WO2013093425A1 - Réacteur catalytique et structure catalytique - Google Patents

Réacteur catalytique et structure catalytique Download PDF

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Publication number
WO2013093425A1
WO2013093425A1 PCT/GB2012/053098 GB2012053098W WO2013093425A1 WO 2013093425 A1 WO2013093425 A1 WO 2013093425A1 GB 2012053098 W GB2012053098 W GB 2012053098W WO 2013093425 A1 WO2013093425 A1 WO 2013093425A1
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Prior art keywords
reactor
catalytic
combustion
channels
catalyst
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PCT/GB2012/053098
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English (en)
Inventor
David James West
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Compactgtl Limited
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Publication of WO2013093425A1 publication Critical patent/WO2013093425A1/fr

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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • 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
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2453—Plates arranged 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2451—Geometry of the reactor
    • B01J2219/2456—Geometry of the plates
    • B01J2219/2459—Corrugated plates
    • 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
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2461—Heat exchange aspects
    • B01J2219/2462—Heat exchange aspects the reactants being in indirect heat exchange with a non reacting heat exchange medium
    • B01J2219/2464—Independent temperature control in various sections of 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
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2461—Heat exchange aspects
    • B01J2219/2465—Two reactions in indirect heat exchange with 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2477—Construction materials of the catalysts
    • B01J2219/2479—Catalysts coated on the surface of plates or inserts
    • 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
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2476—Construction materials
    • B01J2219/2483—Construction materials of the plates
    • B01J2219/2485—Metals or alloys
    • 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
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2491—Other constructional details
    • B01J2219/2497—Size aspects, i.e. concrete sizes are being mentioned in the classified document
    • 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
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2491—Other constructional details
    • B01J2219/2498—Additional structures inserted in the channels, e.g. plates, catalyst holding meshes
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • 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
    • 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

Definitions

  • the present invention relates to a reactor for performing chemical reactions which involve heat transfer, the reactor defining channels in which there is a catalyst structure for a combustion reaction, and to a catalyst structure for use in such a reactor.
  • catalytic reactor consisting of a stack of metal sheets that define first and second flow channels, where catalyst is provided on removable inserts such as corrugated foils within the flow channels, is described for example in WO
  • WO 2010/067097 also describes a catalytic reactor in which a catalyst insert may comprise one or more corrugated foils.
  • the two sets of channels enable heat transfer to take place between the contents of those channels.
  • steam methane reforming is an endothermic reaction that requires an elevated temperature, typically above 750 °C; and the requisite heat may be provided by a combustion reaction taking place in the other set of channels within the catalytic reactor.
  • a reactor defining first and second flow channels within the reactor, each flow channel having an inlet and an outlet, with a removable combustion catalyst insert provided in each of those channels in which a combustion reaction is to occur, the combustion catalyst insert comprising a first portion including active catalytic material, a second portion having a catalytic activity less than 0.2 times the catalytic activity of the first portion, and a third portion including active catalytic material and having an activity at least 0.3 times that of the first portion, wherein the first portion, the second portion, and the third portion are progressively further from the inlet.
  • a combustible gas mixture is supplied to the inlet, and flows successively past the first portion, the second portion and the third portion.
  • the variation in catalytic activity of the successive catalyst portions controls the rate of combustion, and therefore controls the temperature distribution.
  • additional components such as fuel
  • the section of the flow channel containing the combustion catalyst insert has only a single inlet.
  • the catalytic activity of equal lengths of catalyst structure can be compared in an experimental test in which a combustible gas mixture is passed over the catalyst structures placed in turn within a channel, holding the temperature at the channel wall at a constant value, for example l OCO, and holding the gas composition and flow rate constant.
  • the catalytic activity can be assessed by determining the proportion of a combustible gas such as hydrogen which undergoes combustion.
  • the second portion may have a catalytic activity about 0.1 times the catalytic activity of the first portion, or it may have no catalytic activity. It has been found that an oxidised aluminium-containing steel alloy which has an alumina surface can have a catalytic activity between 0.075 and 0.130 times that of a normal combustion catalyst; whereas a steel alloy which does not contain aluminium, such as stainless- steel, is suitable where catalytic activity is not required.
  • the third portion may have a catalytic activity approximately the same as that of the first portion, as both these portions are intended to bring about combustion.
  • the catalytic activity of the third portion may be between 0.5 and 5.0 times that of the first portion, or between 0.75 and 2.0 times that of the first portion. Indeed they may have equal catalytic activity.
  • the catalytic activity of the third portion may be graded along its length, for example by varying the concentration of active catalytic material.
  • the length of the first portion is between 5 mm and 100 mm; and the length of the second portion is between 20 mm and 300 mm; and the third portion occupies the remainder of the length of the channel.
  • the first portion may be of length between 10 mm and 35 mm, for example 35 mm; while the second portion may be of length between 50 mm and 200 mm, for example 100 mm.
  • the first portion may be between 0.5% and 15% of the total length of the catalyst within the channel, for example 1 % or 5% of the total length; the second portion may be between 2% and 45%, for example 5% or 20%; the third portion may be more than 50% of the total length, for example 75%.
  • Each portion may be at least 5 mm long.
  • the effect of the first portion is to initiate the catalytic combustion reaction, but the length of the first portion is sufficiently short that no more than 15%, and more typically no more than 10%, of the combustible gas undergoes reaction.
  • the first portion raises the temperature of the combustible gas mixture.
  • the second portion may have low catalytic activity, so catalytic combustion occurs at a low rate, maintaining an elevated temperature.
  • the present invention is particularly applicable where an endothermic reaction is to take place in channels which are in thermal contact with the channels in which combustion occurs, the channels for the endothermic reaction incorporating a catalyst for the endothermic reaction, but in which a distributor region of the endothermic reaction channel contains no catalyst for the endothermic reaction.
  • the first portion and the second portion of the catalyst insert in the combustion channels may be arranged adjacent to the distributor region of the endothermic reaction channel. The first portion and the second portion of the catalyst insert provide sufficient heat to suppress any heat loss from the gases supplied to the distributor region.
  • the reactor may also include a non-catalytic insert adjacent to the inlet of each channel for combustion, the non-catalytic insert comprising one or more foils which subdivide the flow channel adjacent to the inlet into a multiplicity of narrow flow paths which are narrower than the maximum gap size for preventing flame propagation.
  • a non-catalytic insert may be made of a stainless-steel which does not form an alumina surface. It would typically be of length at least 30 mm, but no more than 100 mm long, for example 50 mm or 60 mm. The provision of such a non-catalytic insert is described in EP 2 015 865 B (CompactGTL pic).
  • the first flow channels and the second flow channels may extend in parallel directions, within a reactor block, and the combustible gas mixture and the endothermic reaction mixture flow in the same direction (co-flow).
  • the flow channels may be of length at least 300 mm, and may be at least 500 mm, but usually no longer than about 1000 mm. A length of between 500 mm and 700 mm, for example 600 mm may be advantageous. It has been found that co-flow operation gives better temperature control, and less risk of hot-spots.
  • each first flow channel (the channels for the combustion reaction) and each second flow channel (the channels for the endothermic reaction) contains a removable catalyst structure to catalyse the respective reaction
  • each catalyst structure may comprise a metal substrate, and incorporate an appropriate catalytic material.
  • Each such catalyst structure may be shaped so as to subdivide the flow channel into a multiplicity of parallel flow sub-channels.
  • Each catalyst structure may include a ceramic support material on the metal substrate, which provides a support for the catalyst.
  • the metal substrate provides strength to the catalyst structure and enhances thermal transfer by conduction.
  • the metal substrate may be of a steel alloy that forms an adherent surface coating of aluminium oxide when heated, for example a ferritic steel alloy that incorporates aluminium (eg Fecralloy (TM)).
  • the substrate may be a foil, a wire mesh or a felt sheet, which may be corrugated, dimpled or pleated; the preferred substrate is a thin metal foil for example of thickness less than 150 ⁇ , which is corrugated to define the longitudinal sub-channels.
  • the substrate may comprise either a single corrugated foils or an assembly of foils, which may be bonded together, for example by spot welding.
  • the corrugations may be square, rectangular, trapezoidal or hexagonal in cross-section; or arcuate or sinusoidal; or they may be of zigzag shape, defining triangular corrugations, or a sawtooth shape, for example with sloping portions connected by flat peaks.
  • the corrugations typically run parallel to the length of the foils. In some alternative configurations, the corrugations may be non- parallel or even perpendicular to the length of the foil.
  • the corrugated foils may be spaced apart by foils that are flat or substantially flat, to ensure they do not intermesh.
  • Such flat foils are not necessary if the adjacent foils have corrugations that are not parallel, or are otherwise shaped to ensure the foils they do not intermesh. For example if the peaks and troughs are defined by flat portions of the profile, and the flat portions in adjacent foils are aligned with each other, then the foils will not intermesh.
  • flat foils may also be corrugated at a very small amplitude, for example to provide a total height of less than about 0.2 mm, for example 0.1 mm, as this makes them slightly less flexible and so easier to work with during assembly.
  • the direction of the corrugation of the substantially flat foil may be lengthwise along the foil or, alternatively, may be transverse.
  • the shape of the corrugations of the flat foils may be sawtooth or rippled.
  • the foils may be of thickness in the range 20-150 ⁇ , for example 50 ⁇ . A thicker foil, for example 100 ⁇ thick, may provide benefits in enhanced heat transfer.
  • the overall height of the insert is more repeatable and controllable than a stack in which identical corrugated foils are deployed.
  • the metal substrate would be provided with a catalyst on at least some of the surfaces.
  • the substrate may be coated with ceramic support material, for example based on alumina, and this would be impregnated with active catalytic material appropriate for the reaction that is to take place in the corresponding channel.
  • the ceramic coating may be applied by techniques such as dip coating, or spraying, to achieve a ceramic thickness between 10 ⁇ and 100 ⁇ , depending on the reaction.
  • the coating may be applied to separate foils before they are stacked together, or even after such foils have been bonded together.
  • the second portion of the catalyst insert may comprise a length of a steel alloy that forms an adherent surface coating of aluminium oxide when heated, for example a ferritic steel alloy that incorporates aluminium (eg Fecralloy (TM)), which has been oxidised to ensure that the surface is of alumina.
  • a ferritic steel alloy that incorporates aluminium (eg Fecralloy (TM))
  • TM Fecralloy
  • Such an oxidised surface has a catalytic activity for combustion about 0.1 times that of a conventional combustion catalyst.
  • the first portion and the third portion preferably include a metal substrate and a ceramic support material, such as a coating of alumina, and this would be impregnated with active catalytic material.
  • the active catalytic material may be platinum, or palladium oxide. Palladium and platinum have been previously suggested as suitable active catalytic materials for a combustion catalyst. Platinum is catalytically active in the metal form, rather than the oxide form, and is stable as the metal; and it has a higher light-off temperature than palladium. Platinum is active at high temperatures, and not particularly active at temperatures below about 600 °C. However, it tends to undergo deactivation at temperatures above about 795°C.
  • Palladium is catalytically active in the oxide form, and significantly less active in the metal form, and in the presence of a low oxygen partial pressure the transformation from the oxide to the metal may occur, with a consequential reduction in the catalytic activity, particularly at high temperatures.
  • palladium oxide is active at lower temperatures than platinum, for example between 400 °C and 700 °C.
  • the first portion may comprise palladium oxide
  • the third portion may comprise palladium oxide and also platinum.
  • the reactor consists of a block, typically of metal, which defines the first and second flow channels.
  • the first and second flow channels may be defined by grooves in plates arranged as a stack, or by spacing strips and plates in a stack, the stack then being bonded together.
  • the flow channels may be defined by thin metal sheets that are castellated and stacked alternately with flat sheets; the edges of the flow channels may be defined by sealing strips.
  • the stack of plates forming the reactor is bonded together for example by diffusion bonding, brazing, or hot isostatic pressing.
  • the stack of plates, after being bonded together, provides the requisite structure to ensure that the reactor can resist the differential pressures and thermal stresses that are applied during operation; the catalyst insert does not have to provide structural support. Consequently the catalyst inserts can be non-structural, as they do not have to hold the walls of the channels apart during operation.
  • the channels may be square in cross-section, or may be of height either greater than or less than the width, where the height refers to the dimension in the direction of the stack, that is to say in the direction for heat transfer.
  • the plates might be 0.5 m wide and 1 .0 m long, or 0.6 m wide and 0.8 m long; and they may define channels 7 mm high and 6 mm wide, or 3 mm high and 10 mm wide, or 10 mm high and 5 mm wide. These dimensions are merely exemplary, and the skilled person will recognise that many different shapes and sizes are equally suitable.
  • Arranging the first and second flow channels to alternate in the stack helps ensure good heat transfer between fluids in those channels.
  • the first flow channels may be those for combustion (to generate heat) and the second flow channels may be for steam/methane reforming (which requires heat).
  • the catalyst inserts are inserted into the channels, and can be removed for replacement.
  • the present invention provides a combustion catalyst insert for use in such a reactor, the combustion catalyst insert comprising a first portion including active catalytic material, a second portion having a catalytic activity less than 0.2 times the catalytic activity of the active catalytic material, and a third portion including active catalytic material with an activity at least four times greater than that of the second portion, such that after insertion into a combustion flow channel the first portion, the second portion, and the third portion are progressively further from the inlet.
  • Figure 1 shows a schematic perspective view, partly in section, of part of a reactor block suitable for steam/methane reforming and including catalyst inserts (the section being on the line 1 -1 of figure 2);
  • Figure 2 shows a side view of the assembled reactor block of figure 1 showing the flow paths
  • Figures 3a and 3b show plan views of parts of the reactor block of figure 1 during assembly
  • Figure 4 shows a side view of a catalyst insert of Figure 1 .
  • the invention is applicable to a process for making synthesis gas, that is to say a mixture of carbon monoxide and hydrogen, from natural gas by steam reforming.
  • the synthesis gas may, for example, subsequently be used to make longer-chain hydrocarbons by a Fischer-Tropsch synthesis.
  • the steam reforming reaction is brought about by mixing steam and methane, and contacting the mixture with a suitable catalyst at an elevated temperature so the steam and methane react to form carbon monoxide and hydrogen.
  • the steam reforming reaction is
  • the heat may be provided by catalytic combustion, for example of hydrocarbons and/or hydrogen mixed with air, so combustion takes place over a combustion catalyst within adjacent flow channels within the reforming reactor.
  • the reactor block 10 defines channels for a catalytic combustion process and channels for steam methane reforming.
  • the reactor 10 consists of a stack of plates that are rectangular in plan view, each plate being of corrosion resistant high-temperature alloy such as Inconel 625, Incoloy 800HT or Haynes HR-120.
  • Flat plates 12, typically of thickness in the range 0.5 to 4 mm, in this case 2.0 mm thick, are arranged alternately with castellated plates 14 or 15, so the castellations define channels 16 or 17.
  • the castellated plates 14 and 15 are arranged in the stack alternately.
  • the wavelengths of the castellations in the castellated plates 14 and 15 may be different from each other, but in the embodiment shown in the figure the wavelengths are the same, so that in each case successive fins or ligaments are 7 mm apart.
  • the castellated plates 14 and 15 may be referred to as fin structures.
  • At each end of the stack is a flat end plate 19, which in this case is also of thickness 2.0 mm.
  • each castellated sheet 14 or 15 in figure 1 there might be many more, for example over seventy channels in a reactor block 10 of overall width about 500 mm.
  • the stack of plates would be assembled and bonded together typically by diffusion bonding, brazing, or hot isostatic pressing.
  • a respective catalyst insert 22 or 24 (only one of each are shown in Figure 1 ), carrying a catalyst for the respective reaction.
  • These inserts 22 and 24 comprise a metal substrate and a ceramic coating acting as a support for the active catalytic material.
  • each insert 22, 24 comprises a stack of corrugated foils and flat foils occupying the respective flow channel 16 or 17, each foil being of thickness less than 0.2 mm, for example 100 ⁇ ; the stacks shown in figure 1 consist of three corrugated foils separated by two flat foils, bonded together.
  • the channels 16 and 17 in this example are 6 mm high and 7 mm wide, while the catalyst inserts 22 and 24 in this case are 5.4 mm high and 6.6 mm wide, so providing a degree of clearance from the walls of the channels 16 and 17. This is necessary to allow for tolerances in manufacture of the reactor block 10.
  • FIG 2 there is shown a side view of the assembled reactor block 10.
  • the gas mixture undergoing combustion enters a header 30 at one end of the reactor block 10 (top, as shown) and after passing through a baffle plate flame arrestor 31 follows the flow channels 17 that extend straight along most of the length of the reactor 10.
  • the gas mixture that is to undergo the steam methane reforming reaction enters a header 34 at the side of the one end of the reactor block 10 (top left, as shown), passes through a baffle plate 35 and then changes direction through 90° to flow through the flow channels 16 that extend straight along most of the length of the reactor block 10, to emerge through a header 36 at the other end (bottom, as shown), this flow path being shown as a chain dotted line S.
  • the arrangement is therefore such that the flows are co-current; and is such that each of the flow channels 16 and 17 is straight along most of it length, and communicates with a header 30 or 36 at an end of the reactor block 10, so that the catalyst inserts 22 and 24 can be readily inserted before the headers 30 or 36 are attached.
  • Each of the flat plates 12 shown in figure 1 is, in this example, of dimensions
  • FIG 3a there is shown a plan view of a portion of the reactor block 10 during assembly, showing the castellated plate 15 (this view being in a plane parallel to that of the view of figure 2).
  • the castellated plate 15 is of length 800 mm, and of width 460 mm, and the side bars 18 are of width 20 mm.
  • the top end of the castellated plate 15 is aligned with the top edge of the flat plate 12, so it is open (to communicate with the header 30).
  • One of the side bars 18 (the left one as shown) is 1 .0 m long, and is joined to an equivalent end bar 18a that extends across the end.
  • FIG 3b there is shown a view, equivalent to that of figure 3a, but showing a castellated plate 14.
  • the castellated plate 14 is again of length 800 mm, and of width 460 mm, and the side bars 18 are of width 20 mm.
  • the bottom end of the castellated plate 14 is aligned with the bottom edge of the flat plate 12, so it is open (to communicate with the header 36).
  • One of the side bars 18 (the right one as shown) is 1 .0 m long, and is joined to an equivalent end bar 18a that extends across the end. There is consequently a 180 mm wide gap at the top left- hand corner (to communicate with the header 34).
  • a first portion 26 has castellations parallel to the end bar 18a, and extends to the edge of the stack (so as to communicate with the header 34), while the other portion 27 has castellations parallel to those in the castellated plate 14.
  • castellated plate 15 and the portion of castellated plate 27 may be integral with each other, as they have identical and parallel castellations; and similarly the castellated plate 14 and the adjacent portion of castellated plate 27 may be integral with each other.
  • the castellations on the triangular portions 26 and 27 have the same shape as those on the channel-defining portions 14 or 15.
  • the triangular portions 26 and 27 may be omitted, to leave a gas distribution space between the flat plates 12 through which the gas flows between the end of the castellated plate 14 or 15 and the header 32, 34 at the side of the block 10.
  • catalyst inserts 22 and 24 are inserted into the reaction channels 16 and 17.
  • the catalyst inserts 24 for insertion in the channels 17 for combustion are of length 800 mm and incorporate active catalytic material along 600 mm of their length, corresponding to the bottom three-quarters of the straight channels as shown in plan in figure 3a, this portion being indicated by the arrow P.
  • An adjacent portion Q1 of length 150 mm of the inserts 24 is of low catalytic activity, while the remaining portion Q2, closest to the inlet, of length 50 mm, incorporates active catalytic material.
  • the catalyst inserts 22 are of length 800 mm, and as indicated by the arrow R active catalytic material is provided along the portion occupying the upper three-quarters of the straight channels as shown in plan in figure 3b; the other 200 mm of the length of the inserts 22 as indicated by the arrow Q3 are non-catalytic.
  • a wire mesh or grille may be attached across the bottom end of the reactor block 10 so that the catalyst inserts 22 do not fall out of the flow channels 16 when the reactor block 10 is in its upright position (as shown in figure 2). It will hence be appreciated that the major part of the active catalytic materials on the inserts 22 and 24 are present in those portions P and R of the flow channels 16 and 17 which are immediately adjacent to each other.
  • headers 30, 32, 34 and 36 might then be attached to the reactor block 10.
  • each insert 22 and 24 comprise a metal substrate and a ceramic coating acting as a catalyst or catalyst support.
  • the metal substrate of each insert 22, 24 comprises a stacked assembly of corrugated foils and flat foils occupying the respective flow channel 16 or 17, each foil being of thickness less than 0.2 mm, for example 50 ⁇ or 100 ⁇ ; the assemblies shown in figure 1 consist of three corrugated foils separated by two flat foils, bonded together.
  • the total length of each insert 22 and 24 is 800 mm, and all the foils are 800 mm long in this example.
  • the insert 24 consists of three corrugated foils 41 separated by two flat foils 42. Each foil is of the appropriate width to fit in the corresponding channel, 6.6 mm wide in this example.
  • the foils are spot welded together at multiple positions 40.
  • Each foil 41 and 42 is of Fecralloy steel alloy, and is heat treated an oxygen-containing atmosphere so as to have an alumina surface.
  • the portion Q1 which is to be of low activity is not treated further, but the other portions P and Q2 are provided with a surface coating of ceramic, such as alumina, which bonds to the surface and provides a catalyst support.
  • the portion Q2 is then impregnated with 10% palladium oxide, while the portion P is impregnated to a level of 10% with a mixture of platinum and palladium oxide.
  • the reactor can be operated such that there is little or no loss of heat from the reforming gas mixture as it flows through the distribution region that links the header 34 to the channels 16. This is achieved by the limited degree of combustion due to the portions Q1 and Q2 in the combustion channels adjacent to the distribution region.
  • the reactor 10 may also include a non-catalytic insert (not shown) adjacent to the inlet of each channel 17 for combustion, the non-catalytic insert comprising one or more foils which subdivide the flow channel 17 adjacent to the inlet into narrow flow paths which are narrower than the maximum gap size for preventing flame propagation.
  • This non-catalytic insert may be made of a stainless- steel which does not form an alumina surface. It may for example be of length 50 mm. In this case the catalytic insert 24 would have to be 50 mm shorter, to provide space for the non-catalytic insert adjacent to the inlet, for example the portion Q1 may be of length 1 10 mm, while the remaining portion Q2 is of length 40 mm.
  • the safe quenching distance or quenching gap which is the maximum channel width that ensures suppression of all flame propagation at a specific pressure and temperature. If the channel gap is greater than the quenching gap, flame propagation may be possible, and a flame may become a deflagration, that is a combustion wave propagating at subsonic velocity. In practice the maximum gap (at which flame propagation is suppressed) is actually significantly larger than the quenching gap, at least for channels of a rectangular cross-section, and is approximately equal to the detonation cell size.
  • the quench gap is about 0.1 mm, but the maximum gap size is about 5 mm.
  • the maximum gap size with hydrogen in oxygen is about 1 .2 mm.
  • each channel 17 for combustion may contain an insert of length 800 mm comprising a non-catalytic metal support, for example consisting of corrugated and flat foils of a non-aluminium-containing stainless-steel.
  • One end portion P of length 600 mm is provided with a coating of a ceramic such as zirconia or alumina, which is impregnated with a combustion catalyst such as a Pd/Pt mixture, as described above.
  • a combustion catalyst such as a Pd/Pt mixture
  • An adjacent portion Q1 of length 1 10 mm is uncoated, so it has negligible catalytic activity.
  • An adjacent portion Q2 of length 40 mm is coated with a coating of a ceramic which is impregnated with a combustion catalyst such as palladium oxide. This leaves an end portion of length 50 mm which is uncoated, so it has negligible catalytic activity.
  • the uncoated end portion acts as a flame suppressor, so as explained above it must subdivide the flow channel 17 adjacent to the inlet into narrow flow paths which are narrower than the "limiting gap size".
  • the flow paths are the same throughout the length of the insert, as they are defined by the size of the corrugations, so the flow paths throughout the length of the insert are narrower than the "limiting gap size”.

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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)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un réacteur (10) qui définit des premier et second canaux d'écoulement (16, 17), un insert de catalyseur de combustion amovible (24) étant disposé dans chacun de ces canaux (17) dans lesquels une réaction de combustion doit se produire. L'insert de catalyseur de combustion comprend une première partie (Q2) comprenant une matière catalytique active, une deuxième partie (Q1) ayant une activité catalytique inférieure à 0,2 fois l'activité catalytique de la première partie (Q2), et une troisième partie (P) comprenant une matière catalytique active avec une activité au moins 0,3 fois celle de la première partie (Q2). La première partie (Q2), la deuxième partie (Q1) et la troisième partie (P) sont progressivement plus éloignées à partir de l'entrée ; et elles peuvent être formées d'une seule pièce.
PCT/GB2012/053098 2011-12-22 2012-12-12 Réacteur catalytique et structure catalytique WO2013093425A1 (fr)

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GBGB1122193.4A GB201122193D0 (en) 2011-12-22 2011-12-22 Catalytic reactor and catalyst structure
GB1122193.4 2011-12-22

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WO2013093425A1 true WO2013093425A1 (fr) 2013-06-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014096779A1 (fr) * 2012-12-17 2014-06-26 Compactgtl Limited Réacteur chimique multi-canaux

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5281128A (en) * 1990-11-26 1994-01-25 Catalytica, Inc. Multistage process for combusting fuel mixtures
DE19855769A1 (de) * 1998-12-03 2000-06-08 Dbb Fuel Cell Engines Gmbh Katalytisch beheizte Komponente für einen chemischen Reaktor
US6159358A (en) * 1998-09-08 2000-12-12 Uop Llc Process and apparatus using plate arrangement for reactant heating and preheating
US20020054837A1 (en) * 1998-06-29 2002-05-09 Fumio Abe Reformer
DE10110465A1 (de) * 2001-03-05 2002-10-02 Vodafone Pilotentwicklung Gmbh Reaktor
WO2003033131A1 (fr) 2001-10-12 2003-04-24 Gtl Microsystems Ag Reacteur catalytique
US20050235560A1 (en) * 2004-02-14 2005-10-27 Oliver Marquardt Integrated reactor for the thermal coupling of reactions and method for controlling the temperature field in such a reactor
US20060035182A1 (en) 2004-08-13 2006-02-16 Hesse David J Detonation safety in microchannels
US20070258872A1 (en) * 2006-05-08 2007-11-08 Compactgtl Plc Catalytic reactor
US20070258883A1 (en) * 2006-05-08 2007-11-08 Compactgtl Plc Catalyst structure for a rapid reaction
US20080131341A1 (en) * 2000-01-11 2008-06-05 Michael Joseph Bowe Catalytic reactor
WO2010067097A2 (fr) 2008-12-11 2010-06-17 Compactgtl Plc Fonctionnement de réacteur chimique

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5281128A (en) * 1990-11-26 1994-01-25 Catalytica, Inc. Multistage process for combusting fuel mixtures
US20020054837A1 (en) * 1998-06-29 2002-05-09 Fumio Abe Reformer
US6159358A (en) * 1998-09-08 2000-12-12 Uop Llc Process and apparatus using plate arrangement for reactant heating and preheating
DE19855769A1 (de) * 1998-12-03 2000-06-08 Dbb Fuel Cell Engines Gmbh Katalytisch beheizte Komponente für einen chemischen Reaktor
US20080131341A1 (en) * 2000-01-11 2008-06-05 Michael Joseph Bowe Catalytic reactor
DE10110465A1 (de) * 2001-03-05 2002-10-02 Vodafone Pilotentwicklung Gmbh Reaktor
WO2003033131A1 (fr) 2001-10-12 2003-04-24 Gtl Microsystems Ag Reacteur catalytique
US20050235560A1 (en) * 2004-02-14 2005-10-27 Oliver Marquardt Integrated reactor for the thermal coupling of reactions and method for controlling the temperature field in such a reactor
US20060035182A1 (en) 2004-08-13 2006-02-16 Hesse David J Detonation safety in microchannels
US20070258872A1 (en) * 2006-05-08 2007-11-08 Compactgtl Plc Catalytic reactor
US20070258883A1 (en) * 2006-05-08 2007-11-08 Compactgtl Plc Catalyst structure for a rapid reaction
EP2015865B1 (fr) 2006-05-08 2012-01-04 CompactGTL plc Réacteur catalytique comprenant des premiers et des seconds canaux d'écoulement disposés de facon alternée
WO2010067097A2 (fr) 2008-12-11 2010-06-17 Compactgtl Plc Fonctionnement de réacteur chimique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014096779A1 (fr) * 2012-12-17 2014-06-26 Compactgtl Limited Réacteur chimique multi-canaux

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TW201338860A (zh) 2013-10-01

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