WO2012143096A1 - Membrane reactor for producing hydrogen - Google Patents

Membrane reactor for producing hydrogen Download PDF

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Publication number
WO2012143096A1
WO2012143096A1 PCT/EP2012/001530 EP2012001530W WO2012143096A1 WO 2012143096 A1 WO2012143096 A1 WO 2012143096A1 EP 2012001530 W EP2012001530 W EP 2012001530W WO 2012143096 A1 WO2012143096 A1 WO 2012143096A1
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WO
WIPO (PCT)
Prior art keywords
jacket tube
longitudinal axis
space
partition
reactor
Prior art date
Application number
PCT/EP2012/001530
Other languages
German (de)
French (fr)
Inventor
Hans-Jörg ZANDER
Axel Behrens
Klemens Wawrzinek
Fokke Bokker
Benjamin Dittmar
Bernhard BEESE
Original Assignee
Linde Aktiengesellschaft
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 Linde Aktiengesellschaft filed Critical Linde Aktiengesellschaft
Publication of WO2012143096A1 publication Critical patent/WO2012143096A1/en

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Classifications

    • 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
    • C01B3/384—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 the catalyst being continuously externally heated
    • 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
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
    • 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
    • B01J8/0242—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 vertical
    • B01J8/0257—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 vertical in a cylindrical annular shaped bed
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • 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
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • the invention relates to a reactor for the production of hydrogen, comprising a reaction chamber enclosed by a jacket tube with a catalyst arranged therein, for carrying out a steam reforming, an at least partially selectively hydrogen-permeable partition which forms a discharge space arranged between the inside and the longitudinal axis of the jacket tube, can be removed from the reactor via the hydrogen, as well as a feed device via which feedstocks can be introduced into the reaction space at one end of the jacket tube.
  • Such a device which is referred to hereinafter as a membrane reactor, is known for example from the patent applications EP0167101 and WO2010 / 000375.
  • the selectively hydrogen-permeable partition wall is arranged here in the form of one or more membrane tubes in a jacket tube, wherein the longitudinal axes of the membrane or tubes run parallel to the longitudinal axis of the jacket tube.
  • the apparatus may be used for steam reforming of a hydrocarbonaceous feed.
  • the hydrocarbon-containing use such as
  • Jacket tube introduced into the reaction chamber, where it is reacted with the aid of a suitable catalyst mainly in hydrogen and carbon dioxide.
  • the hydrogen formed is continuously withdrawn from the reaction space via the selectively hydrogen-permeable partition wall and passed on with high purity.
  • the removal of the hydrogen from the reaction space is with a
  • the free space within the jacket tube is completely filled with catalyst, so that there is catalyst both in the space between the inside of the jacket tube and the partition wall, as well as in the space between the partition wall and the longitudinal axis of the jacket tube.
  • the heat required for the total endothermic reactions is the reaction space on the
  • Object of the present invention is therefore to provide a reactor of the initially
  • Catalyst material is.
  • the invention makes it possible to increase the average temperature of the catalyst arranged in the reaction space, whereby it can be used much more effectively than is possible according to the prior art. In addition, the risk of soot formation can be significantly reduced.
  • a partition wall comprises at least five membrane tubes, which are arranged so that their longitudinal axes all lie on a cylinder jacket whose longitudinal axis coincides with the longitudinal axis of the jacket tube.
  • Membrane tubes can be arranged arbitrarily. Preferably, however, the center distances of immediately adjacent membrane tubes are each the same size.
  • the circumference of the cylinder jacket can be chosen so that touch the membrane tubes arranged on it. With such an arrangement, however, thermally induced stresses and possibly damage to the membrane tubes may occur during operation of the reactor according to the invention. In addition, part of the valuable membrane surface is not for separation purposes
  • Feeding device for the starting materials is located. This construction allows a reduction of the overall height and a simplified handling of the reactor, since hydrogen formed in the reaction space can be withdrawn via the same end of the jacket tube via which the starting materials can be introduced into the reaction space.
  • Jacket tube can be used.
  • a further preferred embodiment of the invention provides that at least a portion of the space located between the longitudinal axis of the jacket tube and the partition wall by a gas-tight wall, preferably directly to the
  • Dividing wall connects, is separated from the reaction space. This allows the
  • FIG. 1 shows a longitudinal section of a preferred embodiment of the reactor according to the invention.
  • the reactor R comprises a jacket tube M, between the inside I and
  • the partition wall T preferably consists of more than five membrane tubes, which are arranged on a cylinder jacket whose longitudinal axis coincides with the longitudinal axis L of the jacket tube.
  • the space between the inside I of the jacket tube M and the partition wall T forms a reaction space Z, which is filled with catalyst material K, while the space between the partition wall T and the longitudinal axis L of the jacket tube M is free of catalyst material.
  • Catalyst K with a small distance a protective grid S attached.
  • feedstocks 1 such as, for example, steam and methane
  • feed device not shown
  • catalytic support to carbon dioxide and hydrogen.
  • a gas-tight wall W between the partition wall T and the longitudinal axis L of the jacket tube M is arranged. In which located between the longitudinal axis L of the jacket tube M and the partition wall T,
  • catalyst-free space runs a connected to the exhaust space A (compound not shown) exhaust pipe B, on the formed in the catalyst material K.
  • Hydrogen 3 can be withdrawn as a permeate with high purity from the reactor R, while predominantly consisting of carbon dioxide retentate 2 via a take-off device (not shown) can be derived from the reactor.
  • the diameter of the exhaust pipe B can be selected so that it simultaneously performs the tasks of the gas-tight wall W.

Abstract

The invention relates to a reactor (R) for producing hydrogen (3), comprising a reaction chamber (Z) that is enclosed by a tubular jacket (M) and has a catalyst (K) suitable for carrying out a steam reforming arranged therein, a partition (T) that is selectively hydrogen-permeable at least in some areas and forms a discharge chamber (A) disposed between the inner face (I) and the longitudinal axis (L) of the tubular jacket (M), via which hydrogen (3) can be withdrawn from the reactor (R), and a feeding device, via which charge materials (1) can be introduced into the reaction chamber (Z) at one end of the tubular jacket (M). The reactor (R) is characterized in that the chamber arranged between the longitudinal axis (L) of the tubular jacket (M) and the partition (T) is free from catalyst material.

Description

Beschreibung  description
Membranreaktor zur Erzeugung von Wasserstoff Membrane reactor for the production of hydrogen
Die Erfindung betrifft einen Reaktor zur Erzeugung von Wasserstoff, aufweisend einen von einem Mantelrohr umschlossenen Reaktionsraum mit einem darin angeordneten, zur Durchführung einer Dampfreformierung geeigneten Katalysator, eine zumindest abschnittsweise selektiv wasserstoffdurchlässige Trennwand, die einen zwischen der Innenseite und der Längsachse des Mantelrohres angeordneten Abzugsraum bildet, über den Wasserstoff aus dem Reaktor abziehbar ist, sowie eine Zuführeinrichtung, über die Einsatzstoffe an einem Ende des Mantelrohres in den Reaktionsraum einleitbar sind. The invention relates to a reactor for the production of hydrogen, comprising a reaction chamber enclosed by a jacket tube with a catalyst arranged therein, for carrying out a steam reforming, an at least partially selectively hydrogen-permeable partition which forms a discharge space arranged between the inside and the longitudinal axis of the jacket tube, can be removed from the reactor via the hydrogen, as well as a feed device via which feedstocks can be introduced into the reaction space at one end of the jacket tube.
Eine derartige Vorrichtung, die im Weiteren als Membranreaktor bezeichnet wird, ist beispielsweise aus den Patentanmeldungen EP0167101 und WO2010/000375 bekannt. Die selektiv wasserstoffdurchlässige Trennwand ist hier in Form eines oder mehrerer Membranrohre in einem Mantelrohr angeordnet, wobei die Längsachsen des oder der Membranrohre parallel zur Längsachse des Mantelrohres verlaufen. Die Vorrichtung kann zur Dampfreformierung eines kohlenwasserstoffhaltigen Einsatzes verwendet werden. Dabei wird der kohlenwasserstoffhaltige Einsatz, wie Such a device, which is referred to hereinafter as a membrane reactor, is known for example from the patent applications EP0167101 and WO2010 / 000375. The selectively hydrogen-permeable partition wall is arranged here in the form of one or more membrane tubes in a jacket tube, wherein the longitudinal axes of the membrane or tubes run parallel to the longitudinal axis of the jacket tube. The apparatus may be used for steam reforming of a hydrocarbonaceous feed. In this case, the hydrocarbon-containing use, such as
beispielsweise Methan, gemeinsam mit Wasserdampf an einem Ende des For example, methane, along with water vapor at one end of the
Mantelrohres in den Reaktionsraum eingeleitet, wo er mit Hilfe eines geeigneten Katalysators vorwiegend in Wasserstoff und Kohlendioxid umgesetzt wird. Im Jacket tube introduced into the reaction chamber, where it is reacted with the aid of a suitable catalyst mainly in hydrogen and carbon dioxide. in the
Wesentlichen laufen hierbei eine Reformierungs- und eine Konvertierungsreaktion nach den folgenden Reaktionsgleichungen ab: CnHm + nH20 <=> nCO + (m/2+n)H2 Essentially, a reforming reaction and a conversion reaction proceed according to the following reaction equations: C n H m + nH 2 O <== nCO + (m / 2 + n) H 2
CO + H20 o C02 + H2 CO + H 2 0 o C0 2 + H 2
Der gebildete Wasserstoff wird über die selektiv wasserstoffdurchlässige Trennwand kontinuierlich aus dem Reaktionsraum abgezogen und mit hoher Reinheit weiter geführt. Das Abziehen des Wasserstoffs aus dem Reaktionsraum ist mit einerThe hydrogen formed is continuously withdrawn from the reaction space via the selectively hydrogen-permeable partition wall and passed on with high purity. The removal of the hydrogen from the reaction space is with a
Gleichgewichtsverschiebung der im Reaktionsraum ablaufenden Reaktionen zur Seite der Produkte verbunden. Dies bewirkt eine höhere Wasserstoffausbeute bei gleichzeitiger Verminderung der Kohlenmonoxidkonzentration. Entscheidend für die Trennleistung der Membran ist die Höhe des zwischen ihrer Retentatseite, die dem Reaktionsraum zugewandt ist, und der dieser gegenüber liegenden sog. Permeatseite bestehenden Unterschieds des Wasserstoff-Partialdrucks; je größer dieser Equilibrium shift associated with the reactions occurring in the reaction space to the side of the products. This causes a higher hydrogen yield at simultaneous reduction of the carbon monoxide concentration. Decisive for the separation performance of the membrane is the height of between its retentate, which faces the reaction space, and the opposite of this so-called. Permeatseite existing difference in the hydrogen partial pressure; the bigger this one
Unterschied, umso höher ist die Trennleistung. Difference, the higher the separation efficiency.
Nach dem Stand der Technik ist der freie Raum innerhalb des Mantelrohres vollständig mit Katalysator gefüllt, so dass sich sowohl im Raum zwischen der Innenseite des Mantelrohres und der Trennwand, als auch im Raum zwischen der Trennwand und der Längsachse des Mantelrohres Katalysator befindet. Die für die insgesamt endotherm verlaufenden Reaktionen benötigte Wärme wird dem Reaktionsraum über die According to the prior art, the free space within the jacket tube is completely filled with catalyst, so that there is catalyst both in the space between the inside of the jacket tube and the partition wall, as well as in the space between the partition wall and the longitudinal axis of the jacket tube. The heat required for the total endothermic reactions is the reaction space on the
Außenseite des Mantelrohres zugeführt, wodurch die Temperatur in radialer Richtung von außen nach innen abnimmt. Der sich direkt an die Innenseite des Mantelrohres anschließende Katalysator bildet einen Schutz für die Trennwand, deren Temperatur i.Allg. einen vergleichsweise niedrigen Grenzwert nicht überschreiten darf. Weiter innen angeordneter Katalysator weist eine noch niedrigere Temperatur als die Outside of the jacket tube supplied, whereby the temperature decreases in the radial direction from outside to inside. The catalyst which adjoins directly to the inside of the jacket tube forms a protection for the partition, the temperature of which i.Allg. may not exceed a comparatively low limit. Further inwardly disposed catalyst has an even lower temperature than that
Trennwand auf, wodurch in diesem Bereich des Reaktionsraumes eine wesentlich geringere Umsatzleistung erzielt werden kann, als in dem unmittelbar an die Innenseite des Mantelrohres angrenzenden Bereich. Außerdem begünstigen die niedrigen Temperaturen die Bildung von Ruß. Partition on, whereby in this region of the reaction chamber, a much lower sales performance can be achieved, as in the immediately adjacent to the inside of the jacket tube area. In addition, the low temperatures favor the formation of soot.
Aufgabe der vorliegenden Erfindung ist daher, einen Reaktor der eingangs Object of the present invention is therefore to provide a reactor of the initially
beschriebenen Art anzugeben, durch den die Nachteile des Standes der Technik überwunden werden. To specify type described by which the disadvantages of the prior art are overcome.
Die gestellte Aufgabe wird erfindungsgemäß dadurch gelöst, dass der zwischen der Längsachse des Mantelrohres und der Trennwand gelegene Raum frei von The stated object is achieved in that the space between the longitudinal axis of the jacket tube and the partition wall free of space
Katalysatormaterial ist. Die Erfindung erlaubt es, die mittlere Temperatur des im Reaktionsraum angeordneten Katalysators zu erhöhen, wodurch er wesentlich effektiver genutzt werden kann, als dies nach dem Stand der Technik möglich ist. Darüber hinaus kann die Gefahr einer Rußbildung deutlich verringert werden. Für den Aufbau der selektiv wasserstoffdurchlässigen Trennwand können Catalyst material is. The invention makes it possible to increase the average temperature of the catalyst arranged in the reaction space, whereby it can be used much more effectively than is possible according to the prior art. In addition, the risk of soot formation can be significantly reduced. For the construction of the selectively hydrogen-permeable partition can
Membranrohre eingesetzt werden, wie sie beispielsweise aus dem Stand der Technik bekannt sind. Vorzugsweise umfasst eine Trennwand wenigstens fünf Membranrohre, die so angeordnet sind, dass ihre Längsachsen alle auf einem Zylindermantel liegen, dessen Längsachse mit der Längsachse des Mantelrohres zusammenfällt. Die Membrane tubes are used, as for example from the prior art are known. Preferably, a partition wall comprises at least five membrane tubes, which are arranged so that their longitudinal axes all lie on a cylinder jacket whose longitudinal axis coincides with the longitudinal axis of the jacket tube. The
Membranrohre können dabei beliebig angeordnet sein. Vorzugsweise sind jedoch die Achsabstände unmittelbar benachbarter Membranrohre jeweils gleich groß. Membrane tubes can be arranged arbitrarily. Preferably, however, the center distances of immediately adjacent membrane tubes are each the same size.
Der Umfang des Zylindermantels kann so gewählt werden, dass sich die auf ihm angeordneten Membranrohre berühren. Bei einer solchen Anordnung kann es jedoch während des Betriebs des erfindungsgemäßen Reaktors zu thermisch induzierten Spannungen und evtl. zu Beschädigungen der Membranrohre kommen. Darüber hinaus steht ein Teil der wertvollen Membranfläche nicht für Trennzwecke zur The circumference of the cylinder jacket can be chosen so that touch the membrane tubes arranged on it. With such an arrangement, however, thermally induced stresses and possibly damage to the membrane tubes may occur during operation of the reactor according to the invention. In addition, part of the valuable membrane surface is not for separation purposes
Verfügung. Es wird daher vorgeschlagen, die Membranrohre mit einem endlichen Abstand zueinander anzuordnen, wobei die Achsabstände unmittelbar benachbarter Membranrohre vorzugsweise kleiner sind als der zweifache Durchmesser eines Membranrohres. Available. It is therefore proposed to arrange the membrane tubes with a finite distance from each other, wherein the axial distances of immediately adjacent membrane tubes are preferably smaller than twice the diameter of a membrane tube.
Eine bevorzugte Ausgestaltung der Erfindung sieht vor, dass ein mit dem durch die selektiv wasserstoffdurchlässige Trennwand gebildeten Abzugsraum verbundenes Abzugsrohr durch den zwischen der Längsachse des Mantelrohres und der Trennwand gelegene Raum zu dem Ende des Mantelrohres verläuft, an dem sich die A preferred embodiment of the invention provides that an exhaust pipe connected to the exhaust space formed by the selectively hydrogen-permeable partition wall extends through the space located between the longitudinal axis of the jacket pipe and the partition wall to the end of the jacket tube on which the
Zuführeinrichtung für die Einsatzstoffe befindet. Diese Bauweise ermöglicht eine Reduzierung der Bauhöhe sowie eine vereinfachte Handhabung des Reaktors, da im Reaktionsraum gebildeter Wasserstoff über dasselbe Ende des Mantelrohres abgezogen werden kann, über das die Einsatzstoffe in den Reaktionsraum einleitbar sind. Darüber hinaus kann das Abzugsrohr zur Befestigung der Trennwand im  Feeding device for the starting materials is located. This construction allows a reduction of the overall height and a simplified handling of the reactor, since hydrogen formed in the reaction space can be withdrawn via the same end of the jacket tube via which the starting materials can be introduced into the reaction space. In addition, the exhaust pipe for fixing the partition in
Mantelrohr verwendet werden. Jacket tube can be used.
Eine weitere bevorzugte Ausgestaltung der Erfindung sieht vor, dass wenigstens ein Teil des zwischen der Längsachse des Mantelrohres und der Trennwand gelegenen Raumes durch eine gasdichte Wand, die sich vorzugsweise unmittelbar an die A further preferred embodiment of the invention provides that at least a portion of the space located between the longitudinal axis of the jacket tube and the partition wall by a gas-tight wall, preferably directly to the
Trennwand anschließt, vom Reaktionsraum abgetrennt ist. Hierdurch kann die Dividing wall connects, is separated from the reaction space. This allows the
Ausbildung von Bypass-Strömungen verhindert oder zumindest minimiert werden, die im Betrieb des Reaktors den Katalysator umgehen. Derartige Strömungen vermindern die Umsatzleistung des Reaktors und können zu unerwünschten Nebenreaktionen führen. Besonders bevorzugt ist die gasdichte Wand durch das Abzugsrohr gebildet. Im Folgenden soll die Erfindung anhand eines in der Figur 1 schematisch dargestellten Ausführungsbeispiels näher erläutert werden. Die Figur 1 zeigt eine bevorzugte Ausführungsform des erfindungsgemäßen Reaktors im Längsschnitt. Preventing or at least minimizing the formation of by-pass flows bypassing the catalyst during operation of the reactor. Such flows reduce the conversion efficiency of the reactor and can lead to undesirable side reactions. Particularly preferably, the gas-tight wall is formed by the exhaust pipe. In the following, the invention will be explained in more detail with reference to an exemplary embodiment shown schematically in FIG. FIG. 1 shows a longitudinal section of a preferred embodiment of the reactor according to the invention.
Der Reaktor R umfasst ein Mantelrohr M, zwischen dessen Innenseite I und The reactor R comprises a jacket tube M, between the inside I and
Längsachse L eine selektiv wasserstoffdurchlässige Trennwand T angeordnet ist, die einen Abzugsraum A bildet. Die Trennwand T besteht vorzugsweise aus mehr als fünf Membranröhrchen, die auf einem Zylindermantel angeordnet sind, dessen Längsachse mit der Längsachse L des Mantelrohres zusammenfällt. Der Raum zwischen der Innenseite I des Mantelrohrs M und der Trennwand T bildet einen Reaktionsraum Z, der mit Katalysatormaterial K gefüllt ist, während der Raum zwischen der Trennwand T und der Längsachse L des Mantelrohres M frei von Katalysatormaterial ist. Zum Schutz vor mechanischen Beschädigungen ist zwischen der Trennwand T und dem Longitudinal axis L is a selectively hydrogen-permeable partition T is arranged, which forms a discharge space A. The partition wall T preferably consists of more than five membrane tubes, which are arranged on a cylinder jacket whose longitudinal axis coincides with the longitudinal axis L of the jacket tube. The space between the inside I of the jacket tube M and the partition wall T forms a reaction space Z, which is filled with catalyst material K, while the space between the partition wall T and the longitudinal axis L of the jacket tube M is free of catalyst material. To protect against mechanical damage is between the partition T and the
Katalysatormaterial K mit geringem Abstand ein Schutzgitter S angebracht. Im Betrieb des Reaktors R werden Einsatzstoffe 1 , wie beispielsweise Wasserdampf und Methan, über eine Zuführeinrichtung (nicht dargestellt) in den Reaktionsraum Z eingeleitet und dort mit katalytischer Unterstützung zu Kohlendioxid und Wasserstoff umgesetzt. Um zu verhindern, dass noch nicht umgesetzte Einsatzstoffe als Bypass-Ströme am Katalysatormaterial K vorbeigeführt werden, ist eine gasdichte Wand W zwischen der Trennwand T und der Längsachse L des Mantelrohrs M angeordnet. In dem zwischen der Längsachse L des Mantelrohres M und der Trennwand T gelegenen, Catalyst K with a small distance a protective grid S attached. During operation of the reactor R, feedstocks 1, such as, for example, steam and methane, are introduced into the reaction space Z via a feed device (not shown) and converted there with catalytic support to carbon dioxide and hydrogen. In order to prevent that unreacted starting materials are bypassed as bypass streams on the catalyst material K, a gas-tight wall W between the partition wall T and the longitudinal axis L of the jacket tube M is arranged. In which located between the longitudinal axis L of the jacket tube M and the partition wall T,
katalysatorfreien Raum verläuft ein mit dem Abzugsraum A verbundenes (Verbindung nicht dargestellt) Abzugsrohr B, über das im Katalysatormaterial K gebildeter catalyst-free space runs a connected to the exhaust space A (compound not shown) exhaust pipe B, on the formed in the catalyst material K.
Wasserstoff 3 als Permeat mit hoher Reinheit aus dem Reaktor R abgezogen werden kann, während vorwiegend aus Kohlendioxid bestehendes Retentat 2 über eine Abzugseinrichtung (nicht dargestellt) aus dem Reaktor ableitbar ist. Der Durchmesser des Abzugsrohres B kann so gewählt werden, dass es gleichzeitig die Aufgaben der gasdichten Wand W übernimmt. Hydrogen 3 can be withdrawn as a permeate with high purity from the reactor R, while predominantly consisting of carbon dioxide retentate 2 via a take-off device (not shown) can be derived from the reactor. The diameter of the exhaust pipe B can be selected so that it simultaneously performs the tasks of the gas-tight wall W.

Claims

Patentansprüche claims
1. Reaktor (R) zur Erzeugung von Wasserstoff (3), aufweisend einen von einem 1. reactor (R) for the production of hydrogen (3), comprising one of a
Mantelrohr (M) umschlossenen Reaktionsraum (Z) mit einem darin angeordneten, zur Durchführung einer Dampfreformierung geeigneten Katalysator (K), eine zumindest abschnittsweise selektiv wasserstoffdurchlässige Trennwand (T), die einen zwischen der Innenseite (I) und der Längsachse (L) des Mantelrohres (M) angeordneten Abzugsraum (A) bildet, über den Wasserstoff (3) aus dem Reaktor (R) abziehbar ist, sowie eine Zuführeinrichtung, über die Einsatzstoffe (1) an einem Ende des Mantelrohres (M) in den Reaktionsraum (Z) einleitbar sind, dadurch gekennzeichnet, dass der zwischen der Längsachse (L) des  Jacket tube (M) enclosed reaction space (Z) arranged therein, suitable for carrying out a steam reforming catalyst (K), an at least partially selectively hydrogen-permeable partition (T), one between the inside (I) and the longitudinal axis (L) of the jacket tube (M) arranged deduction space (A), via the hydrogen (3) from the reactor (R) is removable, and a feed device, via the starting materials (1) at one end of the jacket tube (M) in the reaction chamber (Z) can be introduced are characterized in that between the longitudinal axis (L) of the
Mantelrohres (M) und der Trennwand (T) gelegene Raum frei von  Jacket tube (M) and the partition (T) located space free of
Katalysatormaterial ist.  Catalyst material is.
2. Reaktor nach Anspruch 1 , dadurch gekennzeichnet, dass die Trennwand (T) wenigstens fünf Membranrohre umfasst, deren Längsachsen alle auf einem Zylindermantel angeordnet sind, dessen Längsachse mit der Längsachse (L) des Mantelrohres (M) zusammenfällt. 2. Reactor according to claim 1, characterized in that the partition wall (T) comprises at least five membrane tubes whose longitudinal axes are all arranged on a cylinder jacket whose longitudinal axis coincides with the longitudinal axis (L) of the jacket tube (M).
3. Reaktor nach Anspruch 2, dadurch gekennzeichnet, dass die Achsabstände 3. Reactor according to claim 2, characterized in that the axial distances
unmittelbar benachbarter Membranrohre jeweils gleich groß sind.  immediately adjacent membrane tubes are the same size.
4. Reaktor nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, dass die Achsabstände unmittelbar benachbarter Membranrohre kleiner sind als der zweifache Durchmesser eines Membranrohres. 4. Reactor according to one of claims 2 or 3, characterized in that the axial distances of immediately adjacent membrane tubes are smaller than twice the diameter of a membrane tube.
5. Reaktor nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass ein mit dem durch die selektiv wasserstoffdurchlässige Trennwand (T) gebildeten 5. Reactor according to one of claims 1 to 4, characterized in that one with the through the selectively hydrogen-permeable partition (T) formed
Abzugsraum (A) verbundenes Abzugsrohr (B) durch den zwischen der  Deduction space (A) connected exhaust pipe (B) by the between the
Längsachse (L) des Mantelrohres (M) und der Trennwand (T) gelegenen Raum zu dem Ende des Mantelrohres (M) verläuft, an dem sich die Zuführeinrichtung für die Einsatzstoffe (1) befindet.  Longitudinal axis (L) of the jacket tube (M) and the partition (T) located space to the end of the jacket tube (M), at which the feed device for the starting materials (1) is located.
6. Reaktor nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass 6. Reactor according to one of claims 1 to 5, characterized in that
wenigstens ein Teil des zwischen der Längsachse (L) des Mantelrohres (M) und der Trennwand (T) gelegenen Raumes durch eine gasdichte Wand (W) vom Reaktionsraum (Z) abgetrennt ist. at least part of the space located between the longitudinal axis (L) of the jacket tube (M) and the partition (T) is separated from the reaction space (Z) by a gas-tight wall (W).
7. Reaktor nach Anspruch 6, dadurch gekennzeichnet, dass die gasdichte Wand (W) durch das Abzugsrohr (B) gebildet ist. 7. Reactor according to claim 6, characterized in that the gas-tight wall (W) through the exhaust pipe (B) is formed.
PCT/EP2012/001530 2011-04-21 2012-04-05 Membrane reactor for producing hydrogen WO2012143096A1 (en)

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US11322766B2 (en) 2020-05-28 2022-05-03 Saudi Arabian Oil Company Direct hydrocarbon metal supported solid oxide fuel cell
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US11583824B2 (en) 2020-06-18 2023-02-21 Saudi Arabian Oil Company Hydrogen production with membrane reformer
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US11718575B2 (en) 2021-08-12 2023-08-08 Saudi Arabian Oil Company Methanol production via dry reforming and methanol synthesis in a vessel
US11787759B2 (en) 2021-08-12 2023-10-17 Saudi Arabian Oil Company Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel
US11617981B1 (en) 2022-01-03 2023-04-04 Saudi Arabian Oil Company Method for capturing CO2 with assisted vapor compression

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