US20070034551A1 - Apparatus and method for removing sulfur from a hydrocarbon fuel - Google Patents

Apparatus and method for removing sulfur from a hydrocarbon fuel Download PDF

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US20070034551A1
US20070034551A1 US11/537,992 US53799206A US2007034551A1 US 20070034551 A1 US20070034551 A1 US 20070034551A1 US 53799206 A US53799206 A US 53799206A US 2007034551 A1 US2007034551 A1 US 2007034551A1
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reactor
fuel
sulfur
combustion
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Bard LINDSTROM
Per EKDUNGE
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Volvo Technology AB
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Assigned to VOLVO TECHNOLOGY CORPORATION reassignment VOLVO TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EKDUNGE, PER, LINDSTROM, BARD
Publication of US20070034551A1 publication Critical patent/US20070034551A1/en
Priority to US12/024,653 priority Critical patent/US7785380B2/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675Removal of sulfur
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/52Hydrogen sulfide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/304Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/306Organic sulfur compounds, e.g. mercaptans
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/308Carbonoxysulfide COS
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435Catalytic purification
    • C01B2203/044Selective oxidation of carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0455Purification by non-catalytic desulfurisation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0485Composition of the impurity the impurity being a sulfur compound
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258Pre-treatment of the feed
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • the invention generally relates to an apparatus and method for removing sulfur from a hydrocarbon fuel.
  • the invention relates to a system for catalytic treatment of a hydrocarbon fuel.
  • Hydrocarbon fuels such as diesel, gasoline and natural gas, have generally a sulfur content that in most cases needs to be reduced of environmental reasons and/or because sulfur is a potent poison for catalysts and catalytic processes.
  • Sulfur is present in hydrocarbon fuels in the form of a variety of sulfur compounds.
  • the sulfur can be removed from the fuel in an industrial hydrodesulfurization process (HDS) before the hydrocarbon fuel comes into actual use, such as in combustion or reformation.
  • HDS may be suitable for large-scale industrial processes where large quantities of hydrogen are available, but it is a costly and complicated process and therefore not suitable in other applications, such as automotive and fuel cell applications.
  • Another method is to remove sulfur after a fuel reforming step, such as steam reforming or partial oxidation, in which step the fuel is catalytically reformed into smaller hydrocarbons and hydrogen, and in which the sulfur is converted into H 2 S.
  • a fuel reforming step such as steam reforming or partial oxidation
  • the fuel is catalytically reformed into smaller hydrocarbons and hydrogen
  • the sulfur is converted into H 2 S.
  • This method is relatively effective and useful in many situations.
  • H 2 S can readily be removed from a gaseous stream by passing the sulfur-containing gas over a material that can react with the sulfur, such as ZnO, and thereby purge the gas stream of sulfur.
  • this method has the disadvantage that the catalyst in the reactor will suffer from poisoning which results in short lifetimes for the catalytic system.
  • U.S. 2003/0188475 describes an example of a fuel reforming system where the sulfur trap has been incorporated after the catalytic reformer.
  • the fuel is initially vaporized and then catalytically converted in an autothermal reformer into a hydrogen rich gas before passed over the sulfur trap.
  • the product is then fed via a water gas shift reactor and a catalytic preferential oxidation reactor to a fuel cell.
  • One object of the present invention is to provide an apparatus and a method for removing sulfur from a hydrocarbon fuel that eliminates or at least reduces the problems related to sulfur contamination of catalysts in a system for catalytic treatment of a hydrocarbon fuel.
  • the invention concerns an apparatus for removing sulfur from a hydrocarbon fuel, and the invention is characterized in that the apparatus comprises a combustion reactor and a sulfur trap.
  • the combustion reactor is adapted to operate with an air-to-fuel ratio below 1.0 and in the presence of steam.
  • the sulfur trap is located downstream of the combustion reactor and is adapted to remove sulfur compounds formed in the combustion reactor.
  • Such a combustion reactor operates in the absence of catalysts and converts parts of the fuel into smaller components as well as converts the fuel content of sulfur compounds into easily removeable compounds such as H 2 S.
  • the sulfur can be removed from a catalytic system before the catalysts in the system have come into contact with the sulfur.
  • the present invention thereby eliminates, or at least minimizes sulfur poisoning of the catalysts in the catalytic reactor and thereby increases the life time of the catalytic part of the system.
  • the invention also concerns a method for removing sulfur from a hydrocarbon fuel that is characterized in that the fuel in a first step is fed to a combustion reactor that operates with an air-to-fuel ratio below 1.0 and in the presence of steam. In a second step the fuel is fed to a sulfur trap located downstream of the combustion reactor and the sulfur trap is adapted to remove sulfur compounds formed in the combustion reactor.
  • This method makes it possible to remove the sulfur from the fuel before the fuel comes into contact with any catalysts that would be present in a catalytic reactor in a subsequent step of a method for catalytic treatment of a hydrocarbon fuel.
  • FIG. 1 schematically illustrates one advantageous embodiment of the invention.
  • hydrocarbon fuel relates to any hydrocarbon fluid suitable for being used as a fuel, such as diesel, gasoline, ethanol, methanol, di-methyl ether and aviation fuels.
  • FIG. 1 schematically shows an advantageous embodiment of the invention.
  • Hydrocarbon fuel 1 and steam/air 2 is fed to a combustion reactor 3 in which the hydrocarbon fuel is combusted under fuel rich conditions; i.e., the air-to-fuel ratio is below 1, in the presence of steam.
  • the hydrocarbon fuel is partially broken down into smaller molecules and all or most of the sulfur is converted into H 2 S.
  • a sulfur trap 4 is located downstream the combustion reactor 4 .
  • the sulfur compounds generally H 2 S, are removed from the hydrocarbon fuel.
  • a catalytic reactor 5 in which the fuel is further converted catalytically, is located further downstream in the system.
  • the catalytic reactor 5 could be a steam reformer or a partial oxidation reactor.
  • the combination of a combustion reactor 3 and a sulfur trap 4 i.e., the apparatus for removing sulfur from a hydrocarbon fuel according to the invention, is located upstream of the catalytic reactor 5 thus providing an effective way of preventing catalysts in a catalytic system from being exposed to sulfur from the combusted hydrocarbon fuel.
  • the combustion reactor 3 converts the various sulfur compounds into certain sulfur compounds, such as H 2 S, that are easily separated from the fuel. To achieve this, it is important that the fuel-to-steam and air-to-fuel ratios be adapted to the selected fuel so that the rich fuel combustion process is stable. In many situations it is a principle aim to reform or convert the fuel to a large degree, and in these cases it is advantageous if the combustion reactor 3 not only converts sulfur compounds, but also converts the hydrocarbon fuel into smaller molecules as efficiently as possible. In such a situation, the combustion reactor 3 works as a pre-reformer. To enhance such pre-reforming reactions, it is advantageous to mix the steam with the air before injecting the air/steam into the combustion reactor 3 .
  • the combustion reactor 3 is optimally operated with air-to-fuel ratios (lamda) between around 0.2-0.5, depending on the hydrocarbon used, but other air-to-fuel ratios can also give a satisfactory result.
  • Steam is required in this step because it is used in the conversion of the sulfur compounds and it is also used for controlling the temperature in the reactor. Suitable temperature depends on such things as the type of hydrocarbon fuel used, but a typical suitable temperature is 350° C.
  • the steam-to-fuel ratio depends to a large degree on the type of fuel.
  • the operating temperature of catalytic fuel reforming reactors such as steam reformers and partial oxidation reactors, in which the fuel is close to completely converted to small molecules, is much higher than in the combustion reactor 3 .
  • Typical temperatures are in the approximate range of 800-1200° C.
  • a suitable combustion process for the combustion reactor 3 is the so called “cold flame combustion” process or the “cool blue flame combustion” process, each of which are well known combustion reaction scenarios.
  • H 2 S Most of the sulfur compounds formed in the combustion reactor 3 in the type of combustion reaction described above will be H 2 S. This compound can easily be separated by means of conventional sulfur traps such as those containing ZnO.
  • Another sulfur compound that may be formed in the combustion reactor 3 is COS.
  • the amounts of COS formed depends on the operational conditions of the combustion reactor 3 , but generally the amounts will be much smaller than the amounts of H 2 S.
  • the sulfur trap is preferably a separate unit that can be replaced after some time when the adsorption material has been consumed to a certain prescribed degree.
  • FIG. 1 only gives a schematic view of the system. Naturally, the system may comprise further catalytic reactors and/or sulfur traps. For instance, in some cases it may be necessary to implement a further sulfur trap downstream the catalytic reactor 5 , as in a catalytic reforming system where some of the catalysts in subsequent catalytic reactors are ultra-sensitive to sulfur.
  • the catalytic reactor 5 or plurality of catalytic reactors located downstream of the sulfur trap 4 can be of various types relating to, for instance, the following catalytic processes: autothermal reforming, catalytic reforming, partial oxidation, steam reforming, exhaust gas catalytic oxidation, exhaust gas catalytic reduction, catalytic combustion, preferential oxidation and fuel cells.
  • autothermal reforming catalytic reforming, partial oxidation, steam reforming, exhaust gas catalytic oxidation, exhaust gas catalytic reduction, catalytic combustion, preferential oxidation and fuel cells.
  • the fuel is further broken down and in many cases it is an advantage if the combustion reactor 3 works as a pre-reformer as mentioned above.

Abstract

Method and apparatus for removing sulfur from a hydrocarbon fuel. The apparatus includes a combustion reactor (3) and a sulfur trap (4) and the combustion reactor (3) is adapted to operate with an air-to-fuel ratio below 1 and in the presence of steam. The sulfur trap (4) is located downstream the combustion reactor (3) and is adapted to remove sulfur compounds formed in the combustion reactor (3).

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • The present application is a continuation patent application of International Application No. PCT/SE2005/000490 filed 1 Apr. 2005 which is published in English pursuant to Article 21(2) of the Patent Cooperation Treaty and which claims priority to Swedish Application No. 0400904-9 filed 2 Apr. 2004. Said applications are expressly incorporated herein by reference in their entireties.
  • FIELD
  • The invention generally relates to an apparatus and method for removing sulfur from a hydrocarbon fuel. In particular, the invention relates to a system for catalytic treatment of a hydrocarbon fuel.
  • BACKGROUND
  • Hydrocarbon fuels, such as diesel, gasoline and natural gas, have generally a sulfur content that in most cases needs to be reduced of environmental reasons and/or because sulfur is a potent poison for catalysts and catalytic processes.
  • Sulfur is present in hydrocarbon fuels in the form of a variety of sulfur compounds. The sulfur can be removed from the fuel in an industrial hydrodesulfurization process (HDS) before the hydrocarbon fuel comes into actual use, such as in combustion or reformation. HDS may be suitable for large-scale industrial processes where large quantities of hydrogen are available, but it is a costly and complicated process and therefore not suitable in other applications, such as automotive and fuel cell applications.
  • Another method is to remove sulfur after a fuel reforming step, such as steam reforming or partial oxidation, in which step the fuel is catalytically reformed into smaller hydrocarbons and hydrogen, and in which the sulfur is converted into H2S. This method is relatively effective and useful in many situations. H2S can readily be removed from a gaseous stream by passing the sulfur-containing gas over a material that can react with the sulfur, such as ZnO, and thereby purge the gas stream of sulfur. However, this method has the disadvantage that the catalyst in the reactor will suffer from poisoning which results in short lifetimes for the catalytic system.
  • U.S. 2003/0188475 describes an example of a fuel reforming system where the sulfur trap has been incorporated after the catalytic reformer. In the disclosed system the fuel is initially vaporized and then catalytically converted in an autothermal reformer into a hydrogen rich gas before passed over the sulfur trap. The product is then fed via a water gas shift reactor and a catalytic preferential oxidation reactor to a fuel cell.
  • To avoid or at least reduce the problems related to sulfur contamination of catalysts, focus has generally been set on developing catalysts that are more resistant to sulfur or catalysts that are less expensive so that each replacement of poisoned catalyst becomes less costly.
  • SUMMARY
  • One object of the present invention is to provide an apparatus and a method for removing sulfur from a hydrocarbon fuel that eliminates or at least reduces the problems related to sulfur contamination of catalysts in a system for catalytic treatment of a hydrocarbon fuel.
  • The invention concerns an apparatus for removing sulfur from a hydrocarbon fuel, and the invention is characterized in that the apparatus comprises a combustion reactor and a sulfur trap. The combustion reactor is adapted to operate with an air-to-fuel ratio below 1.0 and in the presence of steam. The sulfur trap is located downstream of the combustion reactor and is adapted to remove sulfur compounds formed in the combustion reactor. Such a combustion reactor operates in the absence of catalysts and converts parts of the fuel into smaller components as well as converts the fuel content of sulfur compounds into easily removeable compounds such as H2S. By locating the sulfur trap between the combustion reactor and a subsequent catalytic reactor, the sulfur can be removed from a catalytic system before the catalysts in the system have come into contact with the sulfur. The present invention thereby eliminates, or at least minimizes sulfur poisoning of the catalysts in the catalytic reactor and thereby increases the life time of the catalytic part of the system.
  • The invention also concerns a method for removing sulfur from a hydrocarbon fuel that is characterized in that the fuel in a first step is fed to a combustion reactor that operates with an air-to-fuel ratio below 1.0 and in the presence of steam. In a second step the fuel is fed to a sulfur trap located downstream of the combustion reactor and the sulfur trap is adapted to remove sulfur compounds formed in the combustion reactor. This method makes it possible to remove the sulfur from the fuel before the fuel comes into contact with any catalysts that would be present in a catalytic reactor in a subsequent step of a method for catalytic treatment of a hydrocarbon fuel.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The invention will now be described in more detail with reference to the following drawings in which FIG. 1 schematically illustrates one advantageous embodiment of the invention.
  • DETAILED DESCRIPTION
  • In this context, hydrocarbon fuel relates to any hydrocarbon fluid suitable for being used as a fuel, such as diesel, gasoline, ethanol, methanol, di-methyl ether and aviation fuels.
  • FIG. 1 schematically shows an advantageous embodiment of the invention. Hydrocarbon fuel 1 and steam/air 2 is fed to a combustion reactor 3 in which the hydrocarbon fuel is combusted under fuel rich conditions; i.e., the air-to-fuel ratio is below 1, in the presence of steam. In this combustion reaction the hydrocarbon fuel is partially broken down into smaller molecules and all or most of the sulfur is converted into H2S. A sulfur trap 4 is located downstream the combustion reactor 4. By contacting the outgoing flow from the combustion reactor 3 with the sulfur trap 4, the sulfur compounds, generally H2S, are removed from the hydrocarbon fuel. A catalytic reactor 5, in which the fuel is further converted catalytically, is located further downstream in the system. Typically, the catalytic reactor 5 could be a steam reformer or a partial oxidation reactor.
  • The combination of a combustion reactor 3 and a sulfur trap 4; i.e., the apparatus for removing sulfur from a hydrocarbon fuel according to the invention, is located upstream of the catalytic reactor 5 thus providing an effective way of preventing catalysts in a catalytic system from being exposed to sulfur from the combusted hydrocarbon fuel.
  • It is noteworthy that the combustion reactor 3 converts the various sulfur compounds into certain sulfur compounds, such as H2S, that are easily separated from the fuel. To achieve this, it is important that the fuel-to-steam and air-to-fuel ratios be adapted to the selected fuel so that the rich fuel combustion process is stable. In many situations it is a principle aim to reform or convert the fuel to a large degree, and in these cases it is advantageous if the combustion reactor 3 not only converts sulfur compounds, but also converts the hydrocarbon fuel into smaller molecules as efficiently as possible. In such a situation, the combustion reactor 3 works as a pre-reformer. To enhance such pre-reforming reactions, it is advantageous to mix the steam with the air before injecting the air/steam into the combustion reactor 3.
  • The combustion reactor 3 is optimally operated with air-to-fuel ratios (lamda) between around 0.2-0.5, depending on the hydrocarbon used, but other air-to-fuel ratios can also give a satisfactory result. Steam is required in this step because it is used in the conversion of the sulfur compounds and it is also used for controlling the temperature in the reactor. Suitable temperature depends on such things as the type of hydrocarbon fuel used, but a typical suitable temperature is 350° C. The steam-to-fuel ratio depends to a large degree on the type of fuel.
  • The operating temperature of catalytic fuel reforming reactors such as steam reformers and partial oxidation reactors, in which the fuel is close to completely converted to small molecules, is much higher than in the combustion reactor 3. Typical temperatures are in the approximate range of 800-1200° C.
  • A suitable combustion process for the combustion reactor 3 is the so called “cold flame combustion” process or the “cool blue flame combustion” process, each of which are well known combustion reaction scenarios.
  • Most of the sulfur compounds formed in the combustion reactor 3 in the type of combustion reaction described above will be H2S. This compound can easily be separated by means of conventional sulfur traps such as those containing ZnO. Another sulfur compound that may be formed in the combustion reactor 3 is COS. The amounts of COS formed depends on the operational conditions of the combustion reactor 3, but generally the amounts will be much smaller than the amounts of H2S. By choosing a sulfur trap with a suitable material, both H2S and COS can be simultaneously removed. The sulfur trap is preferably a separate unit that can be replaced after some time when the adsorption material has been consumed to a certain prescribed degree. It should be noted that FIG. 1 only gives a schematic view of the system. Naturally, the system may comprise further catalytic reactors and/or sulfur traps. For instance, in some cases it may be necessary to implement a further sulfur trap downstream the catalytic reactor 5, as in a catalytic reforming system where some of the catalysts in subsequent catalytic reactors are ultra-sensitive to sulfur.
  • The invention is not limited to the above described embodiments, but a number of modifications are possible within the frame of the patent claims.
  • For instance, the catalytic reactor 5, or plurality of catalytic reactors located downstream of the sulfur trap 4 can be of various types relating to, for instance, the following catalytic processes: autothermal reforming, catalytic reforming, partial oxidation, steam reforming, exhaust gas catalytic oxidation, exhaust gas catalytic reduction, catalytic combustion, preferential oxidation and fuel cells. In these processes the fuel is further broken down and in many cases it is an advantage if the combustion reactor 3 works as a pre-reformer as mentioned above.

Claims (19)

1. An apparatus for removing sulfur from a hydrocarbon fuel, said apparatus comprising:
a combustion reactor (3) and a sulfur trap (4), said combustion reactor (3) being adapted to operate such that combustion of the fuel is performed with an air-to-fuel ratio below 1 and in the presence of steam, and wherein said sulfur trap (4) is located downstream the combustion reactor (3) and is adapted to remove sulfur compounds in the combustion reactor (3).
2. The apparatus as recited in claim 1, wherein the combustion reactor (3) is adapted to operate with an air-to-fuel ratio between 0.2 and 0.5.
3. The apparatus as recited in claim 1, wherein the combustion reactor (3) is adapted to break down at least long hydrocarbon molecules into smaller molecules during operation.
4. The apparatus as recited in claim 1, wherein the combustion reactor (3) is adapted to convert a large fraction of the fuel content of sulfur compounds into H2S during operation.
5. The apparatus as recited in claim 1, wherein the combustion reactor (3) is adapted to operate at a temperature of approximately 300-400° C.
6. The apparatus as recited in claim 1, wherein the sulfur trap (4) contains ZnO.
7. A system for catalytic treatment of a hydrocarbon fuel, said system comprising:
a catalytic reactor (5) located downstream of a combustion reactor (3) and a sulfur trap (4), said combustion reactor (3) being adapted to operate such that combustion of the fuel is performed with an air-to-fuel ratio below 1 and in the presence of steam, and wherein said sulfur trap (4) is located downstream the combustion reactor (3) and is adapted to remove sulfur compounds in the combustion reactor (3).
8. The system as recited in claim 7, wherein the catalytic reactor (5) is a fuel reforming reactor.
9. The system as recited in claim 7, wherein the catalytic reactor (5) is a fuel reforming reactor chosen from the group comprising; a steam reformer, an autothermal reformer and a partial oxidation reactor.
10. The system as recited in claim 7, wherein the system further comprises a plurality of at least one of catalytic reactors and sulfur traps.
11. A method for removing sulfur from a hydrocarbon fuel, said method comprising:
feeding hydrocarbon fuel to a combustion reactor (3) and in which combustion of the fuel is performed with an air-to-fuel ratio below 1 and in the presence of steam; and
feeding the fuel to a sulfur trap (4) located downstream of the combustion reactor (3), said sulfur trap (4) being adapted to remove sulfur compounds formed in the combustion reactor (3).
12. The method as recited in claim 11, wherein the combustion reactor (3) operates with an air-to-fuel ratio between 0.2 and 0.5.
13. The method as recited in claim 11, wherein the combustion reactor (3) breaks down at least long hydrocarbon molecules into smaller molecules.
14. The method as recited in claim 11, wherein the combustion reactor (3) converts a large fraction of the fuel content of sulfur compounds into H2S.
15. The method as recited in claim 11, wherein the combustion reactor (3) operates at a temperature of approximately 300-400° C.
16. The method as recited in claim 11, wherein the sulfur trap (4) is of a type containing ZnO.
17. The method as recited in claim 11, wherein the method further comprises utilizing a catalytic reactor (5) for removing sulfur from the hydrocarbon fuel, and wherein said combustion chamber (3) and sulfur trap (4) are located upstream the catalytic reactor (5).
18. The method as recited in claim 17, wherein the catalytic reactor (5) operates as a fuel reforming reactor, such as a steam reformer or a partial oxidation reactor.
19. The method as recited in claim 17, wherein the fuel is further treated in at least one of catalytic reactors and sulfur traps.
US11/537,992 2004-04-02 2006-10-02 Apparatus and method for removing sulfur from a hydrocarbon fuel Abandoned US20070034551A1 (en)

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US12/024,653 US7785380B2 (en) 2004-04-02 2008-02-01 Method for removing sulfur from a hydrocarbon fuel

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SE0400904A SE0400904D0 (en) 2004-04-02 2004-04-02 Apparatus and method for removing sulfur from a hydrocarbon fuel
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ATE496677T1 (en) 2011-02-15
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WO2005094972A1 (en) 2005-10-13
US20090101544A1 (en) 2009-04-23
US7785380B2 (en) 2010-08-31
EP1735081B1 (en) 2011-01-26

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