+

WO2004043587A1 - Demarrage rapide de reformeurs auto-thermiques - Google Patents

Demarrage rapide de reformeurs auto-thermiques Download PDF

Info

Publication number
WO2004043587A1
WO2004043587A1 PCT/US2003/036258 US0336258W WO2004043587A1 WO 2004043587 A1 WO2004043587 A1 WO 2004043587A1 US 0336258 W US0336258 W US 0336258W WO 2004043587 A1 WO2004043587 A1 WO 2004043587A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
lightoff
temperature
housing
fuel
Prior art date
Application number
PCT/US2003/036258
Other languages
English (en)
Inventor
Yanlong Shi
Jian Lian Zhao
Original Assignee
Nuvera Fuel Cells, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nuvera Fuel Cells, Inc. filed Critical Nuvera Fuel Cells, Inc.
Priority to US10/534,685 priority Critical patent/US20050245620A1/en
Priority to AU2003291530A priority patent/AU2003291530A1/en
Publication of WO2004043587A1 publication Critical patent/WO2004043587A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0438—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being placed next to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0442—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being placed in separate reactors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • 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
    • C01B3/40—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 characterised by the catalyst
    • 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
    • B01J2208/00716—Means for reactor start-up
    • 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
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/16—Controlling the process
    • C01B2203/1604—Starting up the process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • Autothermal reformers are one of the principal types of reactor for generating hydrogen via the steam reforming of fuel and water into a mixture containing hydrogen and other gases.
  • the steam reforming reaction is well known.
  • a fuel in gaseous form typically a hydrocarbon or an alcohol
  • steam at elevated temperature, usually in the presence of a catalyst.
  • the fuel and water are converted into hydrogen and carbon monoxide.
  • methane methane as an example, the "reforming" reaction is:
  • the resulting hydrogen-containing gas is used for any of several purposes, but particularly for the generation of electricity using a fuel cell.
  • the steam reforming reaction is endothermic (absorbs heat), and so heat must be supplied to the system to drive the reaction.
  • "pure" steam reforming the heat is supplied from an outside source to the catalyst bed. This is typically done by combusting a fuel, although other heat sources can be used. In the combustion of methane, for example,
  • the heat needed for reforming amounts to about the combustion of one methane for every three reformed. (Similar ratios apply to other fuels.)
  • the need to transport heat from an outside source to a catalyst bed can be an obstacle to rapid startup or rapid change of operating parameters in a steam reformer.
  • This can be avoided by the use of other forms of steam reforming, most commonly called “autothermal reforming”, or “partial oxidation reforming", h autothermal reforming, fuel, steam and also a controlled amount of air are mixed and injected into the reactor.
  • the oxygen in the air then reacts with some of the fuel, usually in the presence of a catalyst, thereby producing heat.
  • the heat is absorbed by the reforming reaction of fuel and steam, as described above, which is occurring at the same time in the same catalyst bed.
  • the amount of heat required for the reforming reaction can be generated in a controlled way by controlling the ratio of the inlet air to the amount of fuel being reformed.
  • the system must initially be heated, so that the catalyst reaches an effective operating temperature. It therefore has required preheating by hot gas, or electricity, or by pre-combustion or local ignition, to start up a cold ATR reactor. While this is not difficult in a large, fixed chemical plant, it is much more difficult in a mobile reformer, for example in a vehicle, or in a small reformer at a non- industrial site, such as in a distributed electric power generating system. Such small reformers often need to undergo cold startup several or many times per day. h these reformers, the ATR type of reaction is useful because creating the required heat in the bed itself is much quicker than supplying it via heat transfer through a heat exchanger. The problem still remains of how to start the reaction in the first place.
  • the ATR catalyst must fulfill several requirements, which at present conflict to some extent. In addition to having as low a low light-off temperature as feasible, the catalyst must efficiently convert all components of the fuel into hydrogen after lighting off.
  • a few fuels are nearly mono-component (e.g., natural gas; some alcohols), but many practically important fuels, particularly gasoline and other petroleum derivatives, are mixtures of many components.
  • Gasoline for example, contains both light alkanes, such as octanes, and aromatic compounds, such as napthalenes. The latter are considerably more difficult to reform, and are very demanding in terms of catalyst properties. These properties are shared by most petroleum products (kerosine, naptha, jet fuel etc.) and by many natural or refined feedstocks, including liquids from coal and tar, and the like.
  • a catalyst for rapid startup of an autothermal reformer comprises at least two catalyst portions in sequence in an ATR reactor.
  • a first, upstream catalyst portion is selected to have a comparatively low light-off temperature.
  • a second catalyst portion, downstream of the first, is selected for optimal reforming of the fuel, and in particular of aromatics or other species in the fuel that are difficult to reform completely.
  • the catalysts may be in sequential containers. More preferably, they are layered in a common bed for optimization of heat transfer from the first catalyst to the second catalyst. More preferably, the catalysts are monoliths, and the monoliths are mounted in a common housing for direct transfer of heat from the first, low-light-off catalyst to the second catalyst.
  • the catalysts types may also be mixed, particularly in a granular bed. However, it is preferred to have the upstream portion of the bed enriched in the first catalyst, and to have the second catalyst predominate in the most downstream portion of the bed, in order to talce maximum advantage of the distinctive properties of the catalysts. Hence, granular or pelleted catalysts may be packed into the reactor in two layers, but some mixing the interface is not detrimental. A more complex gradient is typically used only if experimental results show that it is more effective. (Simple layering will tend to be effective because heat generated by the low-lightoff catalyst flows downstream to the higher lightoff catalyst.) With catalysts on monolithic supports, the supports are positioned in the reactor in the appropriate order.
  • a catalyst system for rapid startup of an autothermal reformer comprises a first, upstream portion having at least a majority of a first catalyst having a first lightoff temperature, and a second, downstream portion having at least a majority of a second catalyst having a second, higher lightoff temperature, wherein the difference between the first and second lightoff temperatures is at least about 25 deg. C.
  • the respective catalysts can be housed in a common housing, or they can be housed in separate housings, with a gas flow path connecting the first housing to the second housing.
  • a method for providing rapid startup in an autothermal reforming reaction comprises providing a first catalyst portion for conducting an autothermal reforming reaction, the first catalyst portion having a first lightoff temperature; providing a second catalyst portion for conducting an autothermal reforming reaction in fluid communication with the first catalyst portion, the second catalyst portion having a second lightoff temperature that is at least 25 deg. C higher than the first lightoff temperature; heating at least part of the first catalyst portion to the first lightoff temperature; and flowing a mixture comprising at least air and fuel over the heated first catalyst portion to create heat by reaction of the air and fuel.
  • Fig. 1 shows catalyst bed temperatures and hydrogen output plotted as a function of time for a low lightoff temperature catalyst pellet bed under simulated ATR conditions
  • Fig. 2 shows catalyst bed temperatures plotted as a function of time for a low lightoff temperature catalyst coated onto a metal monolith under simulated ATR conditions
  • Fig. 3 shows catalyst bed temperatures as a function of time for a low lightoff temperature catalyst and a high lightoff temperature catalyst under simulated ATR conditions
  • Figs. 4 A and 4B are schematic illustrations of autothermal reformers employing the catalyst system of the present invention. DETAILED DESCRIPTION OF THE INVENTION
  • a description of preferred embodiments of the invention follows. Demonstration of the effectiveness of the combination of the invention may be confirmed by simple experimentation, similar in scope to the experimentation required to select the appropriate amount and geometric arrangement of any catalyst for a given process flow.
  • a sample of a low light-off temperature catalyst is obtained from a supplier, or synthesized. Its light-off temperature is measured. Its ability to reform more difficult hydrocarbons in a mixture, for example gasoline, is also evaluated, typically at various temperatures. Standard evaluation methods are used. These include use of analytical instrumentation to determine completeness of conversion of the fuel; use of temperature sensors at various places in the apparatus; and variation of flow rate to then determine the functional capacity of the catalyst.
  • the results may be used to model the behavior of the catalyst, so that the effects of variations in bed volume and geometry, etc., can be calculated.
  • a sample of a high light-off temperature high efficiency reforming catalyst is obtained or made. Its efficiency at completely reforming difficult fuels, such as gasoline and the like, is measured using similar procedures, particularly as a function of temperature.
  • the two catalysts are placed in order in an ATR catalyst bed, with the first low light-off catalyst arranged upstream of the second high light-off catalyst.
  • the relative thicknesses of the two catalysts can be estimated from models, and confirmed or adjusted by experiment.
  • the presence of the low lightoff catalyst will cause the catalyst bed to warm up to the desired operating temperature significantly faster than can be obtained with the high lightoff catalyst alone. This is found despite the likelihood that the desired operating temperature, usually 600 deg. C or more, is typically higher than the lightoff temperature of either catalyst.
  • the low lightoff catalyst will begin to operate much sooner than will the high lightoff catalyst, and will rapidly raise bed temperature to a level at which both catalysts are operative and generating heat.
  • the major time savings is in the difference in the time required under external heating to get the low-light off catalyst up to ignition temperature, as opposed to the high light-off catalyst.
  • Types of catalysts can be compared, and preferred catalyst pairs selected. Testing of additional batches of the selected catalysts will normally be done. The efficacy of the paired catalysts will normally be evident from the analytical data collected - i.e., faster temperature rise, with complete conversion of all species at temperature, with minimum volume. A more dramatic difference will be seen by reversing the order of the catalysts, putting the high lightoff catalyst first. The resulting bed will typically compare unfavorably with either catalyst alone, because it will light off no faster, or not greatly faster, than the high lightoff catalyst alone, while the conversion efficiency for difficult species of fuel will typically not be as good as that of an equivalent volume composed entirely of high lightoff high- efficiency catalyst.
  • High-efficiency, high-lightoff temperature catalysts are known, and include commercially available materials. Detailed compositions of catalysts are often proprietary to their manufacturers, so that selection is typically done by product name rather than detailed chemical composition, hi the experiments shown below, a catalyst was obtained from the dmc 2 unit of the OMG AG & Co. (Postfach 1351, D- 63403 Hanau, Rodenbacher Clice 4, D-63457 Hanau- Maschinen, Germany) as type 383.
  • Low temperature lightoff materials are less common - partially because of the difficulty of achieving high efficiency with these materials. Compositions with low lightoff temperatures have been described in US Patent No. 6,110,861 to Krumpelt et al. A sample of this material in pellet form was obtained from ANL (Argonne National Laboratories). A sample of material believed to be substantially similar was prepared by Sud-Chemie, hie. (P.O. Box 32370, Louisville, KY) on a FeCrAloy® metal monolith as sample FCR-HC1. These catalysts had a lightoff temperature in the range of about 150 - 180 deg. C for fuel reforming, and had reasonable catalytic efficiency except for the aromatics and similar complex species in gasoline.
  • the power to the heater is selected to warm the catalyst bed until lightoff of the catalysts is obtained over a particular time. This can be a prolonged period, depending on the power selected; most of the warm-up period is not shown in the data below.
  • WGHSV wet gas hourly space velocity.
  • Phi ( ⁇ ) is the ratio of the air theoretically required to oxidize all the fuel to the amount of air actually supplied; in effect, the reciprocal of the percentage of fuel burned.
  • Fig. 1 the properties of a sample of low lightoff temperature catalyst, specifically the low lightoff catalyst pellet from Argonne National Laboratories (ANL) mentioned above, are shown by way of a plot of catalyst bed inlet and outlet temperature, and amount of hydrogen production, as a function of time.
  • ANL Argonne National Laboratories
  • a mixture of vaporized fuel, air and steam is fed into a reactor bed, and the catalyst is gradually raised in temperature to simulate the operation of a reformer.
  • the temperatures of the catalyst bed inlet and outlet are shown (diamonds and squares, respectively), and the yield of hydrogen observed is shown (triangles).
  • the temperatures of the inlet and outlet are the same, until a temperature in the bed of about 180 deg. C is reached, at about 18 minutes of heating.
  • Figure 1 was conducted on a pellet bed.
  • Figure 2 the same ANL catalyst is coated onto a metal monolith, which has less thermal mass and better thermal conductivity.
  • the value of 3.7 is theoretically correct; the value of 2.5 reflects having additional air present for faster warmup, resulting in additional oxidation of fuel during the warmup stage.
  • Figure 2 shows that lightoff is achieved rapidly, and warmup is nearly complete at about 6 to 8 minutes.
  • the inlet and outlet temperatures of the low lightoff catalyst start to rise when the inlet temperature of the gas reaches about 200 deg. C.
  • the high lightoff catalyst is inactive until the inlet feed is preheated to over 400 deg. C, after which it also lights off promptly and shows rising temperatures both at the inlet and the outlet of the bed. (The humped behavior of the high temperature catalyst's inlet temperature is a feature of this particular catalyst.)
  • the low-lightoff catalyst should have a lightoff temperature that is at least about 25 deg. C lower than the lightoff temperature of the other catalyst, and larger lightoff temperature differentials, such as 50 deg C, 75 deg C, 100 deg C, 150 deg C, and 200 deg. C or more, are preferred.
  • Figs. 4A and 4B Examples of an autothermal reformer (ATR) embodying the principles of the present invention are shown in Figs. 4A and 4B.
  • Fig. 4A is a schematic of an authothermal reformer with an upstream catalyst portion 14 and a downstream catalyst portion 16 enclosed in a common housing.
  • the upstream catalyst portion 14 has a first catalyst with a comparatively low light-off temperature
  • the downstream portion 16 has a second catalyst with a higher light-off temperature.
  • the catalysts can be mixed in the housing to some extent, and in some embodiments, the composition of the catalysts can be graded within the housing. In general, however, the low light-off catalyst forms the major component at the upstream end 10 of the housing, and the high light-off catalyst is the major component at the downstream end 11 of the housing.
  • fuel 20, steam 22 and also a controlled amount of air 24 are optionally premixed and then injected into the upstream end 10 of the housing 12.
  • the oxygen in the air reacts with fuel over catalyst beds 14, 16, thereby producing heat.
  • the heat is absorbed by the endothermic reforming reaction of fuel and steam, which occurs at the same time over the catalyst beds.
  • a preheat mechanism 18 is arranged to heat the catalyst(s) to their respective light-off temperature(s), after which the autothermal reaction becomes largely self-sustaining.
  • Any conventional preheat means can be employed, such as by preheating the catalysts with hot gas, electrically heating the beds, or by heat transfer from a combustion reaction, such as from an external burner.
  • the reactor is initially heated by another source, such as hot gas from a burner, the low light-off catalyst in the first portion 14 will begin to operate much sooner than will the high light-off catalyst.
  • the heat created by the oxidation reaction over the first catalyst is sufficient to maintain or increase the catalyst's activity, as well as to quickly heat the second downstream catalyst to its light-off temperature.
  • the reformer thus reaches normal operating conditions significantly faster than in conventional ATR reactors.
  • Fig. 4B shows a similar reactor, except in this case, the reactor comprises two separate housings, 28 and 30, connected by a flow path 32 for the passage of gas from the first housing 28 to the second housing 30.
  • the first, lower light-off temperature catalyst 14 forms the major component of the catalyst bed in the upstream housing 28, and the second, higher light-off temperature catalyst 16 forms the major component of the catalyst bed in the downstream housing 30.
  • the operation of this embodiment is substantially the same as described in connection with Fig. 4A.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

Selon cette invention, le démarrage de reformeurs auto-thermiques servant à la production d'hydrogène est simplifié grâce à un procédé consistant à disposer un premier lit de catalyseur de reformeur auto-thermique (14) contenant un catalyseur à allumage à basse température ainsi qu'un second catalyseur dans un second lit (16) ou dans une seconde partie du premier lit (14), ce qui permet d'obtenir un catalyseur de reformage à la vapeur amélioré. Cette combinaison permet de répondre efficacement aux besoins de démarrage de reformeurs à vapeur petits ou mobiles.
PCT/US2003/036258 2002-11-13 2003-11-13 Demarrage rapide de reformeurs auto-thermiques WO2004043587A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/534,685 US20050245620A1 (en) 2003-11-13 2003-11-13 Fast startup in autothermal reformers
AU2003291530A AU2003291530A1 (en) 2002-11-13 2003-11-13 Fast startup in autothermal reformers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42595402P 2002-11-13 2002-11-13
US60/425,954 2002-11-13

Publications (1)

Publication Number Publication Date
WO2004043587A1 true WO2004043587A1 (fr) 2004-05-27

Family

ID=32313085

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/036258 WO2004043587A1 (fr) 2002-11-13 2003-11-13 Demarrage rapide de reformeurs auto-thermiques

Country Status (2)

Country Link
AU (1) AU2003291530A1 (fr)
WO (1) WO2004043587A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7172638B2 (en) * 2002-04-29 2007-02-06 General Motors Corporation Staged air autothermal reformer for improved startup and operation
WO2007029872A3 (fr) * 2005-09-08 2007-11-15 Casio Computer Co Ltd Reacteur et appareil electronique
EP1935846A4 (fr) * 2005-09-21 2011-10-12 Nippon Oil Corp Procédé de démarrage de reformeur autothermique
EP4434615A1 (fr) * 2023-03-24 2024-09-25 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé de production d'un produit gazeux de synthèse comprenant de l'hydrogène

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464606A (en) * 1994-05-27 1995-11-07 Ballard Power Systems Inc. Two-stage water gas shift conversion method
US5797737A (en) * 1996-01-15 1998-08-25 Institute Francais Du Petrole Catalytic combustion system with multistage fuel injection
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464606A (en) * 1994-05-27 1995-11-07 Ballard Power Systems Inc. Two-stage water gas shift conversion method
US5797737A (en) * 1996-01-15 1998-08-25 Institute Francais Du Petrole Catalytic combustion system with multistage fuel injection
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

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7172638B2 (en) * 2002-04-29 2007-02-06 General Motors Corporation Staged air autothermal reformer for improved startup and operation
WO2007029872A3 (fr) * 2005-09-08 2007-11-15 Casio Computer Co Ltd Reacteur et appareil electronique
US7713317B2 (en) 2005-09-08 2010-05-11 Casio Computer Co., Ltd. Reformer for power supply of a portable electronic device
EP1935846A4 (fr) * 2005-09-21 2011-10-12 Nippon Oil Corp Procédé de démarrage de reformeur autothermique
JP5124277B2 (ja) * 2005-09-21 2013-01-23 Ｊｘ日鉱日石エネルギー株式会社 オートサーマル改質器の起動方法
TWI398406B (zh) * 2005-09-21 2013-06-11 Nippon Oil Corp Automatic starting method of thermal reformer
EP4434615A1 (fr) * 2023-03-24 2024-09-25 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé de production d'un produit gazeux de synthèse comprenant de l'hydrogène
WO2024200012A1 (fr) * 2023-03-24 2024-10-03 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé de production d'un produit de gaz de synthèse comprenant de l'hydrogène

Also Published As

Publication number Publication date
AU2003291530A1 (en) 2004-06-03

Similar Documents

Publication Publication Date Title
CN100368753C (zh) 针对紧凑型燃料处理器开车而加热催化剂的装置和方法
JP4335535B2 (ja) 単一チャンバーのコンパクトな燃料処理装置
KR100891928B1 (ko) 단일 챔버 콤팩트 연료 처리장치
CN100519707C (zh) 快速加热燃料重整反应物的方法与装置
CA2325506C (fr) Production catalytique d'hydrogene
US5458857A (en) Combined reformer and shift reactor
US3522019A (en) Apparatus for generating hydrogen from liquid hydrogen - containing feedstocks
US6190623B1 (en) Apparatus for providing a pure hydrogen stream for use with fuel cells
AU2006264046B2 (en) Compact reforming reactor
Nahar et al. Recent advances in hydrogen production via autothermal reforming process (ATR): a review of patents and research articles
CA2384764A1 (fr) Unite de reformage adiabatique
AU2002226039A1 (en) Apparatus and method for heating catalyst for start-up of a compact fuel processor
WO1996000186A1 (fr) Generateur autonome d'hydrogene
CA2592441C (fr) Conversion thermo-neutre d'hydrocarbures liquides derives du petrole
CN102464300A (zh) 燃料重整装置及其方法
WO2004043587A1 (fr) Demarrage rapide de reformeurs auto-thermiques
US20050245620A1 (en) Fast startup in autothermal reformers
US20070033873A1 (en) Hydrogen gas generator
Yoon et al. Fuel-lean and fuel-rich start-up and shut-down processes in an autothermal reformer
JP2003303610A (ja) 燃料電池システム及びその運転方法並びにオートサーマルリフォーミング装置
JPH0450244B2 (fr)
AU2008200186A1 (en) Dual stack compact fuel processor for producing a hydrogen rich gas

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 10534685

Country of ref document: US

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载