EP1536882A1 - Procede autothermique comprenant une inversion d'ecoulement periodique - Google Patents

Procede autothermique comprenant une inversion d'ecoulement periodique

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Publication number
EP1536882A1
EP1536882A1 EP03757758A EP03757758A EP1536882A1 EP 1536882 A1 EP1536882 A1 EP 1536882A1 EP 03757758 A EP03757758 A EP 03757758A EP 03757758 A EP03757758 A EP 03757758A EP 1536882 A1 EP1536882 A1 EP 1536882A1
Authority
EP
European Patent Office
Prior art keywords
regeneration
fixed bed
temperature
phase
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03757758A
Other languages
German (de)
English (en)
Inventor
Gerhart Eigenberger
Bernd Glöckler
Gregorius Kolios
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.)
Evonik Operations GmbH
Original Assignee
Eigenberger Gerhart
Glockler Bernd
Kolios Gregorius
Evonik Degussa 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 Eigenberger Gerhart, Glockler Bernd, Kolios Gregorius, Evonik Degussa GmbH filed Critical Eigenberger Gerhart
Publication of EP1536882A1 publication Critical patent/EP1536882A1/fr
Withdrawn legal-status Critical Current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
    • B01J8/0285—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
    • 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
    • B01J8/0207—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 the fluid flow within the bed being predominantly horizontal
    • B01J8/0221—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 the fluid flow within the bed being predominantly horizontal in a cylindrical shaped bed
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0403—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 the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423—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 the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0438—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 the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being placed next to each other
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/46—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using discontinuously preheated non-moving solid materials, e.g. blast and run
    • 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
    • B01J2208/00026—Controlling or regulating the heat exchange system
    • B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044—Temperature measurement
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • 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
    • B01J2208/00327—Controlling the temperature by direct heat exchange
    • B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
    • B01J2208/00353—Non-cryogenic fluids
    • B01J2208/00371—Non-cryogenic fluids gaseous
    • 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
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00398—Controlling the temperature using electric heating or cooling elements inside the reactor bed
    • 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
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
    • 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
    • B01J2208/00504—Controlling the temperature by means of a burner
    • 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
    • B01J2208/00522—Controlling the temperature using inert heat absorbing solids outside the bed
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00193—Sensing a parameter
    • B01J2219/00195—Sensing a parameter of the reaction system
    • B01J2219/002—Sensing a parameter of the reaction system inside 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00243—Mathematical modelling
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to an autothermal process for coupling endothermic and exothermic reactions in reactors with periodic flow reversal.
  • these can be high-temperature reactions.
  • thermodynamic equilibrium endothermic synthesis reactions often require high temperatures of 500 to 1000 ° C in order to proceed with a sufficiently high conversion.
  • Typical examples are dehydrogenation and steam reforming of hydrocarbons to produce synthesis gas.
  • the gaseous or vaporous starting materials must first be heated to the reaction temperature and then the required enthalpy of reaction must be supplied to them at high temperature.
  • the heat required for this is provided by an exothermic accompanying reaction, usually a combustion reaction.
  • the present application extends the state of the art laid down in PCT / EP00 / 10928 by concrete inventive configurations for the above-mentioned asymmetrical case in which one endothermic reaction in a cyclical change with an exothermic accompanying reaction in a catalytic fixed bed reactor with periodic change of the flow direction is to be carried out.
  • the invention is based on the following concept: If gaseous or vaporous feedstocks for an endothermic reaction at low temperature are introduced into an adiabatic catalyst bed which is uniformly preheated to a sufficiently high temperature T ma ⁇ , a pronounced temperature which migrates in the direction of flow develops. and turnover front, in which a turnover is reached which corresponds to the equilibrium turnover at the temperature T ma ⁇ .
  • Low temperature is understood to mean the ambient temperature or a temperature which is above or at the temperature at which the substances in question are gaseous or vaporous.
  • a sufficiently high temperature T ma ⁇ is understood to mean a temperature at which the endothermic reaction is so rapid that it largely takes place in a manner controlled by equilibrium and at the same time the equilibrium conversion is sufficient for technical applications.
  • the production phase of the endothermic reaction lasts as long as the reaction front is in the active part of the catalyst bed.
  • the fixed bed cools down in the production phase.
  • the production phase must be followed by a regeneration phase in which the catalyst bed is heated up again to the original uniform temperature T max .
  • the regeneration takes place according to the invention in that a regeneration stream with a low temperature is fed continuously to the reactor during the regeneration phase in countercurrent to the production phase, the
  • Production time corresponds to ⁇ ⁇ .
  • This regeneration gas stream is supplied with heat at several discrete points arranged over the length of the catalytically active region and distributed over the flow cross-section such that the original temperature profile is set again at the end of the regeneration phase.
  • the distance between the feed points is' about to be selected so long as a pure temperature front during the duration of the regeneration passes through the catalyst bed.
  • a further embodiment results if the inlets already have a high temperature.
  • the reaction mixture continuously enters the front end of the reactor and is heated by the fixed bed to the temperature T ma ⁇ necessary for the required conversion, where T m a is greater than or equal to a minimum preheating temperature T j. and reacts in a catalytically active part of the fixed bed, whereby the fixed bed cools down.
  • a regeneration stream with the desired maximum temperature T max is passed through the catalytically active fixed bed until the entire catalytically active area has again reached the maximum temperature T max .
  • Figures 2a and 2b Diagrams of the temperature and turnover curve in the method according to the invention
  • Figure 3 Diagrams for changing the
  • Figure 4 a reactor structure.
  • FIGS. 1 a and 1 b show, using the example of steam reforming of methane and assuming a reaction conversion determined only by the temperature, how the temperature front spreads through the catalyst bed starting from temperature profile 1 or 1 ′.
  • the length coordinate of the catalyst bed is designated z and is given in meters.
  • the temperature rises very quickly from a base temperature TB to the preheating or maximum temperature T max in the fixed bed, while the turnover increases accordingly.
  • An implicit determination equation is given below for the asymptotic final value of the base temperature in a sufficiently long catalyst bed.
  • the higher the preheating temperature T max the slower the front moves and the lower the base temperature T B ( Figure lb).
  • the minimum preheating temperature Ti of the catalyst bed from which a pronounced front is formed under the conditions mentioned, follows from the condition: d 2 x
  • X is the equilibrium conversion of the endothermic reaction which depends on the reaction temperature T. Its gradient
  • Velocity of migration of a fictitious, dissipation-free thermal front which is an inert gas flow with the same
  • the fixed bed reactor should be as in FIG. 2 be sketched.
  • the fixed bed consists of a catalytically active zone and an inert edge zone, which are arranged one behind the other in the direction of flow.
  • the catalytically active zone can also be preceded by a short inert zone.
  • the temperature profile at the beginning of the production phase (state 1) has an increasing one
  • the subsequent inert bed prevents the sales from falling again as the temperature drops.
  • the outlet temperature is constantly at the level of the inlet temperature during this time interval. This prevents sensible heat from being discharged from the reactor.
  • the heat storage capacity of the fixed bed made of catalyst and inert material is largely exhausted and the outlet temperature would then rise (state 2).
  • the dashed lines show the temperature and turnover curves at the end of the production phase.
  • the dotted lines in between represent profiles at times between states 1 and 2.
  • the peripheral zone can also contain a catalyst for a desirable subsequent reaction. However, it must not catalyze the main endothermic reaction.
  • a typical example in the case of steam reforming of methane would be the replacement of the inert peripheral zone with a water gas shift catalyst, in which CO and water vapor are increasingly converted into CO 2 and hydrogen as the temperature drops.
  • the regeneration of the bed from state 2 to state 1 is required to implement an efficient cyclic process.
  • the process conditions during the regeneration phase must meet the following requirements:
  • the profile of the maximum temperature T max is set by regulating the local heat input via temperature sensors which are installed in the vicinity of the feeds and downstream in the direction of the regeneration current.
  • the heat input can z. B. by in the Catalyst bed installed heating elements or by hot gas feed.
  • a solution is particularly preferred in which a reactant for an exothermic reaction is admixed to the regeneration gas stream at the feed points, which reacts automatically at the prevailing temperature and takes place completely, e.g. B. a catalytic combustion.
  • FIG. 3 schematically shows the configuration of a fixed bed reactor with temperature-controlled side feed of a reactant required for the regeneration and the basic change in the temperature fronts during the regeneration time.
  • the temperature controller is labeled TC. It can be seen how the temperature fronts generated at the feed points replenish the broken temperature profile and at the same time a shift of the temperature profile flanks takes place at the entry and exit of the (inert) bed to the starting position.
  • FIG. 4 shows a possible reactor structure according to the invention using the example of steam reforming of methane.
  • the reactor 1 contains an axially structured fixed bed with the inert edge zones 2 and 4 and the catalytically active zone 3, which is filled with a suitable reforming catalyst.
  • Four distributors 5 for feeding an additional stream are integrated in the reactor 1.
  • the distributors are supplied by axially guided supply lines that have good thermal contact with the surrounding fixed bed.
  • the distance between the distributors corresponds to the distance that a fictitious thermal front would cover during the regeneration phase.
  • Thermocouples 6 are installed in the vicinity of the distributors and are used to regulate the temperature of the reactor.
  • the reactor 1 is mixed with a mixture 7 of technically relevant feed composition
  • the distributors 5 are supplied with a fuel 9, for example methane, or the exhaust gas of a pressure swing adsorption system for hydrogen purification.
  • the throughput in the supply lines is set by means of control valves 10 so that the temperature of the measuring points is regulated to 1000 K.
  • a fuel-containing main stream 8 can also be fed to the reactor during the regeneration phase, in which an oxygen-containing gas, e.g. B. air is added.
  • the cyclic process described is characterized by a high level of energy efficiency, since the inlet and outlet take place (relatively) cold in both the production and regeneration period and the high temperature required for the endothermic reaction remains completely in the reactor.
  • Ti is the temperature that the catalyst bed reached at the end of the production phase.
  • An endothermic reaction can advantageously be carried out in the manner described.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention concerne un procédé autothermique permettant d'effectuer des réactions endothermiques dans des réacteurs à lits fixes adiabatiques (4) et faisant intervenir, de manière alternée et cyclique, une phase de production pour la réaction endothermique ainsi qu'une phase de régénération pour l'apport de chaleur. Lors de la phase de production, un mélange réactionnel (7) présentant une faible température pénètre en continu dans le réacteur, par l'extrémité avant, et est chauffé par l'intermédiaire d'un lit fixe jusqu'à ce qu'il atteigne la température Tmax nécessaire à la conversion exigée, Tmax étant supérieure ou égale à la température de préchauffage minimale TI. Puis, ce mélange réactionnel réagit dans une partie catalytiquement active du lit fixe, refroidit simultanément le lit fixe, et sort du réacteur par une zone inerte arrière située en aval de ladite partie catalytiquement active ou par un lit fixe catalytique supplémentaire. Lors de la phase de régénération, un courant de régénération (8) présentant une faible température est introduit en continu dans le réacteur, par l'extrémité arrière, et est retiré à l'avant. La capacité de chauffage totale m< >PCPR DELTA t R du courant de régénération m< >R pour la durée de régénération <TR correspond à une valeur comprise entre 70 et 300 %, de préférence entre 80 et 120 %, de la capacité de chauffage totale m< >pCpp DELTA t p correspondante dudit mélange réactionnel pour la durée de production ?t p. De la chaleur est fournie au niveau de plusieurs emplacements discrets (5) disposés sur la longueur de ladite zone catalytiquement active et est répartie sur la section transversale d'écoulement de façon à permettre le rétablissement d'un profil de températures initial à la fin de ladite phase de régénération.
EP03757758A 2002-08-23 2003-08-13 Procede autothermique comprenant une inversion d'ecoulement periodique Withdrawn EP1536882A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10239547 2002-08-23
DE10239547A DE10239547A1 (de) 2002-08-23 2002-08-23 Autothermes Verfahren zur Kopplung endothermer und exothermer Reaktionen in Reaktoren mit periodischer Strömungsumkehr
PCT/EP2003/008981 WO2004026456A1 (fr) 2002-08-23 2003-08-13 Procede autothermique comprenant une inversion d'ecoulement periodique

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FR2991596B1 (fr) * 2012-06-08 2015-08-07 Arkema France Reaction catalytique avec regeneration en flux inverse
EP3599015A1 (fr) * 2018-07-26 2020-01-29 Yncoris GmbH & Co. KG Procédé de mise en réaction catalytique endothermique d'hydrocarbures de départ réticulés

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DE19953233A1 (de) * 1999-11-04 2001-05-10 Grigorios Kolios Autotherme Reaktorschaltungen zur direkten Kopplung endothermer und exothermer Reaktionen

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