EP4308531A1 - Procédé et installation pour produire un composé cible - Google Patents

Procédé et installation pour produire un composé cible

Info

Publication number
EP4308531A1
EP4308531A1 EP22715020.8A EP22715020A EP4308531A1 EP 4308531 A1 EP4308531 A1 EP 4308531A1 EP 22715020 A EP22715020 A EP 22715020A EP 4308531 A1 EP4308531 A1 EP 4308531A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
temperature
sections
pipe sections
tube
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
EP22715020.8A
Other languages
German (de)
English (en)
Inventor
Mathieu Zellhuber
Martin Schubert
Andreas Meiswinkel
Wolfgang Müller
Ernst Haidegger
Gerhard Mestl
Klaus Wanninger
Peter Scheck
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.)
Clariant International Ltd
Linde GmbH
Original Assignee
Clariant International Ltd
Linde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd, Linde GmbH filed Critical Clariant International Ltd
Publication of EP4308531A1 publication Critical patent/EP4308531A1/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/20—Vanadium, niobium or tantalum
    • C07C2523/22—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/057—Selenium or tellurium; Compounds thereof

Definitions

  • the present invention relates to a method and a plant for the production of a target compound according to the preambles of the corresponding independent patent claims.
  • the principle of the oxidative dehydrogenation (ODH) of paraffins having two to four carbon atoms is known.
  • ODH oxidative dehydrogenation
  • the paraffins mentioned are reacted with oxygen to form the respective olefins and water, among other things.
  • the present invention relates in particular to the oxidative dehydrogenation of ethane to ethylene, also referred to below as ODHE.
  • the present invention is not limited to the oxidative dehydrogenation of ethane, but can also extend to the oxidative dehydrogenation (ODH) of other paraffins such as propane or butane. In this case, the following explanations apply accordingly.
  • ODH(E) may offer advantages over more established olefin production processes such as steam cracking or catalytic dehydrogenation. Due to the exothermic nature of the reactions involved and the practically irreversible formation of water, there is no thermodynamic equilibrium limitation.
  • the ODH(E) can be carried out at comparatively low reaction temperatures. In principle, the catalysts used do not need to be regenerated, since the presence of oxygen enables or causes in situ regeneration. Finally, in contrast to steam cracking, smaller amounts of worthless by-products such as coke are formed.
  • ODH(E) For further details regarding the ODH(E), please refer to relevant literature, e.g. Ivars, F. and Lopez Nieto, JM, Light Alkanes Oxidation: Targets Reached and Current Challenges, in: Duprez, D. and Cavani, F. (eds.) , Handbook of Advanced Methods and Processes in Oxidation Catalysis: From Laboratory to Industry, London 2014: Imperial College Press, pages 767-834, or Gärtner, CA et al., Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects, ChemCatChem, Vol. 5, No. 11, 2013, pages 3196 to 3217, and X. Li, E. Iglesia, Kinetics and Mechanism of Ethane Oxidation to Acetic Acid on Catalysts Based on Mo-V-Nb Oxides, J. Phys. Chem. C, 2008, 112, 15001-15008.
  • MoVNb-based catalyst systems have turned out to be promising for the ODH(E), as for example in F. Cavani et al., "Oxidative dehydrogenation of ethane and propane: How far from commercial Implementation?", Catal. Today, 2007, 127, 113-131. Catalyst systems additionally containing Te can also be used. If a "MoVNb-based catalyst system” or a “MoVTeNb-based catalyst system” is mentioned here, this is understood to mean a catalyst system which has the elements mentioned as a mixed oxide, also expressed as MoVNbO x or MoVTeNbO x . The specification of Te in parentheses stands for its optional presence. The invention is used in particular with such catalyst systems.
  • the required use of oxygen as an oxidizing agent in the ODH(E), especially under slightly diluted conditions, can lead to explosive mixtures within the system.
  • Mixing concepts that can be replaced here to avoid explosive mixtures in certain parts of the plant or reactor areas are known and described, for example, in EP 3476471 A1 for a commercial tube bundle reactor;
  • constructive measures e.g. the installation of flame or detonation barriers, the minimization of free volumes, pressure-resistant design
  • these or other approaches require, in particular, that the relevant ignition temperature is clearly undercut upstream of the actual reactor.
  • the ODH(E) is preferably carried out in fixed bed reactors, in particular in cooled tube bundle reactors, for example with molten salt cooling.
  • reactor bed with a plurality of zones is generally known for strongly exothermic reactions, ie in particular oxidative reactions, which also include ODH(E).
  • oxidative reactions which also include ODH(E).
  • Basics are described for example in WO 2019/243480 A1 of the applicant. This document discloses the principle that different catalyst beds or corresponding reaction zones which have different catalyst loadings and/or catalyst activities per unit volume are used.
  • catalyst poisoning is characterized in particular by the fact that a deactivation front moves in the direction of flow over the respective catalyst bed, i.e. while initial areas of the catalyst bed (i.e. upstream of the deactivation front in the catalyst bed) are partially already completely or almost completely deactivated, the areas point (immediately) downstream the deactivation front still show their complete or almost complete activity.
  • typical troublesome trace components are, in particular, sulfur compounds, phosphorus compounds, nitrogen compounds, metals and their compounds (especially alkali metals, alkaline earth metals and heavy metals), aluminosilicates, halides (especially chlorides) and halogen-containing compounds as well as heavy hydrocarbons.
  • alkaline earth metals and heavy metals mentioned can in particular include Na, K, Cs, Mg, Ca, Al, Si, Fe, Cr, Ni, As, Sb, Hg, Pb and V.
  • oxygen and nitrogen-containing compounds such as oxygenates, alcohols, carbonyl compounds, amines, nitrogen oxides, etc.
  • heavy hydrocarbons - unsaturated and aromatic compounds in particular must be taken into account here - can have a negative effect.
  • the origin of the trace components can usually be found in the origin or provision of oxygen, ethane and water. These components or their derivatives originate on the one hand from the corresponding raw material source, for ODH(E) i.e. from the ethane or associated gas source. On the other hand, for alkali and alkaline earth metals (especially Na, K as well as Mg and Ca) as well as halides (especially chloride), a steam generation system can also lead to a load on the steam if the corresponding water treatment is not sufficiently designed or if it is increased here due to operational disruptions concentrations of interfering trace components.
  • ODH(E) i.e. from the ethane or associated gas source.
  • alkali and alkaline earth metals especially Na, K as well as Mg and Ca
  • halides especially chloride
  • the vapor can also contain dosing chemicals, which serve, for example, to inhibit corrosion and, in particular, can also contain (volatile) nitrogenous components.
  • the oxygen source can also contribute to the entry of disruptive trace components, e.g. from the ambient air or from process-related contamination.
  • the actual reactor is usually preceded by appropriate preparation or processing, which can include e.g. adsorptive, absorptive and/or distillative steps.
  • guard beds which are usually designed as a fixed bed and filled with a suitable guard material, are used to remove trace components. Both adsorptive and reactive mechanisms of action can be used here. Depending on the type and quantity of the trace components to be removed, guard beds that cannot be regenerated can also be regenerable guard beds. Additional equipment and process steps are therefore required here to prepare for use.
  • This preparation for use usually relates to the use of hydrocarbons, while a corresponding water treatment is connected upstream for the steam of the steam production.
  • the oxygen required for an ODH(E) process according to the invention can also be contaminated with impurities, which makes a corresponding additional pre-cleaning necessary.
  • the tube bundle reactors typically used for ODH(E) with up to several tens of thousands of parallel tubes in industrial applications represent complex and cost-intensive constructions or apparatus To make the size and dimensions as compact as possible for structural reasons and for cost reasons.
  • An important parameter here is the length of the individual reaction tube, which must be used as efficiently as possible, so that its length should be kept as short as possible. In particular, volumes that are only filled with inert material should be kept as small as possible, otherwise they are of no commercial use.
  • the object is to keep the time interval between two catalyst changes as long as possible while at the same time producing economically during the running time, ie to achieve the highest possible and most constant possible selectivity or yield of valuable products. This is a minimization of adjustments to the reaction conditions, such as the reaction temperature, necessary. It is therefore necessary to stabilize the reaction conditions.
  • both upstream process steps for processing the feedstock and an inert preheating zone are conventionally used, which, however, is already inside the actual reactor, specifically the respective reaction tube.
  • this inert preheating zone is located in the area of a relatively complex construction and the volume of the reactor is increased by space unused for reaction purposes.
  • the necessary size of this preheating zone is determined by the specific heat transfer (depending in particular on the particle geometry, flow rate, educt gas composition and density, viscosity and heat capacity of the educt gas) and the temperature difference between the feed mixture at the reactor inlet and the required reaction temperature at the beginning of the actual reaction zone.
  • Typical catalysts for heterogeneous catalysis in particular for oxidative processes and in particular for the ODH(E), require a certain minimum temperature, the so-called light-off temperature, for an appreciable reaction to take place. According to the prior art, this light-off temperature is dependent in particular on the catalytically active material used. Since the light-off temperature, in the case of conventionally used catalyst beds, is above the feed temperature of the feed mixture is in the reactor used, the already mentioned preheating zones made of inert material are used.
  • the present invention now makes use of the fact that the activity of a specific catalyst material, and the light-off temperature associated therewith, can be influenced by the production and in particular by a single production step. It was found in particular for the advantageously used MoVNb(Te)0,r catalysts that the calcination conditions have a direct influence on their respective activity. Increased activity is accompanied by a reduced starting temperature.
  • the composition of the catalytically active material remains the same in principle and can in particular be taken from the same synthesis batch.
  • the invention exploits this in the embodiment mentioned by using a catalyst of advantageously the same type and of the same elementary composition with a correspondingly lower light-off temperature and associated higher activity in zones (hereinafter also referred to as "first tube sections") of the reaction tubes of a tube bundle reactor, which were previously used for heating up to the light-off temperature of the zone downstream and filled with inert material.
  • first tube sections zones of the reaction tubes of a tube bundle reactor, which were previously used for heating up to the light-off temperature of the zone downstream and filled with inert material.
  • the present invention proposes a method for producing a target compound, in which a feed mixture at a temperature in a first temperature range is distributed over a plurality of parallel reaction tubes of a tube bundle reactor, in first tube sections of the reaction tubes is subjected to heating to a temperature in a second temperature range, and is subjected to an oxidative catalytic conversion in second pipe sections of the reaction pipes arranged downstream of the first pipe sections using one or more catalysts arranged in the second pipe sections.
  • the heating is carried out at least in part using a catalyst which is arranged in the first tube sections and has a light-off temperature in the first temperature range.
  • the present invention therefore proposes at least partially dispensing with a preheating zone with inert material and instead providing an upstream catalyst bed with a lower light-off temperature or higher activity. It should already be noted at this point that an inert material does not have to be completely dispensed with within the scope of the present invention. This can be used at a suitable point, for example, for uniform distribution of the respective gas streams over the entire cross section of the reaction tubes.
  • the first temperature range can be in particular from 170 to 280° C., preferably from 200 to 270° C. and particularly preferably from 220 to 260° C.
  • the second temperature range is preferably from 280 to 450° C. and particularly preferably at 300 up to 400°C.
  • the temperature in the first temperature range (and thus the onset temperature) is in particular 30 to 110 K, preferably 40 to 80 K and particularly preferably 40 to 60 K below the temperature in the second temperature range (of the main bed).
  • the "light-off temperature” is understood in particular as the temperature at which the catalyst, under technically relevant conditions, more than 10% of the starting material under consideration, i.e. a paraffin in the case of ODH, at which ODH(E)
  • the catalyst arranged in the first tube sections and one or at least one of the several catalysts arranged in the second tube sections advantageously contain at least the metals molybdenum, vanadium, niobium and optionally tellurium, in particular in the form of a corresponding mixed oxide, since, as has been proven according to the invention, the advantageous effects mentioned are particularly pronounced in the case of corresponding catalysts.
  • the catalyst arranged in the first pipe sections and the one or at least one of the plurality of catalysts arranged in the second pipe sections can be produced at least partially from the oxides of the corresponding metals.
  • the catalyst production is therefore extremely inexpensive due to the readily available starting materials.
  • the catalyst arranged in the first pipe sections and the one or at least one of the plurality of catalysts arranged in the second pipe sections advantageously have an identical elemental composition, as already mentioned. This allows the corresponding catalytic converters to be produced easily, with the only differences arising from the different production methods.
  • An “identical elemental composition” should still exist according to the understanding on which this is based, even if the proportions of the individual elements or their compounds between the different catalysts differ by no more than 10%, 5% or 1%.
  • the catalyst arranged in the first pipe sections has an activity that is more than 10% higher than the one or at least one of the plurality of catalysts arranged in the second pipe sections, due to different calcination intensities.
  • the activity can also be higher by 20%, 30% or 40%, for example.
  • the catalyst arranged in the first tube sections advantageously has a temperature of more than 3 K, preferably more, due to the different calcination intensities than 5 K lower, more preferably more than 10 K lower, and particularly preferably more than 15 K lower light-off temperature.
  • a calcination intensity is caused in particular by the calcination procedure, but also, for example, a particularly intensive—eg long-lasting—calcination.
  • the previously customary preheating zone in the reactor with inert material can therefore be filled in whole or in part with a catalyst having the same catalytically active material.
  • a material is advantageously selected which has a very low light-off temperature, which ideally corresponds to the temperature of the educt mixture entering the reactor.
  • a short inert layer can be provided at the reactor tube inlet, i.e. upstream of the very active catalyst layer mentioned with the low light-off temperature (and thus upstream of the first tube sections), in order to create a defined flow profile in the reactor tube and thus defined starting conditions reach (so-called inlet section).
  • the length of such an inlet section is usually at least 10 times the equivalent diameter of an inert particle used, but at most typically less than 50 cm, in particular less than 30 cm or less than 20 cm.
  • a reactive preheating section (in the form of the first pipe sections) follows a possible inert inlet section.
  • An essential function of this reactive preheating section provided according to the invention is that any catalyst poisons that may be contained in the educt stream can already react here with the catalytically active material and/or be adsorbed, since the catalytically active material in the preheating zone is advantageously present in the or corresponds to the following main reaction zones (in the second tube sections).
  • these one or more following main reaction zones are formed by several catalyst beds with a volumetric activity of the beds that increases from the beginning of the reaction tube to the end of the reaction tube, i.e. in the direction of flow (e.g.
  • an active catalyst material is used according to the invention, which corresponds in its chemical composition to the material in the following main reaction zone or zones (i.e. the second tube sections), but is even more active, as already stated in other words explained.
  • Such an even more active MoVTeNbO 4 catalyst is described, for example, in WO 2018/141652 A1 or WO 2018/141653 A1.
  • the volumetric activity of the reactive preheat bed has at least a similar value as the most active main reaction zone.
  • the active material of the reactive preheating zone is subjected to a lower calcination intensity during its production, for example calcined at a lower temperature, and thus has a higher basic activity than the catalyst material of the main reaction zones.
  • the activity can also be increased by adjusting the composition of the catalyst, as described, for example, in WO 2018/141652 A1.
  • the volumetric activity of the reactive preheating zone can exceed the value of the highest volumetric activity of the one or more main reaction zones.
  • the higher volumetric activity usually goes hand in hand with a higher pore volume and/or a higher BET surface area and in particular a lack of inert dilution.
  • the BET surface area represents the mass specific surface area calculated from experimental data according to known methods and is usually given in units of square meters per gram (m 2 g -1 ).
  • the person skilled in the art is familiar with the BET measurement from relevant textbooks and standards, for example DIN ISO 9277:2003-05, "Determination of the specific surface area of solids by gas adsorption using the BET method (ISO 9277:1995)". However, this is not a necessary, mandatory prerequisite for the implementation of the present invention, but relates to a possible embodiment.
  • the specific pore volume of a catalyst can be determined, for example, with the help of nitrogen physisorption measurements.
  • a pore volume and/or a BET surface area in the first tube sections is above, in particular by 15 to 60% above, a maximum pore volume and/or a maximum BET surface area in the second tube sections.
  • the length of such a reactive preheating section is preferably at least ten times the equivalent diameter of a catalyst particle used, but preferably less than 40 cm or less than 30 cm, particularly preferably between 5 and 25 cm.
  • an embodiment is particularly relevant for the technical embodiment in which the length of the reactive preheating in relation to the main reaction zone or zones is less than 0.1, preferably less than 0.07, and particularly preferably less than 0.04.
  • a length of an area in which the catalyst is arranged in the first pipe sections is less than 40 cm in absolute dimensions and/or this length is in relation to a total length of an area in which the one or more catalysts is or are arranged in the second tube sections, less than 0.1.
  • a higher basic activity of the otherwise same chemical material means that the number of active centers of such a material is larger.
  • a larger number of active centers in the reactive preheating section i.e. the first tube sections
  • the reactive preheating section - although a significantly more active catalyst is used - has no significant influence on the overall reactor performance, i.e. the performance of the entirety of the reactive beds (reactive preheating zone and one or more main reaction zones), in terms of conversion and selectivity to commercial products, as can be seen from Figure 2 explained below. Reference is made here to this and the associated Table 3.
  • the function of the reactive preheating zone can therefore be seen in particular in an advantageous extension of the service life of the main reaction zones.
  • the coolant temperature can optionally be increased with increasing deactivation.
  • the functionality of the reactive preheating zone can be monitored by devices that record values that are a measure of the catalyst activity. Monitoring the bed temperature of this reactive preheating zone at at least one point in the bed of this reactive preheating zone, but preferably distributed over a number of points in the bed of the preheating zone, is particularly suitable for this purpose. Analogously, the activity of the main reaction zone can also be recorded very easily online (additionally, of course, by online monitoring of the oxygen content at the reactor outlet and complete regular analyzes of the process gas composition, which, however, are usually not carried out online).
  • the design of the catalysts according to the present invention can be such that a volumetric activity in the first tube sections is above a maximum volumetric activity in the second tube sections due to the different production.
  • the present invention can be used in particular in connection with an ODH of alkanes, so that the feed mixture advantageously contains oxygen and a paraffin, in particular with two to six carbon atoms, and the oxidative reaction as an oxidative dehydrogenation of the paraffin is carried out.
  • One ODH used with particular advantage uses ethane as the paraffin and performs an oxidative dehydrogenation of the ethane (ODHE).
  • the oxidative reaction is advantageously carried out at a catalyst temperature in a range between 240 and 500.degree. C., preferably between 280 and 450.degree. C., in particular between 300 and 400.degree.
  • the starting mixture is advantageously fed to the reactor at a pressure in a pressure range from 1 to 10 bar (absolute), in particular from 2 to 6 bar (absolute). It is therefore a process that operates at comparatively low pressure and in which the above-mentioned advantages of the shortened reaction tube lengths result in a special way.
  • a water content in the feed mixture of between 5 and 95% by volume, in particular between 10 and 50% by volume and more particularly between 14 and 35% by volume.
  • at least one parameter can also be determined, for example, which indicates an activity of the or one of the catalysts, and on this basis a quantity of water in the reaction feed stream based on the at least one determined parameter to be set.
  • an embodiment can be advantageous in which the starting mixture contains ethane and in which the molar ratio of water to ethane in the starting mixture is at least 0.23.
  • the invention can be used independently of the routing of the cooling medium (ie co-current or counter-current).
  • a particular additional advantage can be achieved when the cooling medium—in particular a molten salt—is conducted in countercurrent, since the heat of reaction from the main reaction in the reactive preheating zone can also be partially utilized here.
  • different cooling circuits in combination with different catalyst layers are conceivable (as also specified in more detail in WO 2019/243480 A1).
  • the reactor is designed in such a way that the reactor is explicitly additionally cooled differently in the area of reactive preheating, i.e. the first tube sections, i.e. the possibility of a separate cooling circuit there (with possibly even a different coolant flow direction) consists.
  • this zone can, for example, also be explicitly “switched on” by a corresponding heat input or, if not needed or only slightly, “switched off”.
  • the present invention proposes that the reaction tubes be cooled using one or more cooling media flowing around the reaction tubes.
  • the first pipe sections and the second pipe sections can be cooled with particular advantage using different cooling media, the same cooling medium in different cooling medium circuits, and/or the same or different cooling media in different or the same flow directions.
  • the invention also extends to a plant for producing a target compound with a tube bundle reactor which has a plurality of reaction tubes arranged in parallel, which have first tube sections and second tube sections arranged downstream of the first tube sections, one or more catalysts being arranged in the second tube sections and the Plant has means that are set up to distribute a feed mixture at a temperature in a first temperature range to the reaction tubes, to subject it to heating in the first tube sections to a temperature in a second temperature range, and in the second tube sections using one or the to subject a plurality of catalysts arranged in the second tube sections to an oxidative catalytic conversion.
  • a catalyst is provided for at least part of the heating in the first tube sections, which has a light-off temperature that lies in the first temperature range.
  • Figure 1 illustrates different catalyst activities for catalysts obtained at different calcination temperatures.
  • Figure 2 illustrates temperature profiles for a three-stage catalyst bed with a reactive preheat zone according to one embodiment of the invention.
  • FIG. 3 illustrates a plant according to an embodiment of the present invention in a simplified schematic representation.
  • FIG. 4 illustrates a reactor according to an embodiment of the present invention in a simplified schematic representation.
  • the present invention makes use of the fact that the activity of a specific catalyst material and, in connection therewith, the light-off temperature can be influenced by the production.
  • the composition of the catalytically active material remains the same in principle and can in particular be taken from the same synthesis batch. This surprising effect was found in a catalytic testing of MoVNb(Te)O ⁇ catalyst material of the same synthesis approach and thus the same stoichiometry (composition of elements), but different calcination temperatures.
  • the production of the catalyst material can in principle as in the
  • the metal oxides that are suitable in each case can be subjected to a hydrothermal synthesis.
  • TeC> 2 was suspended in 200 g of distilled water and ground in a planetary ball mill with balls 1 cm in diameter (ZrC> 2 ). The portion containing 500 ml of distilled water was then transferred to a beaker.
  • Nb 2 05 was slurried in 200 g distilled water and ground in the same ball mill. The portion containing 500 ml of distilled water was then transferred to a beaker.
  • a hydrothermal synthesis was carried out in a 40 L autoclave at 190° C./48 h. After the synthesis, it was filtered off using a vacuum pump with a blue band filter, and the filter cake was washed with 5 L of distilled water.
  • Drying took place at 80° C. in a drying cabinet for 3 days and the product was then ground in an impact mill. A solids yield of 0.8 kg was achieved.
  • the subsequent calcination took place at 280° C. for 4 h in air (heating rate 5° C./min air: 1 L/min).
  • the activation took place in a retort at 600° C. for 2 h (heating rate 5° C./min nitrogen: 0.5 L/min).
  • the catalysts produced in this way were tested in an experimental plant 1 under exactly identical conditions (amount of catalyst filled in of 46 g, system pressure of 3.5 bar (abs.), composition of the reaction charge from ethane to oxygen to water (vapor) of 55.3 to 20.7 to 24 (each mol%), GHSV of 1140 (NI_gas/h)/l_catalyst) examined with regard to their activity.
  • the corresponding experimental reactor (usable length 0.9 m, inner diameter of the reaction space 10 mm) is designed as a double tube. The heating or cooling takes place with the aid of a thermal oil bath, with the thermal oil being pumped through the exterior of the reactor and thus heating or cooling the interior/reaction zone at the same time (the reaction is an exothermic reaction).
  • the activity gradations are illustrated in FIG. 1, in which the activity in the form of the ethane conversion in moles per liter of catalyst and hour (i.e. the activity per catalyst volume) is plotted on the left vertical axis (circles in the diagram) and the relative activity in percent on the right vertical axis ( triangles in the graph) versus calcination temperature on the horizontal axis.
  • the values obtained for the respective catalysts or catalyst samples according to Table 1 are shown with C1, C2 and C3. Starting from FIG. 1, it is to be expected that the light-off temperatures of these differently calcined catalysts also differ, ie that the most active material also has the lowest light-off temperature. Table 1 confirms this.
  • the temperature at which the ethane conversion is 10% is defined as the light-off temperature.
  • this light-off temperature can be read almost directly from the experimental data (at a reaction temperature of 250°C - this corresponds to the temperature at the beginning of the catalyst bed and the temperature of the thermal oil bath - the ethane conversion was 9.6%), in the other two catalyst samples 2 and 3 not because the turnover range examined was smaller there.
  • the conversions were determined at at least 4 different temperatures (cf. number of different temperature levels in Table 1), with the number of conversions and temperature levels for all catalyst samples being sufficiently far apart.
  • Arrhenius plot i.e. a plot of the natural logarithm of the reaction rate constant versus the reciprocal of the reaction temperature (in Kelvin), could thus be constructed for each of the catalyst samples.
  • the person skilled in the art is generally familiar with the creation of an Arrhenius plot.
  • the Arrhenius plot provides a straight line with different parameters (slope and intercept) for each of the catalyst samples. With the help of the respective linear equation, the associated reaction rate constant and, via this, the corresponding reaction temperature can be determined for a given ethane conversion.
  • Test plant 2 consists of a tubular reactor with a usable length of 1 m and an internal diameter of 25 mm. The heating and, at the same time, also the cooling took place by means of a salt bath fluidized with nitrogen, in which the reactor is immersed. For technical reasons, air was used as the oxidizing agent instead of pure oxygen, and this experimental plant 2 could only be operated under atmospheric pressure.
  • the other test conditions in this setup were as follows: the amount of catalyst used was 337 g, the composition of the reaction charge from ethane to nitrogen to oxygen to water (vapor) from 11.1 to 46.7 to 6.8 to 35.4 (each mol% ), GHSV of 418 (NLc as /hj/L Kataiysato r.
  • catalyst 2 cf. FIG. 1 and Table 2 was also tested in this experimental plant 2 under the same conditions. The test results are listed in Table 2.
  • catalyst 2 has an ethane conversion of approx. 67% at a salt bath temperature of 322°C.
  • Catalyst 4 on the other hand, only requires a salt bath temperature of 302° C. for a conversion of 64% and at this temperature still has a significantly higher conversion than catalyst 2 at a higher temperature of 310° C. (ethane conversion of catalyst 2 of 53%).
  • reaction rate constant corresponding to this temperature was calculated. The procedure for this is generally known to the person skilled in the art. This reaction rate constant served as a starting point for determining a corresponding Arrhenius line. Since only one measuring point was available for Catalyst 4, the same slope of the Arrhenius straight line as determined for the test conditions in experimental plant 1 was used, assuming that the apparent activation energy is independent of the test conditions.
  • the values in Table 2 marked with an asterisk relate to the pure MoVNbTe oxide catalyst powder (before tableting).
  • silica and wax are added as tableting aids.
  • the porosity of the silica also determines the porosity of the final shaped catalyst body, so that the exact value differs.
  • the nitrogen pore volume of the actual catalyst powder before tableting correlates with the activity.
  • the findings according to the invention explained above are surprising.
  • the activity and light-off behavior of the catalyst samples, which differs according to the invention, can surprisingly be correlated with the data from the catalyst characterization (cf. Tables 1 and 2). by a lesser one Calcination temperature in the catalyst production can be achieved as a new finding, an increase in the specific surface area and even more significantly the specific pore volume.
  • a higher activity is usually associated with a reduced selectivity
  • a high or even constantly high selectivity of the overall reaction bed can nevertheless be achieved.
  • Figure 2 illustrates temperature profiles for a three-stage catalyst bed of the main reaction zone based on a catalyst 2 (see above) with a reactive preheating zone, the material of the reactive preheating zone according to the particularly preferred embodiment having about 1.2 times the basic activity of the catalyst material of the main reaction zone.
  • the reactive preheating zone has its full activity
  • the reactive preheating zone is completely deactivated, i.e. inert, e.g. by poisoning, while the catalyst beds of the main reaction zone remain unchanged at their full activity (i.e. the activity , which occurs after a typical break-in period), which applies to the "poisoning" catalyst deactivation mechanism as explained above.
  • the same coolant temperature was used for both cases. The coolant was fed in countercurrent to the reaction gas.
  • an unchanged reactor function can be maintained without having to adjust the operating parameters, such as the coolant temperature.
  • the coolant temperature usually has to be increased as the deactivation progresses. Within the scope of the invention, this can additionally optionally take place, for example after extensive deactivation of the reactive preheating zone, which extends the overall service life of a corresponding technical reactor.
  • FIG. 3 a plant for the production of olefins according to one embodiment of the invention is illustrated in the form of a greatly simplified plant diagram and is denoted overall by 1.
  • the plant 1 is indicated only schematically.
  • the basic arrangement of the preheating zone and the subsequent reaction zone(s) is shown using a greatly enlarged reaction tube 11, which is not drawn to scale, in a tube bundle reactor 100.
  • a system 1 for ODHE is described below, as mentioned, the present invention is also suitable for use in the ODH of higher hydrocarbons. In this case, the following explanations apply accordingly.
  • the plant 1 has a tube bundle reactor 100 to which, in the example shown, an ethane-containing feed mixture A obtained in any desired manner is fed.
  • the starting mixture A can contain, for example, hydrocarbons taken from a rectification unit (not shown).
  • the feed mixture A can also be preheated, for example, and processed in some other way.
  • the feed mixture A can already contain oxygen and, if appropriate, a reaction moderator such as steam, but corresponding media can also be added upstream or in the tube bundle reactor 100, as not shown separately.
  • a product mixture B is removed from the tube bundle reactor 100 .
  • the tube bundle reactor 100 which is shown in detail in FIG.
  • reaction tubes 10 have a large number of reaction tubes 10 arranged in parallel (only partially designated), which run through a preheating zone 110 and then through several reaction zones 120, 130, 140, three in the example shown .
  • the reaction tubes 10 are surrounded by a jacket area 20 through which a coolant C of the type explained is guided in the example.
  • the representation is greatly simplified because, as mentioned, the reaction tubes 10 can optionally be cooled using a plurality of cooling media flowing around the reaction tubes 10 or different tube sections using different cooling media, the same cooling medium in different cooling medium circuits, and/or the same or different cooling media in same or different directions of flow can be cooled.
  • the starting mixture A is distributed over the reaction tubes 10 in a suitable manner at a temperature in a first temperature range.
  • the reaction tubes each have first tube sections 11, which are located in the preheating zone 110, and second tube sections 12, which are located in the reaction zones 120, 130 and 140.
  • heating takes place to a temperature in a second temperature range, and in the second tube sections 12 of the reaction tubes 10 arranged downstream of the first tube sections 11, the correspondingly preheated feed mixture A is heated using one or more, in the second tube sections 12 arranged catalysts subjected to an oxidative catalytic conversion.
  • the heating is carried out at least in part using a catalyst which is arranged in the first tube sections 11 and has a light-off temperature in the first temperature range, and the use of which already leads to a partial conversion expressly referred to the above explanations.
  • the process gas can in these with washing water or suitable aqueous solution are brought into contact, whereby the process gas is particularly cooled and acetic acid can be washed out of the process gas.
  • the process gas which has at least largely been freed from water and acetic acid can be processed further and subjected to a separation of ethylene. Ethane contained in the process gas can be returned to the reactor 100 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un composé cible, un mélange d'entrée (A) est distribué à une température dans une première plage de température jusqu'à une pluralité de tubes de réaction parallèles (10) d'un réacteur à faisceau tubulaire (100), soumis à un chauffage à une température dans une seconde plage de températures dans des premières parties de tube (11) des tubes de réaction (10), et soumis à une réaction catalytique oxydative dans des secondes parties de tube (12) des tubes de réaction (10) situés en aval des premières parties de tube (11) à l'aide d'un ou de plusieurs catalyseurs disposés dans les secondes parties de tube (12). Le procédé est caractérisé en ce que le chauffage est effectué au moins partiellement à l'aide d'un catalyseur qui est disposé dans les premières parties de tube (11) et qui a une température d'amorçage dans la première plage de température. L'invention concerne également une installation correspondante.
EP22715020.8A 2021-03-15 2022-03-14 Procédé et installation pour produire un composé cible Pending EP4308531A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021202505.6A DE102021202505A1 (de) 2021-03-15 2021-03-15 Verfahren und Anlage zur Herstellung einer Zielverbindung
PCT/EP2022/056572 WO2022194794A1 (fr) 2021-03-15 2022-03-14 Procédé et installation pour produire un composé cible

Publications (1)

Publication Number Publication Date
EP4308531A1 true EP4308531A1 (fr) 2024-01-24

Family

ID=81212783

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22715020.8A Pending EP4308531A1 (fr) 2021-03-15 2022-03-14 Procédé et installation pour produire un composé cible

Country Status (6)

Country Link
US (1) US20240150261A1 (fr)
EP (1) EP4308531A1 (fr)
CN (1) CN117203180A (fr)
CA (1) CA3212561A1 (fr)
DE (1) DE102021202505A1 (fr)
WO (1) WO2022194794A1 (fr)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4426069B2 (ja) * 2000-06-12 2010-03-03 株式会社日本触媒 アクリル酸の製造方法
US11401220B2 (en) * 2016-02-26 2022-08-02 Shell Usa, Inc. Alkane oxidative dehydrogenation (ODH)
EP3339276A1 (fr) 2016-12-22 2018-06-27 Linde Aktiengesellschaft Procédé et installation de production d'une oléfine
DE102017000861A1 (de) 2017-01-31 2018-08-02 Clariant Produkte (Deutschland) Gmbh Synthese eines MoVTeNb-Katalysators aus preisgünstigen Metalloxiden
DE102017000862A1 (de) 2017-01-31 2018-08-02 Clariant Produkte (Deutschland) Gmbh Synthese eines MoVNbTe-Katalysators mit reduziertem Gehalt an Niob und Tellur und höherer Aktivität für die oxidative Dehydrierung von Ethan
DE102017000865A1 (de) 2017-01-31 2018-08-02 Clariant Produkte (Deutschland) Gmbh Synthese eines MoVNbTe-Katalysators mit erhöhter spezifischer Oberfläche und höherer Aktivität für die oxidative Dehyxdrierung von Ethan zu Ethylen
EP3476471A1 (fr) 2017-10-25 2019-05-01 Linde Aktiengesellschaft Procédé et réacteur de formation et de transformation catalytique d'un mélange d'éduits
EP3587383A1 (fr) 2018-06-21 2020-01-01 Linde Aktiengesellschaft Procédé et système de production d'une ou d'une pluralité de olefins et d'un ou d'une pluralité d'acides carboxyliques

Also Published As

Publication number Publication date
CA3212561A1 (fr) 2022-09-22
CN117203180A (zh) 2023-12-08
US20240150261A1 (en) 2024-05-09
DE102021202505A1 (de) 2022-09-15
WO2022194794A1 (fr) 2022-09-22

Similar Documents

Publication Publication Date Title
DE60309464T2 (de) Wismut und phosphor enthaltender katalysatorträger, mit diesem träger hergestellter reformierungskatalysator sowie dessen herstellungsverfahren und verwendung beim reformieren von naphta
DE69327947T2 (de) Verfahren zum behandeln von kohlenwasserstoffen mit einem kombinierten hydrotreating/hydrocracking-katalysatorsystem
EP3558910B1 (fr) Procédé et installation de production d'une oléfine
WO2019243480A1 (fr) Procédé et installation de fabrication d'une ou de plusieurs oléfines et d'un ou de plusieurs acides carboxyliques
EP3519377B1 (fr) Procédé et installation de production d'éthylène et acide acétique
EP0804287B1 (fr) Catalyseur pour la deshydrogenation oxydante d'hydrocarbures paraffiniques et utilisation de ce catalyseur
DE4310971A1 (de) Nickel/Aluminiumoxid-Katalysator, Verfahren zu seiner Herstellung, seine Verwendung sowie Verfahren zur Hydrierung von aromatischen Kohlenwasserstoffen mit Hilfe des Katalysators
EP0262389A1 (fr) Procédé de production d'huiles blanches médicales et de paraffines médicales
DE3410799C2 (fr)
EP0182078A2 (fr) Catalyseur pour les réactions d'oxydation et procédé pour sa préparation
DE1941948C3 (de) Verfahren zur Umwandlung von Kohlenwasserstoffen in Gegenwart von Wasserstoff bei erhöhten Temperaturen und Drücken
DE2512294C2 (fr)
DE69512676T2 (de) KATALYTISCHE DAMPFPHASEN-OXYDATION VON n-BUTAN ZU MALEINSÄUREANHYDRID EINSCHLIESSEND IN-SITU CALCINATION/AKTIVIERUNG DES KATALYSATORS
EP4308531A1 (fr) Procédé et installation pour produire un composé cible
DE3130065A1 (de) Verfahren zur regeneration von katalysatoren
DE2515919C2 (de) Verfahren zur katalytischen hydrierenden Entschwefelung von Vanadium und Nickel enthaltenden Kohlenwasserstoff- Rückstandsölen ohne Katalysatornachbeschickung
DE2447303C2 (fr)
EP4308527A1 (fr) Procédé et système de préparation d'un composé cible
DE2730564C2 (fr)
DE3416224C2 (de) Verfahren zur Herstellung eines Kohleverflüssigungsöls
DE102021202492A1 (de) Verfahren und anlage zur herstellung einer zielverbindung
DE102019127790A1 (de) Neues Katalysatorsystem für die Herstellung von Maleinsäureanhydrid durch katalytische Oxidation von n-Butan
DE102019127789A1 (de) Neues Katalysatorsystem für die Herstellung von Maleinsäureanhydrid durch katalytische Oxidation von n-Butan
WO2011095566A1 (fr) Dispositif réacteur et procédé pour optimiser la mesure des variations de température dans des réacteurs tubulaires
DE3226721C2 (fr)

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: 20231009

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)