AU2017295491B2 - Compact methanol reformer for a submarine - Google Patents

Compact methanol reformer for a submarine Download PDF

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Publication number
AU2017295491B2
AU2017295491B2 AU2017295491A AU2017295491A AU2017295491B2 AU 2017295491 B2 AU2017295491 B2 AU 2017295491B2 AU 2017295491 A AU2017295491 A AU 2017295491A AU 2017295491 A AU2017295491 A AU 2017295491A AU 2017295491 B2 AU2017295491 B2 AU 2017295491B2
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region
reaction
methanol reformer
outer tube
charging
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AU2017295491A1 (en
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Stefan Krummrich
Marc Pein
Dennis Ruser
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ThyssenKrupp AG
ThyssenKrupp Marine Systems GmbH
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ThyssenKrupp AG
ThyssenKrupp Marine Systems GmbH
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Assigned to THYSSENKRUPP MARINE SYSTEMS GMBH, THYSSENKRUPP AG reassignment THYSSENKRUPP MARINE SYSTEMS GMBH Amend patent request/document other than specification (104) Assignors: THYSSENKRUPP AG, THYSSENKRUPP MARINE SYSTEMS GMBH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/065—Feeding reactive fluids
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00203—Coils
    • 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
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/0035—Periodical feeding or evacuation
    • 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
    • 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
    • C01B2203/12—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
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • 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
    • C01B2203/1288—Evaporation of one or more of the different feed components

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

Abstract

The present invention relates to a methanol reformer (10) having a reaction region (20), a charging region (30) and a discharge region (40). The reaction region (20), the charging region (30) and the discharge region (40) are arranged one above the other with the reaction region (20) at the bottom. At least one first coaxial reaction tube (50) is arranged vertically in the reaction region (20), the at least one first coaxial reaction tube (50) having an outer tube region (52) and an inner tube region (54), the outer tube region (52) being filled with a catalyst. The outer tube region (52) is connected to the charging region (30) and the inner tube region (54) is connected to the discharge region (40). A preheating device (100) for preheating the methanol-water mixture is disposed in the reaction region (20).

Description

Compact methanol reformer for a submarine
The invention relates to a methanol reformer for the generation of hydrogen for use in a fuel cell, in particular for use of the methanol reformer on board a water-craft, in particular on board a 5 submarine.
Modern submarines, for example submarine of the class U 212A, have a fuel cell for the generation of energy. Generation of energy is thus possible independently of external air, thus in particular when the submarine is submerged. Currently the hydrogen for this is transported in metal 10 hydride stores, which facilitates safe carrying along of hydrogen.
However, for larger submarines than the vessels of the class U 212A, it may be useful to fall back on methanol instead of metal hydride stores. The disadvantage is that in addition a reformer has to be accommodated on board. In addition, the reformer must also meet the requirements for installation in a submarine, in particular with regard to compactness and robustness.
A heat-exchanger reactor, which comprises parallel tubes, is known from US 2010 / 0254891 A1.
A heat-exchanger reactor, which comprises parallel tubes, is known from WO 2009 / 141 517 A1.
A reactor for steam reforming is known from US 2006 I 0248800 A1.
A reformer for hydrocarbons is known from US 3,172,739 A.
A membrane for a steam reformer is known from EP 1 679 111 A2.
It would be advantageous if the present invention would provide a compact methanol reformer which is suitable for use in a submarine.
The methanol reformer of the invention comprises a reaction region, a charging region and a discharge region, wherein the reaction region, the charging region and the discharge region are arranged one above the other. The reaction region is arranged at the bottom. Hence, both the charging region and the discharge region is arranged above the reaction region. At least one first coaxial reaction tube is arranged vertically in the reaction region, wherein the at least one first coaxial reaction tube comprises an outer tube region and an inner tube region. The outer tube
10985551_1 (GHMatters) P110386.AU
-22017295491 12 Jul 2019 region is connected to the charging region and the inner tube region is connected to the discharge region.
Due to this construction, a structure is produced which comprises no feed inlets on the underside of the methanol reformer, but a stable and fixed base. The reformer may thus be installed well, particularly in spatially confined regions, for example on board a submarine. The methanol reformer may be stored in particular in a vibration-damped and shock-safe manner and thus fulfills the particular requirements of a submarine.
Coaxial reaction tube is understood to mean two conduits with different diameter pushed into one another. The diameter of the conduits is selected so that a gap is formed between the conduits. The gap between the outer conduit and the inner conduit resulting in this arrangement is designated as outer tube region and the space in the inner conduit is designated as inner tube region.
In a further embodiment of the invention, the outer tube region is filled with a catalyst. For example intermetallic compounds, such as for example ΝΪ3ΑΙ, CuZn or NiCr, noble metal catalysts, oxides, such as for example copper-zinc-aluminum mixed oxide, or metal catalysts on oxidic carriers, for example Cu/Zn, Cu/Cr or Cu/Zr on AI2O3, may be used as catalysts.
In a further embodiment of the invention, the reaction region comprises a water inlet and a water outlet. The reaction region may thus be heated or tempered using water as the heat carrier. Since the reaction of methanol and water to form hydrogen, carbon dioxide and carbon monoxide is endothermic and is effected only at elevated temperature, this is advantageous.
In a further embodiment of the invention, water is introduced as a gas through the water inlet and liquid water is discharged through the water outlet. The water inlet is for that purpose preferably arranged in the upper region of the reaction region, the water outlet in the lower region of the reaction region. In addition to the thermal capacity of the water, the enthalpy of evaporation may 30 thus also be utilized for heating.
In a further embodiment of the invention, the reaction region, the charging region and the discharge region are arranged in a housing. It is preferably a cylindrical housing.
10985551_1 (GHMatters) P110386.AU
-32017295491 12 Jul 2019 ln a further embodiment of the invention, the discharge region is arranged above the charging region. The reverse arrangement is equally possible, the further embodiments following therefrom can then be seen accordingly.
Ina further embodiment of the invention, the reaction region and the charging region are separated by a first separating tray and the charging region and the discharge region are separated by a second separating tray. The outer tube region is connected to the first separating tray and the inner tube region is connected to the second separating tray. As a result, the reactants flow from the charging region to the discharge region via the reaction region. In a development of this 10 embodiment, the reaction region comprises a preheating device and a reaction device which are both connected to the charging region. The preheating device and the reaction device are arranged such that the reactants first of all flow through the preheating device in the reaction region, then through the charging region, to be passed to the discharge region via the reaction device in the reaction region.
In a further embodiment of the invention, the at least one first coaxial reaction tube is arranged vertically. Particularly preferably the charging region is arranged above the reaction region and the discharge region above the charging region.
In a further embodiment of the invention, the reaction region comprises a lower base, wherein the at least one first coaxial reaction tube is connected to the lower base by a screw connection. In a particularly preferred embodiment, tension on the at least one first coaxial reaction tube is exerted by the screw connection with the lower base. This tension ensures that the methanol reformer exhibits higher shock resistance. A corresponding methanol reformer is thus particularly suitable 25 for use in the military field, in particular on water-craft, in particular in underwater vehicles. Due to this effect, the lower base may be executed to be weaker and thus thinner compared to a methanol reformer without tension via the at least one first coaxial reaction tube.
In a further embodiment of the invention, the screw connection connects the inner tube region to 30 the outer tube region. The screw connection thus serves at the same time for closing the at least one first coaxial reaction tube and for diverting the gas stream from the outer tube region into the inner tube region.
In a further embodiment of the invention, after removing the screw connection, the catalyst can be 35 removed from the outer tube region or can be introduced into the outer tube region. Since the
10985551_1 (GHMatters) P110386.AU
-42017295491 12 Jul 2019 catalyst conventionally has to be changed within the service life of a reformer, the necessity of access to the outer tube region exists, which may be guaranteed easily by the screw connection. After removing the screw connection, first of all the spent catalyst may be removed from the outer tube region and then new catalyst may be introduced. Then the screw connection is re-introduced 5 and the at least one first coaxial reaction tube is thus closed again. To feed in the catalyst, a device is preferably used which ensures that the inner tube region is not filled with catalyst.
In a further embodiment of the invention, the catalyst is arranged exclusively in the outer tube region. Due to the exclusive arrangement in the outer tube region and for example not in the 10 charging region, a uniform temperature is achieved in the region of the catalyst and thus a uniform reaction of the methanol-water mixture. At the same time, the use of catalyst at less active regions is avoided and thus valuable catalyst saved.
In a further embodiment of the invention, the outer tube region is kept at a temperature of at least 15 230 °C, preferably of at least 250°C, particularly preferably of 270°C.
In a further embodiment of the invention, the outer tube region is kept at a temperature of not more than 310 °C, preferably of not more than 290°C, particularly preferably of 280°C.
In a further embodiment of the invention, the reaction region is heated using steam at a temperature of about 300°C and a pressure between 6 MPa and 10 MPa. The enthalpy of evaporation can thus be utilized for heating. At the same time, the temperature of the liquid phase, which is produced from the phase diagram of water, is set by the pressure.
In a further embodiment of the invention, at least 20 coaxial reaction tubes, preferably at least 50 coaxial reaction tubes, particularly preferably at least 100 coaxial reaction tubes, are arranged in the reaction region.
In a further embodiment of the invention, not more than 500 coaxial reaction tubes, preferably not 30 more than 300 coaxial reaction tubes, particularly preferably not more than 200 coaxial reaction tubes, are arranged in the reaction region.
In a further embodiment of the invention, the catalyst exhibits an average grain size of at most 4 mm, preferably of 2 mm, particularly preferably of 1.5 mm. This avoids in particular bypass flows 35 in regions not filled with catalyst.
10985551_1 (GHMatters) P110386.AU
-52017295491 12 Jul 2019 ln a further embodiment of the invention, the catalyst exhibits an average grain size of at least 0.1 mm, preferably of 0.3 mm, particularly preferably of 0.8 mm.
According to the invention, a preheating device for preheating the methanol-water mixture is arranged in the reaction region. Due to preheating within the reaction region, the methanol-water mixture reaches the catalyst in the outer tube region at exactly the correct temperature of the reaction region, wherein the catalyst in the outer tube region exhibits the same temperature. The change of the temperature in the catalyst comes only due to the enthalpy of reaction.
In a further embodiment of the invention, the preheating device is connected to the charging region and the preheating device comprises an inlet for the methanol-water mixture.
In a further embodiment of the invention, the preheating device consists of several heat-exchanger 15 tubes which are each individually connected to the charging region. Each of the heat-exchanger tubes may be arranged so that the throughflow direction is predominantly vertical to the main flow direction of the heating medium.
In a further embodiment of the invention, the preheating device is designed for preheating a 20 methanol-water mixture by at least 15°C, preferably by at least 100°C, particularly preferably by at least 175°C. The use of a non-preheated methanol-water mixture at about 20°C is of course particularly simple. However, this may lead to a change in the temperature of the reaction region. The use of non-preheated methanol-water mixture is therefore advantageous for a compact overall construction, the use of preheated methanol-water mixture to simplify process control.
In a further embodiment of the invention, the preheating device for preheating a methanol-water mixture is arranged in the reaction region so that new (cold) methanol-water mixture is introduced in the upper region of the reaction region, wherein the upper region of the reaction region is heated using gaseous water. The cold methanol-water mixture thus comes into contact with the steam in 30 terms of heat engineering, wherein the steam may release a comparatively large quantity of heat to the methanol-water mixture by condensation.
In a further embodiment of the invention, the course of flow in the outer tube region runs from top to bottom. Due to the downwardly directed flow, the formation of a fluidized bed of the catalyst is 35 avoided.
10985551_1 (GHMatters) P110386.AU
-62017295491 12 Jul 2019 ln a further embodiment of the invention, the walls of the reaction region, the walls of the charging region and the walls of the discharge region as well as the at least one first coaxial reaction tube consist of the same material. They thus have the same thermal expansion properties and corrosion properties, which increases the service life of the methanol reformer.
In a further embodiment of the invention, the charging region and the outer tube region are separated by a perforated plate. Escape of the catalyst into the charging region is avoided due to the perforated plate. This is particularly important since the methanol reformer is rotated in advantageous manner by 180° to fill the outer tube region with catalyst, whereby the charging 10 region comes to rest below the reaction region. Without the perforated plate, the catalyst would be filled directly into the charging region. However, since the charging region is not heated, no catalyst should be arranged here, since otherwise catalyst arranged here the methanol-water mixture would be cooled by reaction on the catalyst. This cooled gas mixture would then be released onto the catalyst in the outer tube region at too low a temperature, whereby the effectiveness of the 15 methanol reformer would be lowered.
In a further embodiment of the invention, the methanol reformer comprises a hydrogen liberator and a burner, wherein the residual gas of the hydrogen liberator stripped of the hydrogen is supplied to the burner. Conventionally only about 90% of the hydrogen is separated off and 20 supplied to a fuel cell, since a higher degree of separation is not economically viable. The residual gas with hydrogen and carbon monoxide is combusted using oxygen in order to at least partly generate the energy necessary for the process.
The compact and stable construction of the methanol reformer of the invention makes it preferably 25 suitable for use on board a water-craft, in particular on board a submarine.
The methanol reformer of the invention is illustrated in more detail below using an exemplary embodiment shown in the drawings.
Figure 1 schematic cross-section through a methanol reformer
Figure 2 plan view of a screw connection
Figure 1 shows a methanol reformer 10 in schematic cross-section. Figure 1 is not true to scale in order to guarantee visibility.
10985551_1 (GHMatters) P110386.AU
-72017295491 12 Jul 2019
The methanol reformer 10 comprises a reaction region 20, a charging region 30 arranged thereabove and a discharge region 40 arranged thereabove. By way of example three coaxial reaction tubes 50, which comprise an outer tube region 52 and an inner tube region 54, are located in the reaction region 20. For example the methanol reformer 10 has 200 coaxial reaction tubes 50 which are arranged vertically in the reaction region 20. The reaction region 20 is heated by means of water which is introduced through the water inlet 60 as a gas at about 300°C and 8 MPa. The water condenses on the coaxial reaction tubes 50. For example the reaction region 20, as shown, is half filled with liquid water which is removed through the water outlet 62. The reaction region 20, the charging region 30 and the discharge region 40 are arranged in a housing 70. The reaction region 20 and the charging region 30 are separated from one another in gas-tight manner by a first separating tray 80. The charging region 30 and the discharge region 40 are separated from one another in gas-tight manner by a second separating tray 82. The outer wall of the outer tube region is connected to the first separating tray 80 so that methanol-water mixture is introduced from the charging region 30 into the outer tube region 52 which is filled with catalyst. Equally, the outer wall of the inner tube region 54 is connected to the second separating tray 82 so that reformed gas mixture may pass from the inner tube region 54 into the discharge region 40. The gas may pass through the screw connection 90 from the outer tube region 52 into the inner tube region 54. At the same time, the coaxial reaction tube is connected to the lower base 84 in shock-resistant manner by the screw connection 90. By removing the screw connection 90, the catalyst may be removed from the outer tube region 52 and the catalyst may be replaced. In order to preheat the methanolwater mixture, the methanol reformer 10 comprises a preheating device 100 which consists here by way of example of two heat-exchanger tubes. Alternatively, the preheating device may also comprise only one connection through the housing 70 and be divided only in the interior of the reaction region 20, for example into two, three or four heat-exchanger tubes. In the transition between the charging region 30 and the outer tube region 52, perforated plates 110 are arranged which allow gas through, but prevent penetration of catalyst into the charging region 30, even if the methanol reformer is rotated for charging with catalyst.
Figure 2 shows a screw connection 90 in an enlarged representation. The screw connection 90 comprises a connection 120, by means of which the outer tube region 52 and the inner tube region are connected to one another so that the gas mixture reacted on the catalyst may be removed.
The connection 120 is advantageously executed so that no catalyst may pass from the outer tube region 52 into the inner tube region 54.
10985551_1 (GHMatters) P110386.AU
-82017295491 12 Jul 2019
Reference numbers
Methanol reformer
Reaction region
30 Charging region
Discharge region
Coaxial reaction tube
Outer tube region
Inner tube region
60 Water inlet
Water outlet
Housing
First separating tray
Second separating tray
84 Lower base
Screw connection
100 Preheating device
110 Perforated plate
120 Connection
10985551_1 (GHMatters) P110386.AU

Claims (20)

Patent claims
1. A methanol reformer having a reaction region, a charging region and a discharge region, wherein the reaction region, the charging region and the discharge region are
2. The methanol reformer as claimed in claim 1, wherein the outer tube region of the at least one first coaxial reaction tube is filled with a catalyst.
3. The methanol reformer as claimed in claims 1 or 2, wherein that the reaction region comprises a water inlet and a water outlet.
4. The methanol reformer as claimed in claim 3, wherein water is introduced as a gas
30 through the water inlet and liquid water is discharged through the water outlet.
5 connection, the catalyst can be removed from the outer tube region or can be introduced into the outer tube region.
5. The methanol reformer as claimed in any one of the preceding claims, wherein the reaction region comprises a lower base, wherein the at least one first coaxial reaction
35 tube is connected to the lower base by a screw connection.
10985551_1 (GHMatters) P110386.AU
- 102017295491 12 Jul 2019
5 arranged one above the other, wherein the reaction region is arranged at the bottom, wherein at least one first coaxial reaction tube is arranged vertically in the reaction region, wherein the at least one first coaxial reaction tube comprises an outer tube region and an inner tube region, wherein the outer tube region is connected to the charging region and the inner tube region is connected to the discharge region, wherein 10 a preheating device for preheating the methanol-water mixture is arranged in the reaction region, wherein the reaction region comprises the preheating device and a reaction device; wherein the reaction device and the preheating device are both connected to a charging region, wherein the preheating device and the reaction device are arranged such that the reactants first flow through the preheating device in the 15 reaction region, then through the charging region, to be passed to the discharge region via the reaction device in the reaction region, wherein the reaction region, the charging region and the discharge region are arranged in a housing, wherein the reaction region and the charging region are separated by a first separating tray, the charging region and the discharge region are separated by a second separating tray, and wherein the 20 outer tube region is connected to the first separating tray and the inner tube region is connected to the second separating tray.
6. The methanol reformer as claimed in claim 5, wherein the screw connection connects the inner tube region to the outer tube region.
7. The methanol reformer as claimed in claims 5 or 6, wherein after removing the screw
8. The methanol reformer as claimed in any one of the preceding claims, wherein the catalyst is arranged exclusively in the outer tube region.
9. The methanol reformer as claimed in any one of the preceding claims, wherein the outer tube region is kept at a temperature of at least 230°C, preferably of at least 250°C, particularly preferably of 270°C.
10 walls of the reaction region, the walls of the charging region and the walls of the discharge region as well as the at least one first coaxial reaction tube consist of the same material.
- 11 2017295491 12 Jul 2019
11. The methanol reformer as claimed in any one of the preceding claims, wherein the
20 reaction region is heated using steam at a temperature of about 300°C and a pressure between 6 MPa and 10 MPa.
12. The methanol reformer as claimed in any one of the preceding claims, wherein at least 20 coaxial reaction tubes, preferably at least coaxial reaction tubes, particularly
25 preferably at least 100 coaxial reaction tubes, are arranged in the reaction region.
13. The methanol reformer as claimed in any one of the preceding claims, wherein not more than 500 coaxial reaction tubes, preferably not more than 300 coaxial reaction tubes, particularly preferably not more than 200 coaxial reaction tubes, are arranged in
30 the reaction region.
14. The methanol reformer as claimed in any one of the preceding claims, wherein the catalyst exhibits an average grain size of at most 4 mm, preferably of 2 mm, particularly preferably of 1.5 mm.
15 charging region and the outer tube region are separated by a perforated plate.
15. The methanol reformer as claimed in any one of the preceding claims, wherein the catalyst exhibits an average grain size of at least 0.1 mm, preferably of 0.3 mm, particularly preferably of 0.8 mm.
10985551_1 (GHMatters) P110386.AU
15 10. The methanol reformer as claimed in any one of the preceding claims, wherein the outer tube region is kept at a temperature of not more than 310 °C, preferably of not more than 290 °C, particularly preferably of 280 °C.
16. The methanol reformer as claimed in any one of the preceding claims, wherein the preheating device is connected to the charging region.
17. The methanol reformer as claimed in any one of the preceding claims, wherein the course of flow in the outer tube region runs from top to bottom.
18. The methanol reformer as claimed in any one of the preceding claims, wherein the
19. The methanol reformer as claimed in any one of the preceding claims, wherein the
20. The methanol reformer as claimed in any one of the preceding claims, wherein the methanol reformer comprises a hydrogen liberator and a burner, wherein the residual gas of the hydrogen liberator stripped of the hydrogen is supplied to the burner.
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CN111717890B (en) * 2019-01-24 2021-08-10 中氢新能技术有限公司 Methanol reformer
KR102215836B1 (en) 2020-12-21 2021-02-16 국방과학연구소 Methanol reformer for a submarine
CN114100524A (en) * 2021-10-15 2022-03-01 山东海氢能源科技有限公司 Methanol hydrogen production reactor

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US20100254891A1 (en) * 2007-07-20 2010-10-07 Ifp Bayonet tube exchanger-reactor allowing operation with pressure differences of the order of 100 bars between the tube side and the shell side

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US20100254891A1 (en) * 2007-07-20 2010-10-07 Ifp Bayonet tube exchanger-reactor allowing operation with pressure differences of the order of 100 bars between the tube side and the shell side

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EP3484607B1 (en) 2020-04-15
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AU2017295491A1 (en) 2019-01-31
DE102016212757A1 (en) 2018-01-18
KR102228364B1 (en) 2021-03-17
WO2018011026A1 (en) 2018-01-18

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