CA2557265C - Compact steam reformer - Google Patents
Compact steam reformer Download PDFInfo
- Publication number
- CA2557265C CA2557265C CA2557265A CA2557265A CA2557265C CA 2557265 C CA2557265 C CA 2557265C CA 2557265 A CA2557265 A CA 2557265A CA 2557265 A CA2557265 A CA 2557265A CA 2557265 C CA2557265 C CA 2557265C
- Authority
- CA
- Canada
- Prior art keywords
- steam reformer
- accordance
- reactor
- compact steam
- pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
- B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
- B01J8/0415—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being superimposed one above the other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
- B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00026—Controlling or regulating the heat exchange system
- B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
- B01J2208/00044—Temperature measurement
- B01J2208/00061—Temperature measurement of the reactants
-
- 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
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00132—Tubes
-
- 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
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00141—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
- B01J2208/00194—Tubes
-
- 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
- B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00477—Controlling the temperature by thermal insulation means
- B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00504—Controlling the temperature by means of a burner
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00539—Pressure
-
- 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
- B01J2208/00716—Means for reactor start-up
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The novel compact steam reformer (1) combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO
cleaning is achieved by careful temperature control at the follow-up reactor (37, 39, 39a). Temperature control is made possible by means of pressure-controlled operation of the evaporator (24).
cleaning is achieved by careful temperature control at the follow-up reactor (37, 39, 39a). Temperature control is made possible by means of pressure-controlled operation of the evaporator (24).
Description
Compact Steam Reformer The invention relates to a compact steam reformer and a method for steam reformation.
In the course of steam reforming hydrocarbons for the generation of hydrogen, the material flow for gas generation and the material flow for heating are kept separately in contrast to auto-thermal reforming. In this way the dilution of the hydrogen with nitrogen from the combustion air is avoided during steam reforming.
A compact steam reformer is known from DE 101 19 083 Al, in which the process water is essentially evaporated by means of the reformate to be cooled. The waste heat from the combustion is recovered by pre-warming the air. NOx formation is avoided by employing the flameless oxidation process. This reformer permits a rapid output regulation and has a degree of effectiveness of up to approximately 80%.
A similar reformer is known from WO 02/085781, which is optimized in respect to its exterior insulation.
These reformers meet the intended expectations.
However, there is the desire for further improvements in regard to the simplification of the process regulation and the efficiency of the heat recovery. Moreover, the reformate must be relieved as much as possible of the addition of CO. This must take place so completely that downstream connected CO-sensitive fuel cells are not damaged.
It is known from EP 1 031 374 A2 to place the CO-containing process gas into a so-called CO oxidator, which is simultaneously used as a reformate cooler. Cooling is achieved by evaporating the inflowing process gas in an evaporator.
According to an aspect of the present invention, there is provided a compact steam reformer comprising: a burner, a reactor which is heated by the burner and is used for generating reformate from fuel and H2O steam, a preheating arrangement for preheating supplied air and/or supplied fuel while recouping exhaust gas heat, which is connected to the burner and whose heat recouping quotient (Delta T1/Delta T2) is greater than 0.5, an annular chamber surrounding the preheating arrangement, through which reformate flows and which is thermally insulated toward the exterior, a pipe evaporator used for the generation of H2O steam under pressure and arranged in the annular chamber, and a follow-up reactor for the extensive removal of carbon monoxide portions of the created reformate, which is also arranged in the annular chamber and is in thermal connection with the pipe evaporator through which water flows.
Another aspect provides a method for steam reforming of fuels by means of a steam reformer having an evaporator for generating H2O steam under pressure and a jet pump connected to the evaporator, wherein the steam generated in the evaporator is supplied to the jet pump as a propellant, wherein by means of adding fuel by suction an H2O steam/fuel mixture is generated for feeding a reactor.
Some embodiments may improve the compact steam reformer mentioned at the outset in regard to the conduct of the process and the efficiency of the heat recovery.
The compact steam reformer in accordance with an embodiment has a reactor which is heated by means of a burner.
-la-A preheating device with a high rate of heat recovery is assigned to the burner. This increases the efficiency of the reforming process. The reformer furthermore has a follow-up reactor, which is designed for performing a shift reaction, follow-up oxidation and/or methane generation from the carbon monoxide portions contained in the raw reformate. The follow-up reactor is in a heat-exchanging connection with a pipe evaporator, which maintains the temperature of the follow-up reactor at a fixed level in a controlled manner. By means of this, the desired selectivity of the follow-up reaction is maintained, even in case of a load change. The pipe evaporator causes the evening-out of the temperature in the follow-up reactor in regard to time, as well as in regard to space. The flow of material in the pipe evaporator causes a heat transport in the follow-up reactor, so that the latter can be rapidly adapted to a load change. This applies in particular if the pipe evaporator and the follow-up reactor operate in accordance with a co-current flow.
By means of the determination of the evaporator temperature the temperature of the follow-up reactor is simultaneously fixed within such narrow limits that the CO
content can be reduced to values of less than 50 ppm. Because of this, catalytic follow-up treatment, filtering or other follow-up treatment of the process gas becomes superfluous.
The gas generated by the compact steam reformer can be directly conducted to hydrogen fuel cells.
The temperature of the follow-up reactor can be set in the simplest way by the regulation of the steam pressure. The steam generation temperature for all operational states is simultaneously fixed, along with the steam pressure. Thus, the close thermal connection between the follow-up reactor and the pressure-regulated evaporator, for example by means of the embodiment of the pipe evaporator as a pipe coil and the arrangement of possible catalyzers in the spaces between the pipes, creates favorable conditions for the generation of low-CO hydrogen.
The compact steam reformer can have a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel- steam mixture of a preselected composition and feeds the reactor. This provides the basis for a particularly simple control of the compact steam reformer by means of control techniques. For example, the amount of steam is controlled by an appropriate metering of feed water amounts. The amount of fuel supplied to the reformer for reforming need not be separately controlled and is instead metered in by the jet pump.
Further details of advantageous embodiments ensue from the drawings, the description or the claims.
Exemplary embodiments of the invention are illustrated in the drawings. Shown are in:
Fig. 1, a compact steam reformer with an attached fuel cell in a schematic representation, Fig. 2, the temperature profile of the process gases in the form of a diagram, Fig. 3, the temperature profile of the heating gases in the form of a diagram, Fig. 4, the compact steam reformer in schematic longitudinal section with the allocation of its work zones to the diagrams in accordance with Figs. 2 and 3.
A steam reformer 1 is represented in longitudinal section in Fig. 1. It has an outer shell 2 of a length L and circular cross section of a diameter D. It can be cylindrical, or also stepped in the form of several cylinders. All connectors 3 are preferably conducted through its upper end 4.
A reformer pipe 5, closed at the bottom, is arranged concentrically inside the shell 2 and at a distance from it.
The annular space provided between the shell 2 and the reformer pipe 5 is filled with an insulating material 6 for thermal insulation. A feed line 7 for a mixture of fuel and steam leads from the upper end 4, extending initially straight and then downward by means of turns through the insulating material 6 to a feed connector 8 at the lower end of the reformer pipe.
The lower, cup-shaped end of the latter constitutes the outer shell of a reactor 9 for performing the actual reforming process. Toward the inside, the reactor 9 is delimited by an inner reformer pipe 11, which is closed off in a cup shape at the bottom and is maintained on the end 4 at the top. A
catalyzer 12 for the reforming process is arranged in the cup-shaped annular space between the lower end of the inner reformer pipe 11 and the lower end of the outer reformer pipe 5. Preferably the reformer pipe 11 is provided with ribs 13, 14 on the inside as well as on the outside, which are used for heat transfer between the catalyzer 12 and a combustion chamber 15, which is enclosed by the reformer pipe 11. A burner 16 is assigned to the combustion chamber and is used for heating the catalyzer 12 and is designed to create a flameless oxidation of the fuel introduced into the combustion chamber 15. A number of gas and air nozzles 17, 18 is provided for this purpose, which are arranged, aligned in the same direction, in a ring and create a large-volume circulation. A hollow-cylindrical guide body 19, which is arranged concentrically with the ring of nozzles can assist the large-volume circulation, which is indicated by arrows in Fig. 1.
The gas nozzles 17, as well as the air nozzles 18, are fed via a preheating arrangement 20, which utilizes waste heat.
Parts of this are lines 21, 22, which are conducted in the form of coils through an exhaust gas conduit 23 formed inside the upper part of the reformer pipe 11. In this way the combustion gas supplied to the combustion chamber 15, as well as the supplied air, are preheated. A high recouperation degree, and therefore cool exhaust gas, is achieved.
Preferably (1-Delta T2/Delta Ti) > greater than 0.8, wherein Delta Ti is the exhaust gas difference between the inlet and outlet of the exhaust gas conduit 23 of the preheating arrangement 20, and Delta T2 is the difference between the exhaust gas temperature at the outlet and the fresh air temperature at the outlet. (1-Delta T2/Delta Ti) is at least greater than 0.5.
In the course of steam reforming hydrocarbons for the generation of hydrogen, the material flow for gas generation and the material flow for heating are kept separately in contrast to auto-thermal reforming. In this way the dilution of the hydrogen with nitrogen from the combustion air is avoided during steam reforming.
A compact steam reformer is known from DE 101 19 083 Al, in which the process water is essentially evaporated by means of the reformate to be cooled. The waste heat from the combustion is recovered by pre-warming the air. NOx formation is avoided by employing the flameless oxidation process. This reformer permits a rapid output regulation and has a degree of effectiveness of up to approximately 80%.
A similar reformer is known from WO 02/085781, which is optimized in respect to its exterior insulation.
These reformers meet the intended expectations.
However, there is the desire for further improvements in regard to the simplification of the process regulation and the efficiency of the heat recovery. Moreover, the reformate must be relieved as much as possible of the addition of CO. This must take place so completely that downstream connected CO-sensitive fuel cells are not damaged.
It is known from EP 1 031 374 A2 to place the CO-containing process gas into a so-called CO oxidator, which is simultaneously used as a reformate cooler. Cooling is achieved by evaporating the inflowing process gas in an evaporator.
According to an aspect of the present invention, there is provided a compact steam reformer comprising: a burner, a reactor which is heated by the burner and is used for generating reformate from fuel and H2O steam, a preheating arrangement for preheating supplied air and/or supplied fuel while recouping exhaust gas heat, which is connected to the burner and whose heat recouping quotient (Delta T1/Delta T2) is greater than 0.5, an annular chamber surrounding the preheating arrangement, through which reformate flows and which is thermally insulated toward the exterior, a pipe evaporator used for the generation of H2O steam under pressure and arranged in the annular chamber, and a follow-up reactor for the extensive removal of carbon monoxide portions of the created reformate, which is also arranged in the annular chamber and is in thermal connection with the pipe evaporator through which water flows.
Another aspect provides a method for steam reforming of fuels by means of a steam reformer having an evaporator for generating H2O steam under pressure and a jet pump connected to the evaporator, wherein the steam generated in the evaporator is supplied to the jet pump as a propellant, wherein by means of adding fuel by suction an H2O steam/fuel mixture is generated for feeding a reactor.
Some embodiments may improve the compact steam reformer mentioned at the outset in regard to the conduct of the process and the efficiency of the heat recovery.
The compact steam reformer in accordance with an embodiment has a reactor which is heated by means of a burner.
-la-A preheating device with a high rate of heat recovery is assigned to the burner. This increases the efficiency of the reforming process. The reformer furthermore has a follow-up reactor, which is designed for performing a shift reaction, follow-up oxidation and/or methane generation from the carbon monoxide portions contained in the raw reformate. The follow-up reactor is in a heat-exchanging connection with a pipe evaporator, which maintains the temperature of the follow-up reactor at a fixed level in a controlled manner. By means of this, the desired selectivity of the follow-up reaction is maintained, even in case of a load change. The pipe evaporator causes the evening-out of the temperature in the follow-up reactor in regard to time, as well as in regard to space. The flow of material in the pipe evaporator causes a heat transport in the follow-up reactor, so that the latter can be rapidly adapted to a load change. This applies in particular if the pipe evaporator and the follow-up reactor operate in accordance with a co-current flow.
By means of the determination of the evaporator temperature the temperature of the follow-up reactor is simultaneously fixed within such narrow limits that the CO
content can be reduced to values of less than 50 ppm. Because of this, catalytic follow-up treatment, filtering or other follow-up treatment of the process gas becomes superfluous.
The gas generated by the compact steam reformer can be directly conducted to hydrogen fuel cells.
The temperature of the follow-up reactor can be set in the simplest way by the regulation of the steam pressure. The steam generation temperature for all operational states is simultaneously fixed, along with the steam pressure. Thus, the close thermal connection between the follow-up reactor and the pressure-regulated evaporator, for example by means of the embodiment of the pipe evaporator as a pipe coil and the arrangement of possible catalyzers in the spaces between the pipes, creates favorable conditions for the generation of low-CO hydrogen.
The compact steam reformer can have a jet pump connected to the pipe evaporator or other evaporator, which generates a fuel- steam mixture of a preselected composition and feeds the reactor. This provides the basis for a particularly simple control of the compact steam reformer by means of control techniques. For example, the amount of steam is controlled by an appropriate metering of feed water amounts. The amount of fuel supplied to the reformer for reforming need not be separately controlled and is instead metered in by the jet pump.
Further details of advantageous embodiments ensue from the drawings, the description or the claims.
Exemplary embodiments of the invention are illustrated in the drawings. Shown are in:
Fig. 1, a compact steam reformer with an attached fuel cell in a schematic representation, Fig. 2, the temperature profile of the process gases in the form of a diagram, Fig. 3, the temperature profile of the heating gases in the form of a diagram, Fig. 4, the compact steam reformer in schematic longitudinal section with the allocation of its work zones to the diagrams in accordance with Figs. 2 and 3.
A steam reformer 1 is represented in longitudinal section in Fig. 1. It has an outer shell 2 of a length L and circular cross section of a diameter D. It can be cylindrical, or also stepped in the form of several cylinders. All connectors 3 are preferably conducted through its upper end 4.
A reformer pipe 5, closed at the bottom, is arranged concentrically inside the shell 2 and at a distance from it.
The annular space provided between the shell 2 and the reformer pipe 5 is filled with an insulating material 6 for thermal insulation. A feed line 7 for a mixture of fuel and steam leads from the upper end 4, extending initially straight and then downward by means of turns through the insulating material 6 to a feed connector 8 at the lower end of the reformer pipe.
The lower, cup-shaped end of the latter constitutes the outer shell of a reactor 9 for performing the actual reforming process. Toward the inside, the reactor 9 is delimited by an inner reformer pipe 11, which is closed off in a cup shape at the bottom and is maintained on the end 4 at the top. A
catalyzer 12 for the reforming process is arranged in the cup-shaped annular space between the lower end of the inner reformer pipe 11 and the lower end of the outer reformer pipe 5. Preferably the reformer pipe 11 is provided with ribs 13, 14 on the inside as well as on the outside, which are used for heat transfer between the catalyzer 12 and a combustion chamber 15, which is enclosed by the reformer pipe 11. A burner 16 is assigned to the combustion chamber and is used for heating the catalyzer 12 and is designed to create a flameless oxidation of the fuel introduced into the combustion chamber 15. A number of gas and air nozzles 17, 18 is provided for this purpose, which are arranged, aligned in the same direction, in a ring and create a large-volume circulation. A hollow-cylindrical guide body 19, which is arranged concentrically with the ring of nozzles can assist the large-volume circulation, which is indicated by arrows in Fig. 1.
The gas nozzles 17, as well as the air nozzles 18, are fed via a preheating arrangement 20, which utilizes waste heat.
Parts of this are lines 21, 22, which are conducted in the form of coils through an exhaust gas conduit 23 formed inside the upper part of the reformer pipe 11. In this way the combustion gas supplied to the combustion chamber 15, as well as the supplied air, are preheated. A high recouperation degree, and therefore cool exhaust gas, is achieved.
Preferably (1-Delta T2/Delta Ti) > greater than 0.8, wherein Delta Ti is the exhaust gas difference between the inlet and outlet of the exhaust gas conduit 23 of the preheating arrangement 20, and Delta T2 is the difference between the exhaust gas temperature at the outlet and the fresh air temperature at the outlet. (1-Delta T2/Delta Ti) is at least greater than 0.5.
An ignition burner Z or an electric heating device can be centrally provided, which are used for preheating the combustion chamber 15 until the start of the flameless oxidation.
The steam reformer 1 so far described contains a steam generator 24 arranged in the annular space 10 between the outer recouperation pipe 5 and the inner recouperation pipe 11 and is coupled with them in a heat-technological manner. Preferably the steam generator 24 is constituted by a pipe coil, which is divided into several sections and is arranged concentrically in respect to the preheating device. A pipe 25 is arranged in-between, which encloses a further annular space 26 together with the inner reformer pipe 11. This space is filled with an insulating material 27 for the thermal insulation of the exhaust gas conduit 23 from the reformate conduit, which is formed between the outer reformer pipe 5 and the pipe 25 through the annular space 10.
The steam generator 24 has a feedwater connector 28, starting from which a first pipe coil section 29 leads through the reformate conduit, which terminates at a reformate outlet 31. The pipe coil section 29 constitutes a water/reformate counterflow radiator operating in a counterflow manner.
The pipe coil 29 leads to a bridging pipe 32, which leads through the space 26 in the axial direction. It then changes back into the outer annular space 10 constituting the reformat conduit, and is continued there as the pipe coil section 33. It constitutes a water heater and simultaneously a reformate shock cooler (quench cooler, section A in Figs. 3 and 5). A gas- permeable annular insulating body 34 is arranged between the pipe coil section 33 and the catalyzer 12, which prevents overheating of the steam generator 24 when there is no load, i.e. in case of a feedwater flow-through of zero or close to zero.
A further pipe coil section 35 follows the pipe coil section 33 and consists of several coils 36, 38 (section B in Figs 3 and 5). These coils 36, 38 have been embedded in a catalyzer, which also fills spaces between coils and constitutes a follow-up reactor. Here, the first coils 36 have been embedded, for example, in a CO-shift catalyzer 37. In the present exemplary embodiment the subsequent coils 38 (section C
in Figs. 3 and 5) have been embedded in a methane-generating catalyst 39. The catalysts 37, 39 can be attached to a suitable catalyst body, such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36, 38, or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
In this way the evaporator 24 is divided into three sections A, B, C, namely the pipe coil section 33 for the at least partial evaporation of the water and shock cooling of the reformate, as well as the sections constituted by the coils 36 and 38, in which the further, to a large extent complete evaporation of the water is provided by heat exchange with the respective catalyzers 37, 39. The catalysts 37, 39 constitute the two-stage follow-up reactor.
The outlet of the evaporator is connected via an ascending pipe 41 with a pressure-control valve 42, which maintains the pressure in the evaporator 24 constant, regardless of the flow through it. The steam emitted by the pressure-control valve 42 is conducted to the propellant nozzle connector 43 of a jet pump 44, whose suction connector 45 is connected to a fuel feed line. Its outlet feeds a mixture of steam and fuel to the feed line 7.
The feedwater connector 28 is provided with feedwater by a feedwater pump 46. The latter is controlled or regulated by a control device 47 on the basis of a temperature of the catalyzer 12 detected by means of a temperature sensor 48 in such a way, that the temperature of the catalyzer 12 is kept constant. Since the air requirement for the burner and the fuel cell are proportional to the energy supply PCH4, and therefore the feedwater temperature, the regulation ratio of the air blower 49 can track in a simple manner the regulation ratio of the feedwater pump 46, which is specified by the control device 47.
Air and combustion gas are supplied via the lines 21, 22. The residue gas from the anode of a fuel cell can be used as the combustion gas.
The reformate is conducted to an anode input of a fuel cell 52. Residue gas generated by the anode is conducted via a line 53 to the preheating arrangement 20. The blower 49 conveys air to the cathode of the fuel cell and to the preheating arrangement 20.
The steam reformer so far described operates as follows:
Reference is made to Figs. 2 to 4. Here, by means of a branch I of a curve, Fig. illustrates the temperature of the gases supplied via the lines 21, 22, namely air and combustion gas. The branch II of the curve illustrates the exhaust gas temperature of the exhaust gas conducted out in counterflow.
The represented temperatures reflect the temperature profile in the steam reformer 1 illustrated in Fig. 4, in particular in its recouperator. The loop-shaped branch III of the curve in Fig. 3 represents the temperature in the combustion chamber 15 in the course of the flameless oxidation. As represented, the gas performs several revolutions through the combustion chamber 15. As can be noted, it is possible at an exhaust gas temperature of, for example, 150 C, to attain an air and gas preheating up to approximately 800 C.
The curve in Fig. 2 represents the temperature profile of the gas to be reformed and already reformed. The branch IV
of the curve indicates the heating of the feedwater in the pipe coil section 29, which is simultaneously a feedwater preheater and a water reformate counterflow cooler. Now the feedwater, which is under pressure and preheated, is conducted to the evaporator 24 at a temperature of slightly above 100 C.
Initially, this is symbolized by the lower horizontal branch V
of the curve. The preheated feedwater enters the evaporator at a point VI. It is brought to the evaporation temperature (curve VIII) in the pipe coil section 33, and then passes through the entire evaporator 24, in which it slowly evaporates. In the course of this it retains its evaporation temperature of 200 C, for example, as illustrated by the horizontal branch VIII of the curve. In the same way as a heating pipe, the pipe evaporator 24 sets a uniform temperature for the follow-up reactor. The evaporation temperature TS is not exceeded. The size of the evaporator temperature is set by means of the evaporator pressure at the pressure-control valve 42.
The temperature profile in accordance with Fig. 2 is also maintained within narrow limits, even in case of load changes, in particular in the last stage. The selectivity of the follow-up reaction is maintained in this way. The temperature setting in the last follow-up reactor stage is here effected solely by pressure control.
From the evaporator 24, the generated steam reaches the jet pump 44. The latter fixes the steam/fuel ratio by means of its ratio between the propellant nozzle diameter and the mixing nozzle diameter. The jet pump 44 aspirates the desired amount of fuel via its suction connector 45 and mixes it with steam.
In the process the steam temperature initially slightly drops (Fig. 2, branch XI of the curve), wherein the temperature of the admixed combustion gas suddenly rises (branch X of the curve). Then the temperature slowly rises until the feed connector 8 is reached (branch XI of the curve). In the catalyzer 12 the temperature of the curve continues to increase in accordance with the branch XII until it reaches the temperature TR, which has been detected by the temperature sensor 49 and is constantly regulated by metering in feedwater.
The reformate generated by the catalyzer 12 leaves the reactor 9 at this temperature. When encountering the first section of the evaporator 24 (pipe coil section 33), the reformate is shock-cooled (Fig. 2, branch XIII of the curve) as section A.
Thereafter, the cooled reformate reaches the catalysts 37 and 39. There, a follow-up reaction for CO conversion takes place. The precise temperature control prevents too great a methane generation, in particular of the existing CO2 portions.
The steam reformer 1 so far described operates inherently stably. An increased reduction of the electrical output Pei worsens the caloric value of the residue gas from the anode. Thus, if the temperature at the temperature sensor 49 drops, the control device increases the feedwater conveyance and therefore the steam generation and the reformate generation. The resultant increase of residue gas from the anode increases the burner output in the combustion chamber 15.
In this way the steam reformer 1 performs an automatic matching to the load.
An actually embodied steam reformer 1 has attained the following characteristic values:
100(VxHu)hydrogen etaR = AAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA in %
(VxHu)process gas + (VxHu)heating gas V [m3/h] - volume flow in standard state Hu [kWh/m3] - caloric value Efficiency of the conversion into hydrogen when heating the reformer with residue gas from the anode:
100(VxHu)hydrogen*
.......... in %
etaR = A ....................AAAAAAA .. .. ..
(VxHu)process gas * hydrogen converted in the fuel cell (typically 75%) Example of the novel reformer:
- Exterior dimensions: L = 0.6 m, D = 0.3 m - Process gas: 1 m3/h natural gas of caloric value of 10 kWh/m3 - Water: 2.5 kg/h at 15 bar (= 3 m3/h steam, S/C = 3) - Heating gas: 0.41 m3/h natural gas of caloric value of 10 kWh/m3 - Reformate: 4 m3/H H2 of caloric value of 3 kWh/m3 - Efficiency etaR = 85%
When heating with residue gas from anode: (25% of H2 from the reformate, incl. CH4 formed during methane generation) - Available hydrogen: 2.7 m3/h of caloric value of 3 kWh/m3 -Efficiency etaR = 81%
The losses of the reformate which can be affected are respectively proportional Delta Tw (Delta Tw is the difference between wall temperature and ambient temperature), Delta T2 and Delta TR (see Fig. 2). They are furthermore a function of the excess steam in the reformate, which is necessary for soot-free reforming and the shift reaction.
The novel compact steam reformer 1 combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO
cleaning is achieved by careful temperature control at the follow-up reactor 37, 39, 39a. Temperature control is made possible by means of pressure-controlled operation of the evaporator 24.
The steam reformer 1 so far described contains a steam generator 24 arranged in the annular space 10 between the outer recouperation pipe 5 and the inner recouperation pipe 11 and is coupled with them in a heat-technological manner. Preferably the steam generator 24 is constituted by a pipe coil, which is divided into several sections and is arranged concentrically in respect to the preheating device. A pipe 25 is arranged in-between, which encloses a further annular space 26 together with the inner reformer pipe 11. This space is filled with an insulating material 27 for the thermal insulation of the exhaust gas conduit 23 from the reformate conduit, which is formed between the outer reformer pipe 5 and the pipe 25 through the annular space 10.
The steam generator 24 has a feedwater connector 28, starting from which a first pipe coil section 29 leads through the reformate conduit, which terminates at a reformate outlet 31. The pipe coil section 29 constitutes a water/reformate counterflow radiator operating in a counterflow manner.
The pipe coil 29 leads to a bridging pipe 32, which leads through the space 26 in the axial direction. It then changes back into the outer annular space 10 constituting the reformat conduit, and is continued there as the pipe coil section 33. It constitutes a water heater and simultaneously a reformate shock cooler (quench cooler, section A in Figs. 3 and 5). A gas- permeable annular insulating body 34 is arranged between the pipe coil section 33 and the catalyzer 12, which prevents overheating of the steam generator 24 when there is no load, i.e. in case of a feedwater flow-through of zero or close to zero.
A further pipe coil section 35 follows the pipe coil section 33 and consists of several coils 36, 38 (section B in Figs 3 and 5). These coils 36, 38 have been embedded in a catalyzer, which also fills spaces between coils and constitutes a follow-up reactor. Here, the first coils 36 have been embedded, for example, in a CO-shift catalyzer 37. In the present exemplary embodiment the subsequent coils 38 (section C
in Figs. 3 and 5) have been embedded in a methane-generating catalyst 39. The catalysts 37, 39 can be attached to a suitable catalyst body, such as a woven wire device or the like, for example, or also deposited as loose bulk material between the coils 36, 38, or can be directly formed on the ribs of an evaporator embodied as a ribbed pipe.
In this way the evaporator 24 is divided into three sections A, B, C, namely the pipe coil section 33 for the at least partial evaporation of the water and shock cooling of the reformate, as well as the sections constituted by the coils 36 and 38, in which the further, to a large extent complete evaporation of the water is provided by heat exchange with the respective catalyzers 37, 39. The catalysts 37, 39 constitute the two-stage follow-up reactor.
The outlet of the evaporator is connected via an ascending pipe 41 with a pressure-control valve 42, which maintains the pressure in the evaporator 24 constant, regardless of the flow through it. The steam emitted by the pressure-control valve 42 is conducted to the propellant nozzle connector 43 of a jet pump 44, whose suction connector 45 is connected to a fuel feed line. Its outlet feeds a mixture of steam and fuel to the feed line 7.
The feedwater connector 28 is provided with feedwater by a feedwater pump 46. The latter is controlled or regulated by a control device 47 on the basis of a temperature of the catalyzer 12 detected by means of a temperature sensor 48 in such a way, that the temperature of the catalyzer 12 is kept constant. Since the air requirement for the burner and the fuel cell are proportional to the energy supply PCH4, and therefore the feedwater temperature, the regulation ratio of the air blower 49 can track in a simple manner the regulation ratio of the feedwater pump 46, which is specified by the control device 47.
Air and combustion gas are supplied via the lines 21, 22. The residue gas from the anode of a fuel cell can be used as the combustion gas.
The reformate is conducted to an anode input of a fuel cell 52. Residue gas generated by the anode is conducted via a line 53 to the preheating arrangement 20. The blower 49 conveys air to the cathode of the fuel cell and to the preheating arrangement 20.
The steam reformer so far described operates as follows:
Reference is made to Figs. 2 to 4. Here, by means of a branch I of a curve, Fig. illustrates the temperature of the gases supplied via the lines 21, 22, namely air and combustion gas. The branch II of the curve illustrates the exhaust gas temperature of the exhaust gas conducted out in counterflow.
The represented temperatures reflect the temperature profile in the steam reformer 1 illustrated in Fig. 4, in particular in its recouperator. The loop-shaped branch III of the curve in Fig. 3 represents the temperature in the combustion chamber 15 in the course of the flameless oxidation. As represented, the gas performs several revolutions through the combustion chamber 15. As can be noted, it is possible at an exhaust gas temperature of, for example, 150 C, to attain an air and gas preheating up to approximately 800 C.
The curve in Fig. 2 represents the temperature profile of the gas to be reformed and already reformed. The branch IV
of the curve indicates the heating of the feedwater in the pipe coil section 29, which is simultaneously a feedwater preheater and a water reformate counterflow cooler. Now the feedwater, which is under pressure and preheated, is conducted to the evaporator 24 at a temperature of slightly above 100 C.
Initially, this is symbolized by the lower horizontal branch V
of the curve. The preheated feedwater enters the evaporator at a point VI. It is brought to the evaporation temperature (curve VIII) in the pipe coil section 33, and then passes through the entire evaporator 24, in which it slowly evaporates. In the course of this it retains its evaporation temperature of 200 C, for example, as illustrated by the horizontal branch VIII of the curve. In the same way as a heating pipe, the pipe evaporator 24 sets a uniform temperature for the follow-up reactor. The evaporation temperature TS is not exceeded. The size of the evaporator temperature is set by means of the evaporator pressure at the pressure-control valve 42.
The temperature profile in accordance with Fig. 2 is also maintained within narrow limits, even in case of load changes, in particular in the last stage. The selectivity of the follow-up reaction is maintained in this way. The temperature setting in the last follow-up reactor stage is here effected solely by pressure control.
From the evaporator 24, the generated steam reaches the jet pump 44. The latter fixes the steam/fuel ratio by means of its ratio between the propellant nozzle diameter and the mixing nozzle diameter. The jet pump 44 aspirates the desired amount of fuel via its suction connector 45 and mixes it with steam.
In the process the steam temperature initially slightly drops (Fig. 2, branch XI of the curve), wherein the temperature of the admixed combustion gas suddenly rises (branch X of the curve). Then the temperature slowly rises until the feed connector 8 is reached (branch XI of the curve). In the catalyzer 12 the temperature of the curve continues to increase in accordance with the branch XII until it reaches the temperature TR, which has been detected by the temperature sensor 49 and is constantly regulated by metering in feedwater.
The reformate generated by the catalyzer 12 leaves the reactor 9 at this temperature. When encountering the first section of the evaporator 24 (pipe coil section 33), the reformate is shock-cooled (Fig. 2, branch XIII of the curve) as section A.
Thereafter, the cooled reformate reaches the catalysts 37 and 39. There, a follow-up reaction for CO conversion takes place. The precise temperature control prevents too great a methane generation, in particular of the existing CO2 portions.
The steam reformer 1 so far described operates inherently stably. An increased reduction of the electrical output Pei worsens the caloric value of the residue gas from the anode. Thus, if the temperature at the temperature sensor 49 drops, the control device increases the feedwater conveyance and therefore the steam generation and the reformate generation. The resultant increase of residue gas from the anode increases the burner output in the combustion chamber 15.
In this way the steam reformer 1 performs an automatic matching to the load.
An actually embodied steam reformer 1 has attained the following characteristic values:
100(VxHu)hydrogen etaR = AAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA in %
(VxHu)process gas + (VxHu)heating gas V [m3/h] - volume flow in standard state Hu [kWh/m3] - caloric value Efficiency of the conversion into hydrogen when heating the reformer with residue gas from the anode:
100(VxHu)hydrogen*
.......... in %
etaR = A ....................AAAAAAA .. .. ..
(VxHu)process gas * hydrogen converted in the fuel cell (typically 75%) Example of the novel reformer:
- Exterior dimensions: L = 0.6 m, D = 0.3 m - Process gas: 1 m3/h natural gas of caloric value of 10 kWh/m3 - Water: 2.5 kg/h at 15 bar (= 3 m3/h steam, S/C = 3) - Heating gas: 0.41 m3/h natural gas of caloric value of 10 kWh/m3 - Reformate: 4 m3/H H2 of caloric value of 3 kWh/m3 - Efficiency etaR = 85%
When heating with residue gas from anode: (25% of H2 from the reformate, incl. CH4 formed during methane generation) - Available hydrogen: 2.7 m3/h of caloric value of 3 kWh/m3 -Efficiency etaR = 81%
The losses of the reformate which can be affected are respectively proportional Delta Tw (Delta Tw is the difference between wall temperature and ambient temperature), Delta T2 and Delta TR (see Fig. 2). They are furthermore a function of the excess steam in the reformate, which is necessary for soot-free reforming and the shift reaction.
The novel compact steam reformer 1 combines in one device the steam reformation of natural gas or other fuel, including subsequent cleaning of CO. Controlled catalytic CO
cleaning is achieved by careful temperature control at the follow-up reactor 37, 39, 39a. Temperature control is made possible by means of pressure-controlled operation of the evaporator 24.
Claims (16)
1. A compact steam reformer comprising:
a burner, a reactor which is heated by the burner and is used for generating reformate from fuel and H2O steam, a preheating arrangement for preheating supplied air and/or supplied fuel while recouping exhaust gas heat, which is connected to the burner and whose heat recouping quotient (Delta T1/Delta T2) is greater than 0.5, an annular chamber surrounding the preheating arrangement, through which reformate flows and which is thermally insulated toward the exterior, a pipe evaporator used for the generation of H2O steam under pressure and arranged in the annular chamber, and a follow-up reactor for the extensive removal of carbon monoxide portions of the created reformate, which is also arranged in the annular chamber and is in thermal connection with the pipe evaporator through which water flows.
a burner, a reactor which is heated by the burner and is used for generating reformate from fuel and H2O steam, a preheating arrangement for preheating supplied air and/or supplied fuel while recouping exhaust gas heat, which is connected to the burner and whose heat recouping quotient (Delta T1/Delta T2) is greater than 0.5, an annular chamber surrounding the preheating arrangement, through which reformate flows and which is thermally insulated toward the exterior, a pipe evaporator used for the generation of H2O steam under pressure and arranged in the annular chamber, and a follow-up reactor for the extensive removal of carbon monoxide portions of the created reformate, which is also arranged in the annular chamber and is in thermal connection with the pipe evaporator through which water flows.
2. The compact steam reformer in accordance with claim 1, wherein the reformate and water flow through the follow-up reactor and the pipe evaporator in the same flow direction.
3. The compact steam reformer in accordance with claim 1, wherein a water/reformate counterflow cooler is connected to the inlet side of the pipe evaporator and the outlet side of the follow-up reactor.
4. The compact steam reformer in accordance with any one of claims 1 to 3, wherein the follow-up reactor contains a shift catalyzer and/or a methane-generating catalyzer and/or a follow-up oxidation catalyzer.
5. The compact steam reformer in accordance with any one of claims 1 to 3, wherein the pipe evaporator is designed as a pressure-proof pipe coil, which defines coil spaces in which a catalyzer for encouraging the follow-up reaction is arranged.
6. The compact steam reformer in accordance with any one of claims 1 to 4, wherein the pipe evaporator is embodied as a pressure-proof ribbed pipe.
7. The compact steam reformer in accordance with any one of claims 1 to 6, wherein a pressure regulator is connected to the outlet of the pipe evaporator.
8. The compact steam reformer in accordance with claim 7, wherein the pressure regulator is adjusted to such a pressure that the evaporation temperature of the water in the evaporation pipe is set to a temperature between 130°C
and 280°C.
and 280°C.
9. The compact steam reformer in accordance with claim 7 or 8, wherein the pressure regulator is configured to maintain pressure in the pipe evaporator constant.
10. The compact steam reformer in accordance with any one of claims 1 to 9, wherein in the area which is in thermal connection with the follow-up reactor, the flow of material in the pipe evaporator contains a liquid phase.
11. The compact steam reformer in accordance with any one of claims 1 to 10, wherein a jet pump is connected to the pipe evaporator, which is used for adding fuel by suction and for generating an H2O steam/fuel mixture for feeding the reactor.
12. The compact steam reformer in accordance with claim 11, wherein the jet pump is an unregulated jet pump.
13. The compact steam reformer in accordance with any one of claims 1 to 11, comprising a regulator for regulating the amount of feedwater fed to the pipe evaporator.
14. The compact steam reformer in accordance with any one of claims 1 to 13, wherein the reactor is connected with a temperature sensor, which is used for affecting the feedwater supply of the pipe evaporator in such a way that the feedwater supply is increased if the temperature drops, and vice versa.
15. The compact steam reformer in accordance with claim 14, wherein the temperature sensor controls a blower for supplying the burner with combustion air.
16. The compact steam reformer in accordance with any one of claims 1 to 15, wherein the burner is at least partially supplied with residue gas from the anode of a connected fuel cell.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004010910A DE102004010910B4 (en) | 2004-03-06 | 2004-03-06 | Compact steam reformer |
DE102004010910.9 | 2004-03-06 | ||
PCT/EP2005/002194 WO2005084771A2 (en) | 2004-03-06 | 2005-03-02 | Compact steam reformer |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2557265A1 CA2557265A1 (en) | 2005-09-15 |
CA2557265C true CA2557265C (en) | 2012-10-30 |
Family
ID=34877449
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2557265A Expired - Fee Related CA2557265C (en) | 2004-03-06 | 2005-03-02 | Compact steam reformer |
Country Status (8)
Country | Link |
---|---|
US (1) | US7608120B2 (en) |
EP (2) | EP2070591A3 (en) |
JP (1) | JP4857258B2 (en) |
KR (1) | KR101202605B1 (en) |
CN (1) | CN100556527C (en) |
CA (1) | CA2557265C (en) |
DE (1) | DE102004010910B4 (en) |
WO (1) | WO2005084771A2 (en) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100599735B1 (en) * | 2004-11-29 | 2006-07-12 | 삼성에스디아이 주식회사 | Fuel cell system and reformer |
JP2007091584A (en) * | 2005-09-27 | 2007-04-12 | Samsung Sdi Co Ltd | Fuel reforming apparatus |
DE102006039039A1 (en) * | 2006-05-23 | 2007-11-29 | Zentrum für Brennstoffzellen-Technik GmbH | Heating of a catalyst stage mounted downstream of a reformer, comprises feeding of air as heat transfer medium into the reformer through supply line, heating the fed medium by heater and thermally coupling the heated up medium in the stage |
JP5130684B2 (en) | 2006-09-27 | 2013-01-30 | カシオ計算機株式会社 | Reaction apparatus and electronic equipment |
DE102006047493B4 (en) * | 2006-10-05 | 2010-01-07 | Ws Reformer Gmbh | Fuel cell system and method for generating electricity and heat from liquid and gaseous fuels |
EP1995516B1 (en) * | 2007-05-23 | 2010-06-02 | WS-Wärmeprozesstechnik GmbH | Recuperator burner with flattened heat exchange pipes |
US9188086B2 (en) | 2008-01-07 | 2015-11-17 | Mcalister Technologies, Llc | Coupled thermochemical reactors and engines, and associated systems and methods |
US8561598B2 (en) * | 2008-01-07 | 2013-10-22 | Mcalister Technologies, Llc | Method and system of thermochemical regeneration to provide oxygenated fuel, for example, with fuel-cooled fuel injectors |
US8441361B2 (en) | 2010-02-13 | 2013-05-14 | Mcallister Technologies, Llc | Methods and apparatuses for detection of properties of fluid conveyance systems |
PL2519342T3 (en) | 2009-12-30 | 2019-03-29 | Hysytech S.R.L. | Endothermic reaction unit and steam reforming device comprising this reaction unit |
CN102844266A (en) | 2010-02-13 | 2012-12-26 | 麦卡利斯特技术有限责任公司 | Chemical processes and reactors for efficiently producing hydrogen fuels and structural materials, and associated systems and methods |
KR20130051492A (en) * | 2010-02-13 | 2013-05-20 | 맥알리스터 테크놀로지즈 엘엘씨 | Reactor vessels with pressure and heat transfer features for producing hydrogenbased fuels and structural elements,and associated systems and methods |
KR20130069610A (en) * | 2010-03-31 | 2013-06-26 | 카운실 오브 사이언티픽 엔드 인더스트리얼 리서치 | Hydrogen/syngas generator |
US8920732B2 (en) | 2011-02-15 | 2014-12-30 | Dcns | Systems and methods for actively controlling steam-to-carbon ratio in hydrogen-producing fuel processing systems |
DE102011013026A1 (en) | 2011-03-04 | 2012-09-06 | Dbi - Gastechnologisches Institut Ggmbh Freiberg | Process and arrangement for steam reforming of hydrocarbon gases |
US8734546B2 (en) | 2011-08-12 | 2014-05-27 | Mcalister Technologies, Llc | Geothermal energization of a non-combustion chemical reactor and associated systems and methods |
US8911703B2 (en) | 2011-08-12 | 2014-12-16 | Mcalister Technologies, Llc | Reducing and/or harvesting drag energy from transport vehicles, including for chemical reactors, and associated systems and methods |
WO2013025645A2 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Systems and methods for collecting and processing permafrost gases, and for cooling permafrost |
WO2013025655A2 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Systems and methods for providing supplemental aqueous thermal energy |
WO2013025659A1 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Reducing and/or harvesting drag energy from transport vehicles, includings for chemical reactors, and associated systems and methods |
EP2742207A4 (en) | 2011-08-12 | 2016-06-29 | Mcalister Technologies Llc | Systems and methods for extracting and processing gases from submerged sources |
WO2013025650A1 (en) | 2011-08-12 | 2013-02-21 | Mcalister Technologies, Llc | Mobile transport platforms for producing hydrogen and structural materials and associated systems and methods |
US8926719B2 (en) | 2013-03-14 | 2015-01-06 | Mcalister Technologies, Llc | Method and apparatus for generating hydrogen from metal |
US20150285534A1 (en) * | 2014-04-02 | 2015-10-08 | King Fahd University Of Petroleum And Minerals | Solar collector with optimal profile for energy distribution on a tubular receiver |
CN104226206A (en) * | 2014-07-28 | 2014-12-24 | 河北新启元能源技术开发股份有限公司 | Pressure difference reducing device using organic solvent to wash reactor |
DE102015120106A1 (en) * | 2015-11-19 | 2017-05-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method and device for adjusting the ignition characteristic of a fuel |
DE102016105492A1 (en) * | 2016-03-23 | 2017-09-28 | Karlsruher Institut für Technologie | Reactor for the production of synthesis gas |
DE102016208843A1 (en) * | 2016-05-23 | 2017-11-23 | Siemens Aktiengesellschaft | Reactor with a jet pump and method of increasing the pressure of a reactant with a jet pump |
CN106025448A (en) * | 2016-07-15 | 2016-10-12 | 郑州佛光发电设备有限公司 | Liquid pipeline built-in compact type aluminum-air fuel cell monomer |
KR101866500B1 (en) * | 2016-11-14 | 2018-07-04 | 한국에너지기술연구원 | Hydrogen production rector including carbon monoxide removing unit |
CN106365118B (en) * | 2016-11-15 | 2018-09-14 | 晋城市阿邦迪能源有限公司 | Methanol steam reforming room with CO purifications and temp monitoring function |
US11480364B2 (en) * | 2017-11-28 | 2022-10-25 | Anderson Industries, Llc | Flameless heater system to generate heat and humidity |
US11285003B2 (en) | 2018-03-20 | 2022-03-29 | Medtronic Vascular, Inc. | Prolapse prevention device and methods of use thereof |
US11026791B2 (en) | 2018-03-20 | 2021-06-08 | Medtronic Vascular, Inc. | Flexible canopy valve repair systems and methods of use |
KR20220100350A (en) | 2021-01-08 | 2022-07-15 | 엘지전자 주식회사 | Reformer |
KR20220100351A (en) | 2021-01-08 | 2022-07-15 | 엘지전자 주식회사 | Reformer |
FR3129608A1 (en) * | 2021-11-30 | 2023-06-02 | Naval Group | REFORMER STRUCTURE |
CN115650165B (en) * | 2022-11-15 | 2024-04-12 | 中国科学院大连化学物理研究所 | Fuel evaporation chamber structure matched with fuel cell hydrogen production reformer for use |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3745047A (en) * | 1970-12-31 | 1973-07-10 | United Aircraft Corp | Proportional action electronic fuel control for fuel cells |
JPS5981416A (en) * | 1982-11-01 | 1984-05-11 | Yoshimitsu Sumiyoshi | Steam reforming method and device therefor |
JPS6270202A (en) * | 1985-09-19 | 1987-03-31 | Fuji Electric Co Ltd | Fuel reforming apparatus for fuel cell |
GB9403198D0 (en) * | 1994-02-19 | 1994-04-13 | Rolls Royce Plc | A solid oxide fuel cell stack |
JPH09241002A (en) * | 1996-03-11 | 1997-09-16 | Fuji Electric Co Ltd | Fuel reformer for fuel cell power generator |
ATE275529T1 (en) * | 1996-06-28 | 2004-09-15 | Matsushita Electric Works Ltd | REFORMING DEVICE FOR PRODUCING A CRACKED GAS WITH REDUCED CO CONTENT. |
US6126908A (en) * | 1996-08-26 | 2000-10-03 | Arthur D. Little, Inc. | Method and apparatus for converting hydrocarbon fuel into hydrogen gas and carbon dioxide |
US6537352B2 (en) * | 1996-10-30 | 2003-03-25 | Idatech, Llc | Hydrogen purification membranes, components and fuel processing systems containing the same |
US5997594A (en) * | 1996-10-30 | 1999-12-07 | Northwest Power Systems, Llc | Steam reformer with internal hydrogen purification |
JPH10223244A (en) * | 1997-02-03 | 1998-08-21 | Fuji Electric Co Ltd | Fuel cell electricity generating apparatus |
DE19721630C1 (en) * | 1997-05-23 | 1999-02-11 | Fraunhofer Ges Forschung | Device for reforming hydrocarbons containing starting materials |
EP1138096B1 (en) * | 1998-10-14 | 2010-10-06 | IdaTech, LLC | Fuel processing system |
DE19907665C2 (en) | 1999-02-23 | 2003-07-31 | Ballard Power Systems | Device for utilizing heat generated during a catalytic reaction |
WO2000063114A1 (en) * | 1999-04-20 | 2000-10-26 | Tokyo Gas Co., Ltd. | Single-pipe cylindrical reformer and operation method therefor |
US6641625B1 (en) * | 1999-05-03 | 2003-11-04 | Nuvera Fuel Cells, Inc. | Integrated hydrocarbon reforming system and controls |
WO2000066487A1 (en) * | 1999-05-03 | 2000-11-09 | Nuvera Fuel Cells | Autothermal reforming system with integrated shift beds, preferential oxidation reactor, auxiliary reactor, and system controls |
DE19954871A1 (en) * | 1999-09-07 | 2001-03-15 | Caloric Anlagenbau Gmbh | Hydrogen recovery from hydrocarbons involves steam reforming in presence of catalyst, separating hydrogen and recycling residual gas stream to reformer |
JP3903710B2 (en) * | 2000-07-25 | 2007-04-11 | 富士電機ホールディングス株式会社 | Fuel reformer and polymer electrolyte fuel cell power generator using the same |
DE10119083C1 (en) | 2001-04-19 | 2002-11-28 | Joachim Alfred Wuenning | Compact steam reformer |
JP2004059415A (en) * | 2002-06-03 | 2004-02-26 | Mitsubishi Heavy Ind Ltd | Fuel reformer and fuel cell power generation system |
JP2004031280A (en) * | 2002-06-28 | 2004-01-29 | Ebara Ballard Corp | Fuel processing device, fuel cell power generation system, fuel processing method and fuel cell power generation method |
JP4520100B2 (en) * | 2003-03-20 | 2010-08-04 | 新日本石油株式会社 | Hydrogen production apparatus and fuel cell system |
-
2004
- 2004-03-06 DE DE102004010910A patent/DE102004010910B4/en not_active Expired - Fee Related
-
2005
- 2005-03-02 EP EP09156079A patent/EP2070591A3/en not_active Withdrawn
- 2005-03-02 EP EP05732059A patent/EP1732658B1/en not_active Expired - Fee Related
- 2005-03-02 WO PCT/EP2005/002194 patent/WO2005084771A2/en not_active Application Discontinuation
- 2005-03-02 CN CNB2005800071843A patent/CN100556527C/en not_active Expired - Fee Related
- 2005-03-02 JP JP2007502236A patent/JP4857258B2/en not_active Expired - Fee Related
- 2005-03-02 KR KR1020067018135A patent/KR101202605B1/en active IP Right Grant
- 2005-03-02 CA CA2557265A patent/CA2557265C/en not_active Expired - Fee Related
-
2006
- 2006-09-02 US US11/514,537 patent/US7608120B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
KR20070019986A (en) | 2007-02-16 |
DE102004010910B4 (en) | 2006-10-26 |
CN1980732A (en) | 2007-06-13 |
CA2557265A1 (en) | 2005-09-15 |
EP2070591A2 (en) | 2009-06-17 |
CN100556527C (en) | 2009-11-04 |
EP1732658A2 (en) | 2006-12-20 |
EP2070591A3 (en) | 2009-08-26 |
EP1732658B1 (en) | 2011-09-14 |
DE102004010910A1 (en) | 2005-09-22 |
JP2007527842A (en) | 2007-10-04 |
KR101202605B1 (en) | 2012-11-19 |
US7608120B2 (en) | 2009-10-27 |
US20070006529A1 (en) | 2007-01-11 |
JP4857258B2 (en) | 2012-01-18 |
WO2005084771A2 (en) | 2005-09-15 |
WO2005084771A3 (en) | 2005-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2557265C (en) | Compact steam reformer | |
US6835354B2 (en) | Integrated reactor | |
AU2006264047B2 (en) | Compact reforming reactor | |
US7074373B1 (en) | Thermally-integrated low temperature water-gas shift reactor apparatus and process | |
KR101299170B1 (en) | Compact reforming reactor | |
US20150129805A1 (en) | Method for producing co and/or h2 in an alternating operation between two operating modes | |
US20020152681A1 (en) | Compact steam reformer | |
CN104411625A (en) | Process for reforming hydrocarbons | |
JP2010513834A (en) | Heat transfer unit for steam generation and gas preheating | |
JP5154272B2 (en) | Fuel cell reformer | |
KR100848047B1 (en) | Highly Efficient, Compact Reformer Unit for Generating Hydrogen from Gaseous Hydrocarbons in the Low Power Range | |
US20100040519A1 (en) | Reformer, reforming unit, and fuel cell system | |
US20060242902A1 (en) | High-temperature reforming | |
US20020090329A1 (en) | Apparatus for a fuel processing system | |
JP2005520768A (en) | Hydrogen generator | |
JP2817236B2 (en) | Methanol reforming reactor | |
US20080019884A1 (en) | Apparatus for Producing Hydrogen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |
Effective date: 20210902 |
|
MKLA | Lapsed |
Effective date: 20200302 |