095A EP3624939A1 EP 3624939 A1 EP3624939 A1 EP 3624939A1 EP 18726095 A EP18726095 A EP 18726095A EP 3624939 A1 EP3624939 A1 EP 3624939A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
ruthenium
regeneration
oxidative
sulfur
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.)
Pending
Application number
EP18726095.5A
Other languages
German (de)
English (en)
Inventor
Andre Rittermeier
Michael Venz
Thomas Burbach
Timm Schmidt
Tim Loddenkemper
Frank Gerhartz
Walther M LLER
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3624939A1 publication Critical patent/EP3624939A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/10—Chlorides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the reaction with sulfur compounds in catalysts containing ruthenium or ruthenium compounds leads in many typical applications to an irreversible reduction in activity which is commonly thought to be due to poisoning.
  • the present invention relates to a process by which the sulfur content of a catalyst containing sulfur in the form of sulfur compounds, ruthenium or ruthenium compounds can be reduced by targeted treatment with a hydrogen chloride-containing stream under non-oxidative conditions that its activity on the activity of a similar catalyst increases, which is not poisoned with sulfur in the form of sulfur compounds.
  • the catalyst is subjected to oxidative post-treatment.
  • the success of this regeneration is exemplified by the catalytic oxidation of hydrogen chloride with oxygen and the oxidation of carbon monoxide with oxygen.
  • a typical field of application for a catalyst containing ruthenium or ruthenium compounds is the production of chlorine by gas phase oxidation of hydrogen chloride with oxygen:
  • This reaction is an equilibrium reaction.
  • the position of the equilibrium shifts with increasing temperature to the detriment of the desired end product. It is therefore advantageous to use catalysts with the highest possible activity, which allow the reaction to proceed at low temperature.
  • the first catalysts for the hydrogen chloride oxidation contained as active component copper chloride or oxide and were already described in 1868 by Deacon. However, they had low activity at low temperature ( ⁇ 400 ° C). Although their activity could be increased by increasing the reaction temperature, it was disadvantageous that the volatility of the active components led to rapid deactivation.
  • Titanium dioxide whose application is described, for example, in the application EP 743277 A1 and tin dioxide whose use is known, for example, from the application DE 10 2006 024 543 A1, appears to be particularly suitable as a support.
  • a sulfur load in the input stream can, for. B. by sulfur-containing raw materials (eg petroleum fractions, natural gas, coal) or upstream processes (eg gas drying with sulfuric acid, sulfur-containing activated carbon) be imprinted. From WO 2007 066 810 AI is z. B. it is known that it foxidation for the lifetime of a ruthenium or ruthenium-containing catalyst for the Chlorwas sVaccino f is crucial to lower the sulfur load in the input stream below 2 ppm. In order to reduce the sulfur load, various oxides are described in this application, on which sulfur components are deposited by reactive means.
  • a disadvantage of this method is that volatile chlorides of these elements can be carried over to the catalyst or peak load in the sulfur load can lead to breakthrough of sulfur compounds.
  • Processes for the regeneration of catalysts containing sulfur in the form of sulfur compounds and containing ruthenium or ruthenium compounds have already been described, but they have many disadvantages. It is known from GB 744 049 A that catalysts containing sulfur in the form of sulfur compounds and containing ruthenium or ruthenium compounds can be regenerated by a wash.
  • the washing liquid are mentioned water, ethanol, acetic acid, cyclohexene, benzene and acetone.
  • a laundry always carries the risk that some of the active components will be discharged with the washing liquid. This can be done both by chemical-physical processes (eg reaction + absorption, solubility) and by mechanical processes (eg abrasion).
  • the catalyst for a laundry must be removed from the reactor used for the target reaction usually.
  • GB 1 278 119 A describes the regeneration of a catalyst containing sulfur in the form of sulfur compounds and containing ruthenium or ruthenium compounds by reducing treatment with an anhydrous hydrogen stream at 430 to 595 ° C., a pressure between 3 and 24 bar and a few other oxidation states. and reduction steps.
  • Such a combination of reducing conditions and high temperatures will lead to a substantial reduction of ruthenium oxides (if present) to metallic ruthenium down to deeper layers.
  • This treatment will subject the catalyst containing ruthenium or ruthenium compounds to drastic changes, which may be undesirable for some applications.
  • pressure-resistant reactors, pipelines and valves must be available for this application, which is why the catalyst for this treatment would normally have to be expanded.
  • US Pat. No. 4,851,380 A describes a process for the regeneration of carbon- and sulfur-contaminated monofunctional, large-pore zeolite reforming catalysts. Therein, a platinum catalyst first becomes an agglomeration procedure in oxygen-containing gas at 900
  • WO 2009 118 095 A3 describes a process by which the sulfur content of a catalyst containing sulfur in the form of sulfur compounds, containing ruthenium or ruthenium compounds by a specific treatment with a hydrogen chloride stream under non-oxidative conditions can be reduced so that its activity increases to the activity of a similar catalyst that is not poisoned with sulfur in the form of sulfur compounds.
  • the catalyst containing ruthenium or ruthenium compounds is present in chlorinated or superficially chlorinated form in the form of a chlorinated or oxychlorinated ruthenium compound or superficially chlorinated or oxychlorinated ruthenium compound.
  • WO 2010 076 296 A1 describes a process for the regeneration of a hydrogen chloride oxidation catalyst comprising ruthenium oxide on a support material, comprising the steps of a) reducing the catalyst with a gas stream containing hydrogen chloride and optionally an inert gas at a temperature of 100 to 800 ° C., b ) Rekalzinieren the catalyst with an oxygen-containing gas stream at a temperature Tem of 150 to 800 ° C.
  • the chlorinated or superficially chlorinated ruthenium oxide catalyst in step a) is reoxidized, which prevents or at least reduces the formation of volatile ruthenium compounds when the catalyst is restarted under reaction conditions.
  • the object of this invention is therefore to provide a long-term effective, gentle and simple process for the regeneration of a catalyst containing sulfur in the form of sulfur compounds and containing ruthenium or ruthenium compounds.
  • the sulfur content of a catalyst containing sulfur in the form of sulfur compounds and containing ruthenium or ruthenium compounds can be reduced by selective treatment with a halogen gas stream, in particular hydrogen chloride-containing gas stream, under non-oxidative conditions with optionally elevated temperature in that its activity increases to the activity of a similar catalyst which has not been poisoned with sulfur in the form of sulfur compounds.
  • a halogen gas stream in particular hydrogen chloride-containing gas stream
  • a subsequent gentle, oxidative treatment in particular consisting of a first process step, which results from the treatment with a vapor-containing gas stream to a gentle anoxidation of the catalyst and also the sulfur compounds, which after the targeted treatment with a Hydrogen halide, in particular hydrogen chloride-containing gas Ström emerged, removed from the reactor and the subsequent piping and apparatus and a second process step, which consists of a targeted treatment with an oxygen-containing stream whose concentration is preferably increased sequentially, the catalyst carefully, as completely as possible Oxidized, resulting in the long-term success of regeneration.
  • a subsequent gentle, oxidative treatment in particular consisting of a first process step, which results from the treatment with a vapor-containing gas stream to a gentle anoxidation of the catalyst and also the sulfur compounds, which after the targeted treatment with a Hydrogen halide, in particular hydrogen chloride-containing gas Ström emerged, removed from the reactor and the subsequent piping and apparatus and a second process step, which consists of a targeted treatment with an oxygen-containing stream
  • the invention relates to a process for the regeneration of a ruthenium or ruthenium compounds-containing catalyst which is poisoned by sulfur in the form of sulfur compounds, characterized in that the catalyst, optionally at elevated temperature, a treatment with a Halogenwas s réelleo ff,
  • hydrogen chloride-containing gas Ström is subjected to non-oxidative conditions and additionally, optionally at reduced temperature, subjected to at least two-stage oxidative Nachb e Stuttgart, wherein in a first process step, the catalyst by treatment with a vapor-containing gas ström partially oxidized and in a second process step the catalyst is further oxidized, preferably fully oxidized, by treatment with an oxygen-containing gas stream, the oxygen concentration of which is preferably increased sequentially.
  • the term "partially oxidized” is understood to mean, in particular, at least 1% oxidation of the catalyst.
  • further oxidation means in particular an oxidation of the catalyst lying above the degree of oxidation of the first oxidative regeneration stage.
  • completely oxidized means, in particular, a 100% oxidation of the catalyst.
  • ruthenium halides in particular ruthenium chlorides, ruthenium oxyhalides, in particular ruthenium oxychlorides, or ruthenium oxides which may be present singly or in a mixture, hydrogen chloride being preferably used for the regeneration of the chlorine-containing ruthenium compounds for regeneration.
  • a small side stream is separated from the main stream to be fed in order to determine the loss of activity and passed through a separate catalyst bed with the same catalyst material, in which a differential conversion is achieved by suitable choice of the contact time.
  • a small portion of the catalyst containing ruthenium or ruthenium compounds (operating catalyst) removed from the reactor transferred to a separate catalyst bed and determined by a model reaction by suitable choice of the contact time of loss of activity in the differential range of sales.
  • Sulfur compounds which can poison (deactivate) catalysts containing ruthenium or ruthenium compounds are preferably one or more compounds selected from the series: H.-SO.,. H 2 S0 3 , S0 3 , S0 2 , SOCl 2 , SC1 2 , S 2 C1 2 , CS 2 , COS, II S and salts of H 2 S0 4 and II. -SO ;.
  • these sulfur compounds are preferably converted under oxidative conditions into sulfur oxides which are incorporated into the catalyst surface, preferably via bridging oxygen or sulfur-metal bonds. Under reducing conditions, the sulfur is preferably incorporated into the catalyst surface via sulfur metal compounds.
  • the sulfur immobilized by the reaction at the catalyst surface can be converted again into volatile sulfur compounds in the form of sulfur compounds, which can be removed from the catalyst surface.
  • the non-oxidative regeneration is carried out under elevated temperature, which is understood to mean the treatment at a temperature above the ambient temperature.
  • the non-oxidative regeneration is carried out in particular at a temperature up to 600 ° C.
  • the regeneration is carried out at a temperature of 200 ° C to 500 ° C, in a particularly preferred embodiment at a temperature of 300 ° C to 450 ° C.
  • the regeneration stream in the non-oxidative process step contains hydrogen halide, preferably hydrogen chloride, the hydrogen halide content preferably being 0.1 to 100% by volume.
  • the halogen content of the regeneration stream is from 1 to 30% by volume, particularly preferably from 5 to 25% by volume.
  • Other constituents of the regeneration stream may in particular be inert gases, e.g. Be nitrogen or argon.
  • the elemental hydrogen halide may also be replaced by substances or substanzmis chungen, the hydrogen halide, i. in particular chlorine, fluorine, bromine, or hydrogen iodide under the described regeneration conditions release or substances or mixtures of substances whose hydrogen and halogen functions achieve a comparable effect as elemental hydrogen halide under the described regeneration conditions.
  • phosgene is mentioned here.
  • Non-oxidative conditions or non-oxidative regeneration are understood here to mean the treatment of the catalyst in a regeneration gas stream which, in particular, has as few oxidizing components as possible.
  • the non-oxidative regeneration gas stream contains only a small amount of oxygen, i. in particular at most 1% by volume, preferably at most 0.2% by volume, particularly preferably at most 0.1% by volume of oxygen.
  • the regeneration stream contains no oxygen.
  • the regeneration period of the first stage is preferably 0.5 hour to 100 hours.
  • the optimal regeneration period depends in particular on the sulfur loading, the regeneration temperature and the content of hydrogen chloride in the regeneration flow.
  • the regeneration can take place either in one step or at several intervals.
  • the regeneration preferably takes place at intervals, the sulfur content and / or the activity of the catalyst being determined between the time intervals.
  • the oxidative regeneration or oxidative treatment is carried out under reduced temperature, which is understood to mean the treatment at a temperature below the temperature of the non-oxidative regeneration of the first process step.
  • the oxidative aftertreatment is carried out independently of the first stage, in particular at a temperature of up to 600.degree. In a preferred embodiment, the oxidative after-treatment is carried out at a temperature of 200 ° C to 500 ° C, in a particularly preferred embodiment at a temperature of 200 ° C to 400 ° C.
  • oxidative treatment is understood to mean the aftertreatment of the catalyst in a regeneration stream which contains oxidizing gases (eg oxygen, steam, N 2 O).
  • oxidizing gases eg oxygen, steam, N 2 O.
  • the gas Ström of the first process step of the oxidative after-treatment contains steam, wherein the steam content is preferably 0.1 to 100 vol .-%. In a preferred embodiment, the steam content is 20 to 80% by volume, more preferably 40 to 60% by volume.
  • Other components of the gas stream may in particular be inert gases, e.g. Be nitrogen or argon.
  • the steam can also be replaced by substances or substances which achieve a comparable effect as steam under the conditions described. By way of example, nitrous oxide (N 2 O) is mentioned here.
  • the gas flow of the first process step of the oxidative after-treatment contains only a small amount of oxygen in the form of O 2, i. in particular at most 1% by volume, preferably at most 0.2% by volume, particularly preferably at most 0.1% by volume of oxygen.
  • the gas Ström of the first process step of the oxidative after-treatment contains no oxygen.
  • the duration of the first process step of the oxidative after-treatment is preferably 0.1 hours to 100 hours. In an unnecessarily long first process step, the ruthenium content of the catalyst can be reduced by leaching unwanted.
  • the optimal duration The first process step of the post-treatment depends in particular on the sulfur loading, the amount of removed sulfur from the catalyst, the total amount of catalyst and the proportion of chlorinated or oxychlorinated ruthenium compounds or superficially chlorinated or oxychlorinated ruthenium compounds.
  • the first process step of the aftertreatment can take place either in one step or at several intervals.
  • the gas Ström of the second process step of the oxidative Nachb emaschine contains oxygen (O2), wherein the oxygen content is preferably 0.1 to 100 vol .-%. In a preferred embodiment, the oxygen content is 20 to 80% by volume, particularly preferably 40 to 60% by volume.
  • the oxygen content is preferably increased continuously or sequentially, more preferably sequentially, during the second process step. When increasing sequentially, this increase in the oxygen content can take place in any number of steps, preferably in 2 to 10 steps, particularly preferably in 2 to 5 steps.
  • Other components of the gas stream may in particular be inert gases, e.g. Be nitrogen or argon.
  • the gas stream of the second process step of aftertreatment contains only a small proportion of chlorine in the form of HCl or CI2, i. in particular at most 1% by volume, preferably at most 0.2% by volume, particularly preferably at most 0.1% by volume of chlorine.
  • the gas stream of the second process step of the Nachb e Stuttgart neither HCl nor CI2.
  • the same conditions HCl and Cl 2 content
  • the duration of the second process step of the aftertreatment is preferably 0.1 hours to 100 hours.
  • the optimum duration of the second process step of the post-treatment depends in particular on the total amount of catalyst and the proportion of chlorinated or oxychlorinated ruthenium compounds or superficially chlorinated or oxychlorinated ruthenium compounds.
  • the second process step of the post-treatment can take place either in one step or at several intervals.
  • the gases which can generally be used for post-treatment often contain impurities (of the order of magnitude of ⁇ 1000 ppm), for example, for technical reasons.
  • impurities e.g., sulfur in the form of sulfur compounds
  • Disturbing impurities are usefully removed from the regeneration gas beforehand.
  • the catalyst remains in the reactor during regeneration, in which the catalytic target reaction (in particular the catalytic gas phase oxidation of HCl) is or was carried out.
  • the regeneration is carried out in countercurrent to the gas flow direction of the reaction gases of the stated target reaction in order to avoid carryover of discharged sulfur components to weakly or non-poisoned catalyst layers.
  • a preferred application is the regeneration of catalysts containing ruthenium or ruthenium compounds for the catalyzed gas phase oxidation of chlorine gas with oxygen, since in this case the required apparatus environment for handling hydrogen chloride is already present and the catalyst must withstand during the reaction of a hydrogen chloride atmosphere.
  • a preferred application is the regeneration of catalysts whose active component consists mainly of supported ruthenium or ruthenium compounds.
  • a particularly preferred application is the regeneration of catalysts containing ruthenium or ruthenium compounds, whose support mainly has a rutile structure.
  • Another particularly preferred application is the regeneration of ruthenium or ruthenium-containing catalysts whose supports contain titanium dioxide, aluminum oxide, zirconium oxide or tin dioxide or mixtures thereof.
  • a preferred application is catalyst regeneration in the context of a multi-step process for isocyanate production, including catalyzed hydrogen chloride oxidation, whose individual process steps are e.g. B. are known in principle from EP 1867631 AI.
  • the novel process is preferably combined with the catalytic gas phase oxidation process known as the Deacon process.
  • 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 ° C, the usual reaction pressure is 1 to 25 bar. Since it is a light-weighting reaction, it is expedient to work at as low temperatures as possible 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. Since no loss of selectivity is to be feared, it may be economically advantageous to work at relatively high pressure and, accordingly, longer residence time than normal pressure.
  • the catalytic hydrogen chloride oxidation can be adiabatic or preferably isothermal or approximately isothermal, batchwise, but preferably continuously or as a fixed bed process, preferably as a fixed bed process, more preferably in tube bundle reactors to heterogeneous catalysts at a reactor temperature of 180 to 500 ° C. 200 to 400 ° C, more preferably 220 to 350 ° C and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, more preferably 1.5 to 17 bar and in particular 2.0 to 15 bar are carried out.
  • catalytic hydrogen chloride oxidation is carried out are fixed bed or fluidized bed reactors.
  • the catalytic hydrogen chloride oxidation can preferably also be carried out in several stages.
  • the conversion of Chlorwas s er sto ff in a single pass may preferably be limited to 15 to 90%, preferably 40 to 90%, particularly preferably 50 to 90%.
  • unreacted hydrogen chloride can be partly or completely recycled to the catalytic hydrogen chloride oxidation.
  • a plurality of reactors with additional intermediate cooling that is to say 2 to 10, preferably 2 to 6, more preferably 2 to 5, in particular 2 to 3, connected in series.
  • the chlorine gas can either be added completely together with the oxygen before the first reactor or distributed over the various reactors.
  • This series connection of individual reactors can also be combined in one apparatus.
  • a preferred purification method for the catalyst can be realized particularly simply as an in situ process by taking a reactor of the reactor cascade from the Deacon process and subjecting the catalyst contained therein to the regeneration according to the invention.
  • Vorrich- Hing is that one uses a structured catalyst packing, in which the catalyst activity increases in the flow direction.
  • Such structuring of the catalyst charge can be effected 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, 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 preferred catalysts for the Deacon process include ruthenium oxides, ruthenium chlorides or other ruthenium compounds.
  • Suitable support materials are, for example, silicon dioxide, graphite, titanium dioxide having a rutile or anatase structure, zirconium oxide, aluminum oxide or mixtures thereof, preferably titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, particularly preferably ⁇ - or ⁇ -aluminum oxide or mixtures thereof.
  • Suitable catalysts can be obtained, for example, by applying ruthenium (III) chloride to the support and then drying or drying and calcining.
  • suitable catalysts may 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 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, more 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, more preferably Magnesium, rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably
  • Suitable shaped catalyst bodies are shaped bodies with any desired shapes, preference being given to tablets, rings, cylinders, stars, carriage wheels or spheres, particular preference being given to rings, cylinders or star strands as molds.
  • the shaped bodies can then be dried at a temperature of 100 to 400 ° C., preferably 100 to 300 ° C., for example under a nitrogen, argon or air atmosphere, and optionally calcined.
  • the moldings are first dried at 100 to 150 ° C and then calcined at 200 to 400 ° C.
  • Example 1a 200 g of SnC pellets (spherical, diameter about 1.9 mm, Alfa Aesar) were impregnated with a solution of 9.99 g of ruthenium chloride n-hydrate in 33.96 ml of ILO and then mixed for 1 h. The moist solid was then dried at 60 ° C in a muffle furnace (air) for 4 h and then calcined for 16 h at 250 ° C.
  • Example lb 100 g TiC pellets (cylindrical, diameter about 2 mm, length 2 to 10 mm, Saint-Gobain) were impregnated with a solution of ruthenium chloride n-hydrate in H 2 O, so that the theoretical Ru content 3 wt .-% amounted to.
  • the moist pellets thus obtained were dried overnight at 60 ° C and introduced in a dry state under a nitrogen purge in a solution of NaOH and 25% hydrazine hydrate in water and allowed to stand for 1 h. Excess water was then evaporated.
  • the moist pellets were dried for 2 h at 60 ° C and then washed with 4x 300 g of water.
  • the moist pellets thus obtained were in the muffle furnace (air) for 20 min. dried at 120 ° C and then calcined for 3 h at 350 ° C.
  • Example 2a 0.5 g of the catalyst pellets prepared according to Example la were initially charged in a quartz reaction tube (diameter 10 mm) and at 320 ° C. for 24 hours with a gas mixture 1 (consisting of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 40 ppm SO2) flows through.
  • a gas mixture 1 consististing of 2 L / h hydrogen chloride, 1 L / h oxygen, 2 L / h nitrogen and 40 ppm SO2
  • Example 2b 0.5 g of the catalyst pellets prepared according to Example 1b were placed in a quartz reaction tube (diameter 10 mm) and at 320 ° C for 24 hours with a Gas mixture 1 (consisting of 2 L of hydrogen chloride, 1 L / h of oxygen, 2 L / h of nitrogen and 40 ppm SO2) flows through.
  • a Gas mixture 1 consisting of 2 L of hydrogen chloride, 1 L / h of oxygen, 2 L / h of nitrogen and 40 ppm SO2 flows through.
  • Example 2c 19.5 g of a ruthenium-supported catalyst 1c (TiC support) were introduced into a nickel reaction tube (diameter 16 mm) and for more than 20,000 hours at variable temperatures with a gas mixture (consisting of 1 mol / h HCl, 2 mol / h O 2 , 2 mol / h N 2 ), and loaded over this time with an unknown composition and amount of sulfur components.
  • a gas mixture consisting of 1 mol / h HCl, 2 mol / h O 2 , 2 mol / h N 2
  • Example 1 1) on ruthenium-supported catalysts (SnO.-Trägyr and TiO.sub.2 carrier).
  • Example 1 0.5 g of the non-poisoned catalyst pellets with the designation la and in each case 0.5 g of the catalyst pellets poisoned according to Example 2 with the designation 2a, 2b and 2c were placed in a quartz reaction tube (diameter 10 mm) and after heating in nitrogen (non-poisoned) first subjected to an activity test and for it at 320 ° C for 18 hours with a gas mixture 2 (consisting of 2 L / h HCl, 8 L / h O2 and 10 L / h N2) flows through.
  • a gas mixture 2 consististing of 2 L / h HCl, 8 L / h O2 and 10 L / h N2 flows through.
  • Example 4 Applying the regeneration conditions from WO 2010 076 296 A1 (regeneration method 2) to supported ruthenium catalysts (SnC support and TiC support) - Comparative Example
  • the mixtures were flowed through for 12 h at 400 ° C with the gas mixture 6 (consisting of 1, 54 L / h HCl and 1, 54 L / h 2 ). Thereafter, the mixtures for 0.5 h at 400 ° C with the gas mixture 7 (consisting of 3.08 L / h of artificial air: 21% O2, 79% 2) were flowed through / calcined. Subsequently, the temperature in the gas mixture 7 was lowered to 320 ° C and the lungs (laR2, 2aR2, 2bR2, 2cR2) for 24 h with gas mixture 5 (consisting of 2 L / h HCl, 1 L / h O 2 ) flows through and the Activity determined.
  • Example 5 Applying the New Regeneration Conditions (Regeneration Method 3) to Ruthenium Supported Catalysts (SnC Support and TiO 2 Support)
  • gas mixture 9 Consisting of 2 L / h of HC and 6.67 L / h of N 2 .
  • the temperature was lowered under regeneration conditions to 260 ° C and for 4 h with gas mixture 10 (consisting of steam) flows through.
  • the following consecutive, oxidative treatment is carried out at 260 ° C: for 0.5 h gas mixture 11 (consisting of 0.33 L / h O 2 and 2 L h N 2 ), for 0.5 h gas mixture 12 (consisting of 0, 66 L / h O2 and 2 L / h N 2 ), for 1 h gas mixture 13 (consisting of 1.33 L / h O2 and 2 L / h N2), and for 2 h gas mixture 14 (consisting of 2 L / h O2 and 2 L / h N 2 ). Subsequently, the temperature in the gas mixture 8 was increased to 320 ° C.
  • Example 6 Applying the New Regeneration Conditions (Regeneration Method 3) to Ruthenium Supported Catalysts (SnOs Support and TiOa Support)
  • oxidative treatment was carried out at 260 ° C: for 0.5 h gas mixture 1 1 (consisting of 0.33 L h O2 and 2 L / h N2), for 0.5 h gas mixture 12 (consisting of 0.66 L / h O 2 and 2 L / h N 2 ), for 1 h gas mixture 13 (consisting of 1.33 L / h O 2 and 2 L / h N 2 ), and for 2 h gas mixture 14 (consisting of 2 L / h O2 and 2 L / h N 2 ).
  • the temperature in the gas mixture 8 was then increased to 320 ° C.
  • gas mixture 8 (consisting of 2 L / h HCl, 1 L / h O 2 and 2 L / h N 2 ) flows through and determines the activity.
  • Example 7 Applying the regeneration conditions based on WO 2009 1 18 095 A3 (regeneration method 3) to ruthenium carrier catalysts (SnOa carrier and TiO 2 carrier) - comparative apples
  • Regeneration method 1 results in a slight increase in activity (+ 4%) with respect to the poisoned catalyst at a low HCl: O 2 ratio (1: 4) for the freshly prepared and poisoned SnC-supported catalyst (2aRl).
  • the regeneration method 1 leads to a greater increase in activity (+16%) with respect to the poisoned catalyst.
  • the regeneration method 1 leads to a sharp increase in activity (+ 57%) with respect to the poisoned catalyst.
  • the activity increases slightly (+ 7%) in relation to the initial activity according to the regeneration method 1.
  • the regeneration method 1 proves to be a suitable method to regenerate ruthenium-supported catalysts operated and restarted at a low HCl: O 2 ratio (1: 4).
  • Regeneration method 2 leads to a reduction of the activity (-4 to -19%) with respect to the poisoned catalyst and the initial activity in the non-poisoned catalyst in all investigated ruthenium-supported catalysts. Thus, the regeneration method 2 does not prove to be a suitable method to regenerate supported ruthenium catalysts.
  • Example 5
  • the regeneration method 3 in the freshly prepared and poisoned SnO.sub .--supported catalyst (2aR.sub.1) leads to a greater increase in activity (+12%) with respect to the poisoned catalyst.
  • regeneration method 3 leads to a reduction in activity (-11%) with respect to the poisoned catalyst.
  • the regeneration method 3 again leads to a greater increase in the activity (+11%) with respect to the poisoned catalyst.
  • the activity increases more (+15%) in relation to the initial activity according to the regeneration method 3.
  • the regeneration method 3 proves to be a suitable method to regenerate ruthenium-supported catalysts operated and restarted at a high HCl: O 2 ratio (2: 1).
  • the regeneration method 1 and the regeneration method 3 were at high HCl to O; Ratio (2: 1) in terms of sulfur removal and activity compared to regeneration.
  • Ratio (2: 1) in terms of sulfur removal and activity compared to regeneration.
  • the SnC-supported catalyst has absorbed much more sulfur from poisoning (6600 ppm) than the TiC-supported catalyst (820 ppm).
  • the sulfur content in the SnC-supported catalyst has decreased by 600 ppm and in the T1O2-supported catalyst by 220 ppm.
  • the sulfur content in the SnC-supported catalyst decreased by 1300 ppm and in the TiC-supported catalyst by 290 ppm.
  • both regeneration methods are suitable for removing sulfur from the supported ruthenium catalysts, but regeneration method 3 removes a larger amount of sulfur from the catalysts.
  • the regeneration method 3 leads to an activity of 99% based on the initial activity in the non-poisoned catalyst in the SnCV-supported catalyst.
  • regeneration method 3 results in an activity of 89% based on the initial activity in the non-poisoned catalyst.
  • the regeneration method 1 in the SnC-supported catalyst leads only to an activity of 39% based on the initial activity in the non-poisoned catalyst.
  • the regeneration method 1 also leads to an activity of only 3% based on the initial activity in the non-poisoned catalyst.
  • regeneration method 1 is suitable for removing sulfur from ruthenium-supported catalysts and for a low HC! To O 2 ratio to regenerate the catalysts, but this is no longer the case with a high HCl to O 2 ratio.
  • regeneration method 3 is suitable for removing sulfur from supported ruthenium catalysts and for regenerating the catalysts at both a low and a high HCl to O 2 ratio.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, qui est contaminé par des composés de soufre. Dans le procédé, le catalyseur est exposé, éventuellement en présence d'une température élevée, à un traitement avec un halogénure d'hydrogène, en particulier avec un flux de gaz contenant du chlorure d'hydrogène dans des conditions non oxydantes et, en supplément, éventuellement en présence d'une température réduite, à un traitement ultérieur oxydant à au moins deux phases.
EP18726095.5A 2017-05-19 2018-05-14 Procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, contaminé Pending EP3624939A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17172042.8A EP3403723A1 (fr) 2017-05-19 2017-05-19 Procédé de régénération d'un catalyseur contenant du ruthénium contaminé ou des composés de ruthénium
PCT/EP2018/062417 WO2018210770A1 (fr) 2017-05-19 2018-05-14 Procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, contaminé

Publications (1)

Publication Number Publication Date
EP3624939A1 true EP3624939A1 (fr) 2020-03-25

Family

ID=58765718

Family Applications (2)

Application Number Title Priority Date Filing Date
EP17172042.8A Withdrawn EP3403723A1 (fr) 2017-05-19 2017-05-19 Procédé de régénération d'un catalyseur contenant du ruthénium contaminé ou des composés de ruthénium
EP18726095.5A Pending EP3624939A1 (fr) 2017-05-19 2018-05-14 Procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, contaminé

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP17172042.8A Withdrawn EP3403723A1 (fr) 2017-05-19 2017-05-19 Procédé de régénération d'un catalyseur contenant du ruthénium contaminé ou des composés de ruthénium

Country Status (6)

Country Link
US (1) US11389791B2 (fr)
EP (2) EP3403723A1 (fr)
JP (1) JP2020520797A (fr)
KR (1) KR20200010239A (fr)
CN (1) CN110621403B (fr)
WO (1) WO2018210770A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3730202A1 (fr) * 2019-04-26 2020-10-28 Covestro Deutschland AG Procédé de nettoyage de gaz de processus corrosifs contenant du soufre
CN112691706A (zh) * 2020-12-23 2021-04-23 中触媒新材料股份有限公司 一种乙醇制乙腈催化剂的再生方法
JP2023072888A (ja) * 2021-11-15 2023-05-25 住友化学株式会社 亜酸化窒素分解用触媒の再生方法および亜酸化窒素の分解方法
CN115155672A (zh) * 2022-06-24 2022-10-11 西安近代化学研究所 一种氯化氢氧化催化剂的再生方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB744049A (en) 1952-06-27 1956-02-01 Edward Bradford Maxted Revivification of poisoned metallic catalysts
DE1065384B (de) * 1954-09-23 1959-09-17 N. V. De Bataafsche Petroleum Maatschappij, Den Haag Verfahren zur Aktivierung Platin enthaltender Katalysatoren
NL6404460A (fr) 1964-04-23 1965-10-25
US3634292A (en) * 1969-02-06 1972-01-11 Universal Oil Prod Co Regeneration of a coke-deactivated catalyst comprising a combination of platinum rhenium and halogen with an alumina carrier material
GB1278119A (en) 1969-12-02 1972-06-14 Universal Oil Prod Co Regeneration of deactivated catalyst containing a platinum group component and a sulfur component
US4851380A (en) 1986-12-19 1989-07-25 Chevron Research Company Process for regenerating sulfur contaminated reforming catalysts
NO961970L (no) 1995-05-18 1996-11-19 Sumitomo Chemical Co Fremgangsmåte for fremstilling av klor
US7247592B2 (en) 2000-09-18 2007-07-24 Osaka Gas Co., Ltd. Method of activating catalyst for carbon monoxide removal
US7318915B2 (en) 2002-01-25 2008-01-15 United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Oxidation-reduction catalyst and its process of use
JP4507615B2 (ja) * 2004-02-04 2010-07-21 住友化学株式会社 塩素の製造方法
US7718145B2 (en) 2005-04-05 2010-05-18 Mitsui Chemicals, Inc. Polyisocyanate production system and gas treatment apparatus
JP4367381B2 (ja) * 2005-06-29 2009-11-18 住友化学株式会社 塩素製造用触媒の賦活方法及び塩素の製造方法
CN101316656A (zh) * 2005-11-30 2008-12-03 住友化学株式会社 担载钌的制造方法和氯的制造方法
JP4785515B2 (ja) 2005-12-08 2011-10-05 住友化学株式会社 塩素の製造方法
US20100303710A1 (en) 2005-12-08 2010-12-02 Sumitomo Chemical Company, Limited Process for producing chlorine
DE102006024543A1 (de) 2006-05-23 2007-11-29 Bayer Materialscience Ag Verfahren zur Herstellung von Chlor durch Gasphasenoxidation
DE102008015406A1 (de) * 2008-03-22 2009-09-24 Bayer Materialscience Ag Verfahren zur Regeneration eines mit Schwefel in Form von Schwefelverbindungen vergifteten, Ruthenium oder Rutheniumverbindungen enthaltenden Katalysators
JP5642706B2 (ja) * 2008-12-30 2014-12-17 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 塩化水素の酸化用のルテニウム及びニッケル含有触媒
PL2384239T3 (pl) * 2008-12-30 2013-04-30 Basf Se Sposób regeneracji zawierającego tlenek rutenu katalizatora utleniania chlorowodoru

Also Published As

Publication number Publication date
US20210154657A1 (en) 2021-05-27
EP3403723A1 (fr) 2018-11-21
KR20200010239A (ko) 2020-01-30
US11389791B2 (en) 2022-07-19
JP2020520797A (ja) 2020-07-16
CN110621403B (zh) 2024-01-26
WO2018210770A1 (fr) 2018-11-22
CN110621403A (zh) 2019-12-27

Similar Documents

Publication Publication Date Title
EP2257372B1 (fr) Procédé de régénération d'un catalyseur contenant du ruthénium ou des composés de ruthénium contaminés par du soufre sous forme de composés de soufre
EP3624939A1 (fr) Procédé de régénération d'un catalyseur contenant un ruthénium ou des composés de ruthénium, contaminé
EP1866239B1 (fr) Procede pour produire du chlore
EP2142470B1 (fr) Procédé d'élimination par condensation-adsorption de composants organiques d'un flux de gaz contenant du chlorure d'hydrogène
DE102007018016A1 (de) Absorptionsprozess zur Entfernung anorganischer Komponenten aus einem Chlorwasserstoff enthaltenden Gasstrom
EP2384239B1 (fr) Procédé de régénération d'un catalyseur contenant de l'oxyde de ruthénium pour l'oxydation du chlorure d'hydrogène
EP2384240A1 (fr) Catalyseur pour l'oxydation de chlorure d'hydrogène contenant du ruthénium et du nickel
DE102007020154A1 (de) Verfahren zur Herstellung von Chlor durch Gasphasenoxidation
DE102009034773A1 (de) Verfahren zur Herstellung von Chlor durch Gasphasenoxidation an nanostrukturierten Rutheniumträgerkatalysatoren
WO2012025483A2 (fr) Catalyseur et procédé pour produire du chlore par une oxydation catalytique en phase gazeuse de chlorure d'hydrogène
WO2010076297A2 (fr) Procédé de récupération de ruthénium dans des catalyseurs usagés contenant de l'oxyde de ruthénium
EP2157198A1 (fr) Procédé de production de ruthénium métallique ou de composés de ruthénium à partir de matières solides contenant du ruthénium
WO2004026761A1 (fr) Procede a lit fixe pour produire du chlore par oxydation catalytique en phase gazeuse de chlorure d'hydrogene
WO2007147781A1 (fr) Masse absorbante et procédé d'extraction de mercure
DE10252859A1 (de) Verfahren zur Herstellung von 1,2-Dichlorethan und von Vinylchlorid
DE102008051694A1 (de) Verfahren zur Abtrennung von Kohlenmonoxid aus einem HCI-Rohgas
WO2004031074A1 (fr) Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene
EP2177268A1 (fr) Catalyseur et procédé de fabrication de chlore par oxydation en phase gazeuse
WO2007134723A2 (fr) Procédé de production de chlore par oxydation en phase gazeuse
DE102007033113A1 (de) Temperaturstabiler Katalysator für die Chlorwasserstoffgasphasenoxidation
WO2020216837A1 (fr) Procédé de nettoyage de gaz de traitement corrosifs contenant du soufre
EP1506133A1 (fr) Procede de fabrication de chlore a partir de gaz chlorhydrique
DE10234908B4 (de) Verfahren zur Herstellung von Chlor aus einem (Chlor)kohlenwasserstoffe enthaltenden Chlorwasserstoffstrom
DE102007033114A1 (de) Verfahren zur Herstellung von Chlor durch Gasphasenoxidation von Chlorwasserstoff
DE102011005897A1 (de) Verfahren zur Bereitstellung von Chlor für chemische Umsetzungen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: COVESTRO DEUTSCHLAND AG

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: COVESTRO INTELLECTUAL PROPERTY GMBH & CO. KG

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20220413

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: COVESTRO DEUTSCHLAND AG