EP4308527A1 - Procédé et système de préparation d'un composé cible - Google Patents

Procédé et système de préparation d'un composé cible

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Publication number
EP4308527A1
EP4308527A1 EP22712938.4A EP22712938A EP4308527A1 EP 4308527 A1 EP4308527 A1 EP 4308527A1 EP 22712938 A EP22712938 A EP 22712938A EP 4308527 A1 EP4308527 A1 EP 4308527A1
Authority
EP
European Patent Office
Prior art keywords
sections
pipe sections
catalyst
tube
catalysts
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
EP22712938.4A
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 EP4308527A1 publication Critical patent/EP4308527A1/fr
Pending legal-status Critical Current

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    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/021—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles comprising a plurality of beds with flow of reactants in parallel
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/06—Details of tube reactors containing solid particles
    • B01J2208/065—Heating or cooling the reactor
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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.
  • low-oxygen conditions are used in industrially relevant oxidative processes such as, for example, the production of maleic anhydride (MA) from butane, butene or benzene or else the two-stage synthesis of acrylic acid from propylene via the intermediate acrolein.
  • Oxygen-depleted air is usually used as the oxidizing agent.
  • DE 19837 519 A1 on the oxidation of propane to acrolein and/or acrylic acid may be mentioned here as an example.
  • a current overview of MSA synthesis which is carried out exclusively with air as the oxidizing agent, can also be found, for example, in PV Mangili et al., "Eco-efficiency and techno-economic analysis for maleic anhydride manufacturing processes", Clean Technol.
  • EP 2 716621 A1, EP 2 716622 A1, WO 2018/115416A1, WO 2018/115418A1, WO 2018/082945 A1 and EP 3339277 A1 by the applicant disclose the supply of pure oxygen in the ODH(E) , e.g. obtained from air separation by distillation, as an alternative to the use of air or oxygen-enriched or -depleted air, but not the associated special requirements for the reaction process and in particular the necessary coordination of the catalyst and reaction process.
  • the provision of oxygen by suitable processes such as air separation by distillation or pressure swing adsorption, as already stated in the applications cited above, is an established technology that can be implemented easily and economically on almost any scale.
  • the ODH(E) is preferably carried out in fixed bed reactors, in particular in cooled tube bundle reactors, for example with molten salt cooling.
  • the use of a reactor bed with a plurality of zones is generally known for strongly exothermic reactions, ie in particular oxidative reactions, which also include ODH(E).
  • Basics are described for example in WO 2019/243480 A1 of the applicant. This writing reveals the principle that different Catalyst beds or corresponding reaction zones which have different catalyst loadings and/or catalyst activities per unit space are used.
  • the tube bundle reactors typically used for the ODH(E) with up to several tens of thousands of parallel tubes in industrial applications represent complex and cost-intensive constructions or apparatus. It is therefore important to make the size and dimensions as compact as possible for both design and 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.
  • the emptying and filling process in the tube bundle reactors mentioned is also extremely complex, so that corresponding tube bundle reactors should be operated as gently as possible in order to ensure a long service life.
  • end regions of the corresponding (single- or multi-layer) catalyst beds in the individual reaction tubes are exposed to particular loads, since the progress of the reaction usually only contains a low residual oxygen concentration.
  • end or “end region” or “terminal ends” etc. is to be understood below as meaning the region in which the gas flowing through the reactor or a corresponding reaction tube leaves the catalyst bed, i.e. is then no longer subjected to any catalytic conversion in the reactor becomes.
  • the catalysts mentioned above require a certain minimum proportion of oxygen in the reaction gas in order not to be destroyed.
  • the oxygen content at the reactor outlet must not exceed a certain limit in order to avoid excessive oxygen enrichment and the possible formation of an explosive atmosphere in the subsequent process steps.
  • downstream oxygen removal is known in order to ensure a sufficient oxygen content at the outlet of the catalyst beds responsible for the conversion to products of value.
  • an "oxygen elimination catalyst” is only mentioned very generally.
  • a combustion of preferably carbon monoxide and possibly hydrocarbons with two and fewer carbon atoms, which can mean a corresponding loss of yield, is presented here for oxygen removal.
  • a material that is independent and different from the actual ODHE catalyst can be used and the underlying reaction is a conversion to carbon monoxide and/or carbon dioxide and water.
  • the oxygen scavenging catalyst is preferably employed in the ODH reactor downstream of the main reaction zone, and while the oxygen scavenging catalyst is similar to the ODH catalyst, it prefers additional elements such as Sb, Pt,
  • Contains Pd and Cu or Fe, ie preferably has a different composition or is even selected from a different class of catalyst.
  • the additional elements mentioned typically also mostly catalyze the conversion to carbon monoxide and/or carbon dioxide and water.
  • 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 requires minimizing adjustments to the reaction conditions, such as the reaction temperature. It is therefore necessary to stabilize the reaction conditions.
  • the present invention now makes use of the fact that the activity—also expressed below in particular as volumetric activity—of a specific catalyst material 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 ⁇ catalysts that the calcination conditions have a direct influence on their respective activity.
  • the composition of the catalytically active material remains the same in principle and can in particular be taken from the same synthesis batch.
  • the lower volumetric activity usually goes hand in hand with a lower pore volume and/or a lower BET surface area.
  • 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 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.
  • the invention exploits this in the embodiment mentioned by using a catalyst of advantageously the same type and of the same elemental composition with lower activity (i.e. a "reactive" catalyst) in terminal zones of the reaction tubes of a tube bundle reactor, which in this way as “polishing "zone can be formed.
  • a catalyst of advantageously the same type and of the same elemental composition with lower activity i.e. a "reactive” catalyst
  • the present invention proposes a process for the production of a target compound, in which a feed mixture at a temperature in a first temperature range is distributed over a multiplicity of reaction tubes of a tube bundle reactor arranged in parallel and subjected to heating to a temperature in a second temperature range in first tube sections of the reaction tubes , 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.
  • a gas mixture flowing out of the second pipe sections is brought into contact with a catalyst arranged in the third pipe sections in third pipe sections arranged downstream of the second pipe sections, the already mentioned "polishing zone" or a corresponding "polishing bed”.
  • a gas mixture flowing out of the third tube sections is removed from the tube bundle reactor without further catalytic conversion.
  • the catalyst beds provided for the catalytic conversion in the third tube sections thus represent the terminal catalyst beds of the tube bundle reactor.
  • the catalyst in this downstream polishing zone may therefore use the same catalytically active material as in the preceding main reaction zone or zones, but is preferably always designed to be relatively inert and thus insensitive to possible (sudden) changes in oxygen concentration .
  • ethane is still converted in this zone by oxidative dehydrogenation to the main product ethylene and the by-product acetic acid.
  • Carbon oxides continue to be formed only in minor amounts. This means that there is still selective added value and an unselective oxidation to form carbon oxides and water, as is the case with the catalysts for eliminating oxygen known from the prior art, is largely avoided.
  • the catalyst arranged in the third tube sections and one or at least one of the plurality of 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 the advantageous effects mentioned are particularly pronounced in the case of corresponding catalysts.
  • the catalyst arranged in the third tube sections and the one or at least one of the plurality of catalysts arranged in the second tube 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 third tube sections and the one or at least one of the plurality of catalysts arranged in the second tube sections advantageously have an identical elemental composition up, 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 third tube sections has an activity caused by different calcination intensities that is at least 10% lower than the one or at least one of the several catalysts arranged in the second tube sections.
  • the activity can also be lower, for example, by at least 20%, 30% or 40%.
  • a calcination intensity is particularly dependent on the calcination procedure, i.e. the technology used in the calcination, but also certain parameters thereof, for example a particularly intensive - e.g.
  • a less active catalyst with basically the same composition for use in the third tube sections can also be a used and thus aged catalyst, ie for example a catalyst from a more active zone, in particular from the zone with the highest activity, which is in a corresponding reactor has reached the minimum service life.
  • oxidative processes such as ODH(E) typically significantly more than 1 year up to several years - there is usually a gradual deactivation of the catalyst or reduction in the catalyst activity, which is usually compensated for by an increase in temperature.
  • the catalyst in particular the part with the highest volumetric activity in a stepped bed, is not so deactivated that it no longer has any activity at all.
  • a used catalyst can also be used for the polishing zone. In this way, part of the used catalyst can be directly reused, which reduces costs in the disposal or recycling of used catalyst or Saves cost in sourcing/manufacturing custom made catalyst for polishing bed.
  • a catalyst with the same catalytically active material can be used in whole or in part in the third tube sections.
  • a material is advantageously chosen that has a lower activity and is therefore extremely slow to react.
  • the downstream polishing zone which is formed by the third tube sections - in which a less active catalyst is used - has no significant influence on the overall reactor performance, i.e. the performance of the entirety of the reactive beds (one or more main reaction zones and polishing zone ), in terms of conversion and selectivity to commercial products, since the predominant conversion takes place in the (single- or multi-layer) catalyst bed of the main reaction zone (i.e. the second tube sections).
  • An adaptation of the overall activity by increasing the temperature is therefore still possible, but can be carried out with a significant time delay or with a reduced gradient using the present invention. This in turn results in a stabilization of the reaction conditions over time.
  • the length of the polishing zone 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 of particular relevance for the technical embodiment in which the length of the downstream polishing zone in relation to the one or more main reaction zones is less than 0.1, preferably less than 0.07 and particularly preferably less than 0. 04 is
  • a length of an area in which the catalyst is arranged in the third 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.
  • the design of the catalysts according to the present invention can be such that a volumetric activity in the third tube sections is below a maximum volumetric activity in the second tube sections due to the different production.
  • a catalyst can also be used in the polishing zone (i.e. the third tube sections) which, according to the above statements, is similar to that of the main reaction zones (i.e. the second tube sections), but which is special for the gas composition is optimized close to the outlet (i.e. in particular a comparatively high ethylene and low oxygen content).
  • Adjustable parameters e.g. composition, parameters obtained by BET analysis and the pore volume are listed below.
  • Physically measurable distinguishing features for the catalysts used can, if necessary, be derived, for example, in particular (but not conclusively) from the BET analysis known to those skilled in the art and/or the pore volume.
  • a pore volume and/or a BET surface area in the third pipe sections can be below, in particular by 15 to 60% below, a maximum pore volume and/or below a maximum BET surface area in the second pipe sections.
  • MoVNbTeO x as in the main reaction zones (ie the second tube sections), it is also possible in particular to use a catalyst which partially differs from the material in the main reaction zones.
  • a catalyst which partially differs from the material in the main reaction zones.
  • it can be a catalyst of the MoVNbO x type (ie without Te).
  • the overall bed layout can be further optimized through a combination of dilution/reactor cooling and modified active material.
  • 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 is carried out as an oxidative dehydrogenation of the paraffin.
  • One ODHE used with particular advantage uses ethane as the paraffin and performs an oxidative dehydrogenation of the ethane.
  • 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 works with comparatively low pressure.
  • 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 applied independently of the routing of the cooling medium (i.e. co-current or counter-current). Likewise, 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 region of the polishing zone, ie the third tube sections, ie there is the possibility of a separate cooling circuit (with possibly even different coolant flow directions).
  • 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, the second pipe sections and the third 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.
  • the second pipe sections are fluidically connected to third pipe sections arranged downstream of the second pipe sections, with a catalyst being arranged in the third pipe sections, which has a volumetric activity that is below the highest volumetric activity of the one or more catalysts arranged in the second pipe sections , and wherein no further catalysts are provided in the tube bundle reactor downstream of the third tube sections.
  • the use of the downstream polishing zone according to the invention i.e. the design of the third pipe sections, achieves advantages that increase the service life of the main catalyst bed, increase the tolerance of the main catalyst bed to disturbances such as deviations in temperature, flow and composition (in particular the oxygen content ), a reduction or minimization of temperature adjustments over the running time (i.e. a stabilization of the reaction conditions) and thus a minimization of a selectivity/yield decrease over time, and an improved guarantee and stabilization of a maximum acceptable oxygen concentration at the reactor outlet.
  • Figure 1 illustrates different catalyst activities for catalysts obtained at different calcination temperatures.
  • FIG. 2 illustrates a plant according to an embodiment of the present invention in a simplified schematic representation.
  • FIG. 3 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 can be influenced by the production.
  • the catalytically active material itself remains of the composition is basically the same 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
  • Example 2 DE 102017000861 A1 described in Example 2.
  • 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 1 cm balls (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. The next morning, the mixture was heated to 80° C., 107.8 g of oxalic acid dihydrate were added to the Nb 2 0s suspension and the mixture was stirred for about 1 hour.
  • 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 test 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 illustrated with C1, C2 and C3.
  • the activity of the catalysts is still further influenced, at least within certain limits, as a function of the calcination temperature (increase or decrease) as long as (even with the same calcination technology) the calcination temperature and duration - i.e. the calcination intensity - is set in such a way that either a solid/crystal phase that is sufficiently stable for catalysis is formed or the solid/crystal phase is not high calcination intensity is damaged.
  • FIG. 2 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 reaction zone(s) and the polishing zone 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, the present invention is also suitable, as mentioned, for use in higher ODH 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. and finally through a polishing zone 150 of the type previously discussed.
  • 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.
  • Third pipe sections 13 are in the polishing zone 150. Heating takes place in the first pipe sections 11 of the reaction pipes 10, and in the second pipe sections 12 of the reaction pipes 10 arranged downstream of the first pipe sections 11, the correspondingly preheated feed mixture A is subjected to an oxidative catalytic conversion using one or more catalysts arranged in the second pipe sections 12 subject.
  • a gas mixture flowing out of the second pipe sections 12 is brought into contact in the third pipe sections 13 arranged downstream of the second pipe sections 12 with a catalyst arranged in the third pipe sections 13, which catalyst has a volumetric activity below the highest volumetric activity of one or the a plurality of catalysts arranged in the second tube sections 12, and a gas mixture flowing out of the third tube sections 13 is removed from the tube bundle reactor 100 without further catalytic conversion.
  • the process gas can be brought into contact with washing water or a suitable aqueous solution, as a result of which the process gas can in particular be 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 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé de préparation d'un composé cible, selon lequel un mélange de charge (A) à une température dans une première plage de température est distribué sur une pluralité de tubes de réaction parallèles (10) d'un réacteur à faisceau tubulaire (100) ; subit un chauffage à une température dans une seconde plage de températures dans des premières parties de tube (11) des tubes de réaction (10) ; et subit une conversion catalytique oxydative dans des deuxièmes parties de tube (12) des tubes de réaction (10), en aval des premières parties de tube (11), à l'aide d'un ou de plusieurs catalyseurs situés dans les deuxièmes parties de tube (12). L'invention est caractérisée en ce que, dans des troisièmes parties de tube (13) situées en aval des deuxièmes parties de tube (12), un mélange gazeux s'écoulant hors des deuxièmes parties de tube (12) est mis en contact avec un catalyseur situé dans les troisièmes parties de tube (13), ledit catalyseur ayant une activité volumétrique qui est inférieure à l'activité volumétrique la plus élevée du ou des catalyseurs situés dans les deuxièmes parties de tube (12), et un mélange gazeux s'écoulant hors des troisièmes parties de tube (13) est retiré du réacteur à faisceau tubulaire (100) sans conversion catalytique supplémentaire. L'invention concerne également un système correspondant.
EP22712938.4A 2021-03-15 2022-03-14 Procédé et système de préparation d'un composé cible Pending EP4308527A1 (fr)

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DE102021202500.5A DE102021202500A1 (de) 2021-03-15 2021-03-15 Verfahren und Anlage zur Herstellung einer Zielverbindung
PCT/EP2022/056573 WO2022194795A1 (fr) 2021-03-15 2022-03-14 Procédé et système de préparation d'un composé cible

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EP (1) EP4308527A1 (fr)
CN (1) CN117203179A (fr)
CA (1) CA3212562A1 (fr)
DE (1) DE102021202500A1 (fr)
WO (1) WO2022194795A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE19837519A1 (de) 1998-08-19 2000-02-24 Basf Ag Verfahren zur Herstellung von Acrolein und/oder Acrylsäure aus Propan
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
US8519210B2 (en) 2009-04-02 2013-08-27 Lummus Technology Inc. Process for producing ethylene via oxidative dehydrogenation (ODH) of ethane
EP2716621A1 (fr) 2012-10-05 2014-04-09 Linde Aktiengesellschaft Installation de réacteur et procédé pour la déshydrogénation oxydative d'alcanes
EP2716622A1 (fr) 2012-10-05 2014-04-09 Linde Aktiengesellschaft Installation de réacteur et procédé pour la déshydrogénation oxydative d'alcanes
RU2730518C2 (ru) 2016-02-26 2020-08-24 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Окислительное дегидрирование алканов (од)
EP3318545A1 (fr) 2016-11-03 2018-05-09 Linde Aktiengesellschaft Procédé et installation de fabrication d'oléfines
EP3339277A1 (fr) 2016-12-22 2018-06-27 Linde Aktiengesellschaft Procédé et installation de production d'une oléfine
EP3339276A1 (fr) 2016-12-22 2018-06-27 Linde Aktiengesellschaft Procédé et installation de production d'une oléfine
EP3339275A1 (fr) 2016-12-22 2018-06-27 Linde Aktiengesellschaft Procédé et installation de production d'éthylène et acide acétique
DE102017000861A1 (de) 2017-01-31 2018-08-02 Clariant Produkte (Deutschland) Gmbh Synthese eines MoVTeNb-Katalysators aus preisgünstigen Metalloxiden
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

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CN117203179A (zh) 2023-12-08
CA3212562A1 (fr) 2022-09-22
WO2022194795A1 (fr) 2022-09-22
US20240158322A1 (en) 2024-05-16

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