WO2004074405A2 - Hydrogen generator for hydrogen desulfurization of hydrocarbon feeds - Google Patents

Hydrogen generator for hydrogen desulfurization of hydrocarbon feeds Download PDF

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Publication number
WO2004074405A2
WO2004074405A2 PCT/US2004/005183 US2004005183W WO2004074405A2 WO 2004074405 A2 WO2004074405 A2 WO 2004074405A2 US 2004005183 W US2004005183 W US 2004005183W WO 2004074405 A2 WO2004074405 A2 WO 2004074405A2
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WO
WIPO (PCT)
Prior art keywords
hydrogen
hydrocarbon feed
source
reformate
desulfurizer
Prior art date
Application number
PCT/US2004/005183
Other languages
French (fr)
Other versions
WO2004074405A3 (en
Inventor
Ke Liu
Richard J. Bellows
John L. Preston, Jr.
Original Assignee
Hydrogensource Llc
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
Priority claimed from US10/369,359 external-priority patent/US20040159584A1/en
Application filed by Hydrogensource Llc filed Critical Hydrogensource Llc
Priority to DE112004000293T priority Critical patent/DE112004000293T5/en
Priority to JP2006503773A priority patent/JP4800923B2/en
Publication of WO2004074405A2 publication Critical patent/WO2004074405A2/en
Publication of WO2004074405A3 publication Critical patent/WO2004074405A3/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing

Definitions

  • This invention relates to using a hydrogen generator, such as a small catalytic partial oxidizer
  • mini-CPO a homogeneous, non-catalytic partial oxidizer (POX) , an auto-thermal reformer (ATR) , a catalytic steam reformer, or a small water hydrolyzer, to generate hydrogen-containing reformate as an input, along with natural gas, liquified petroleum gas, or other hydrocarbon fuels, for hydrogen desulfurization (HDS) in the production of hydrogen from hydrocarbon fuels, for use, for instance, in fuel cell power plants, refineries, or other processes.
  • POX non-catalytic partial oxidizer
  • ATR auto-thermal reformer
  • HDS hydrogen desulfurization
  • Fuel cell power plants use hydrogen as the fuel.
  • Current technology includes conversion of hydrocarbon feeds to hydrogen by passing natural gas through a desulfurizer, a catalytic partial oxidizer (or other reformer), a water-gas shift reactor, and' a preferential carbon monoxide oxidizer for the generation of significant hydrogen for use as a fuel in a fuel cell, in which hydrogen and oxygen on opposite sides of the electrolyte are converted to electricity and water, in the known fashion.
  • hydrogen reformate is generated in a line 13 by a major reformer 14, such as a catalytic partial oxidizer (CPO) , an auto-thermal reformer or a steam reformer, which in turn receives desulfurized hydrocarbon fuel, such as natural gas, over a line 16 from a hydrogen desulfurizer 17.
  • CPO catalytic partial oxidizer
  • the hydrogen desulfurizer 17 receives hydrocarbon fuel over a line 19.
  • the CPO 14 also receives humidified air, from a suitable source such as an enthalpy recovery device, over a line 23.
  • the hydrocarbons in the fuel react with the humidified air on a catalyst, such as rhodium, iridium or zirconia, to produce in the line 13 reformate which, for methane feedstock, is roughly 37% hydrogen,
  • the hydrogen desulfurizer requires hydrogen enrichment in order to convert sulfur compounds, such as thiophene, into hydrogen sulfide, which is captured on adsorbents, such as zinc oxide.
  • This hydrogen is provided by a hydrogen recycle blower 30 which pressurizes hydrogen from a line 31 and applies it over a line 32 to the hydrogen desulfurizer 17.
  • a plurality of valves 34 allow adjustment of the processes, all as is known. Problems with this system include the fact that the hydrogen blower 30 is expensive, and it consumes on the order of 2 k of the power generated by the fuel cell for a 150 kW fuel cell power plant.
  • Objects of the invention include providing hydrogen to a hydrogen desulfurizing unit: which has less "humidity in it than is provided by hydrogen recycled from a reformate stream, which does not require equipment costing several thousand dollars, and which requires substantially no energy for operation; and provision of: improved hydrogen generation, such as for fuel in a fuel cell; a lower cost source of hydrogen-containing reformate; and reduced parasitic power in a fuel cell power plant utilizing hydrogen-containing reformate.
  • This invention is predicated on the discovery that the higher temperature in a hydrogen desulfurizer, which results from using hydrogen generated in a mini-reformer, prevents the carbon monoxide in the reformer product from having any significant adverse effect on the precious metal catalyst (such as platinum) or the adsorption material (such as zinc oxide) in a hydrogen desulfurizer.
  • hydrocarbon feed such as natural gas
  • air are fed to a small hydrogen generator to generate hydrogen rich reformate to be fed to a hydrogen desulfurizer, thereby eliminating the need for a hydrogen recycle blower.
  • the invention reduces cost, power consumption and moisture in the hydrogen gas provided to a hydrogen desulfurizer.
  • the small hydrogen generator is run in a nearly steady state condition, obviating the need for controls; any excess hydrogen that is generated simply becoming part of the fuel stream, which is economically utilized.
  • the invention By providing dry reformate to the hydrogen desulfurizer, the adsorption of sulfur on the zinc oxide is enhanced, reducing sulfur to the parts per billion level, which is significant.
  • the invention also provides a certain amount of heat which raises the desulfurizing process from about 260°C (500°F) to about 350°C (662°F), thereby to aid in the desulfurizing process.
  • the hydrogen generator may be a small catalytic partial oxidizer (mini-CPO) , a homogeneous ' non-catalytic partial oxidizer (mini-POX) , a small auto-thermal reformer (mini-ATR) , a small catalytic steam reformer, a small water electrolyzer, or any other unit that produces hydrogen suitable for use in hydrogen desulfurization, particularly any unit that produces dry hydrogen at an elevated temperature with no parasitic cost or loss of efficiency.
  • mini-CPO small catalytic partial oxidizer
  • mini-POX homogeneous ' non-catalytic partial oxidizer
  • mini-ATR small auto-thermal reformer
  • mini-ATR small catalytic steam reformer
  • small water electrolyzer or any other unit that produces hydrogen suitable for use in hydrogen desulfurization, particularly any unit that produces dry hydrogen at an elevated temperature with no parasitic cost or loss of efficiency.
  • Fig. 1 is a simplified schematic illustration of a hydrogen desulfurizer feeding a major reformer, with recycled hydrogen gas being provided through a hydrogen blower to the hydrogen desulfurizer, as known in the prior art.
  • Fig. 2 is a simplified schematic diagram of a hydrogen desulfurizer being supplied hydrogen rich ' reformate generated by a mini-CPO, in accordance with the present invention.
  • Figs. 3 and 4 are partial, simplified schematic diagrams of the embodiment of Fig. 2 except using a mini- POX and a mini-ATR, respectively.
  • a mini-reformer such as a mini-CPO 36, about the size of a 12 ounce beverage can, receives humidified air through a valve 37 and receives hydrocarbon fuel, such as natural gas, through a fixed orifice 38.
  • the multiplicity of valves and the fixed orifice allows adjusting the correct flows to the mini- CPO, the hydrogen desulfurizer and the major reformer.
  • the fuel which for natural gas, is typically more than 99% methane with traces of sulfur compounds, nitrogen and other hydrocarbons, is converted, along with the humidified air, to reformate, which may comprise roughly 30% hydrogen, 12% CO, and small amounts of other gases such as C0 2 and H 2 0, nitrogen from the humidifier, and unconverted hydrocarbons.
  • reformate which may comprise roughly 30% hydrogen, 12% CO, and small amounts of other gases such as C0 2 and H 2 0, nitrogen from the humidifier, and unconverted hydrocarbons.
  • the reformate produced by the mini-CPO 36 in a line 38 is mixed with the fuel at the inlet to the hydrogen desulfurizer 17. Since no water is applied to the mini- CPO, the reformate is much drier than the reformate generated in the line 31 by the water-shift reactor 26 and preferential CO oxidizer 27 which provides significant humidity in the reformate in the line 31.
  • a drier reformate is provided (about 2.8 mol % steam from the mini-CPO compared with about 8.8 mol % steam in the prior art) to the hydrogen desulfurizer, which enhances the adsorption on zinc oxide and helps to reduce the sulfur to the parts per billion level.
  • the heat input from the mini-CPO helps the hydrogen desulfurizer to run at between 650°F (343°C) and 750°F (400°C) ; these temperatures are high enough so that the carbon monoxide has only a relatively small negative effect on the desulfurizer catalyst.
  • a further benefit of the present invention is that it provides some heat to enhance the desulfurization process.
  • the small hydrogen generator in the embodiment of Fig. 2 is a mini-CPO.
  • the small hydrogen generator may be a mini-POX 36a as illustrated in Fig. 3, a mini-ATR 36b as illustrated in Fig. 4, or it may be a small catalytic steam reformer, a small water electrolyzer, or any other type of hydrogen generator that will produce hydrogen.
  • the small hydrogen generator may operate with dry air, if desired, although humidified air is presently thought to be preferable.
  • the major reformer 14 may be a CPO, a catalytic steam reformer, or an autothermal reformer.
  • the invention may be used in desulfurization processes for other than fuel cell power plants, such as in a refinery, or even in futuristic fuel (e.g., gasoline) stations.
  • the hydrogen generator may be configured with several layers of adsorbent material interspersed with several layers of precious metal hydrogen desulfurizing catalyst material so that the adsorbent may be replaced regularly, without either discarding or sorting through the catalyst to reclaim it, as is disclosed in copending U.S. patent application Serial No. 10/386,317, filed March 11, 2003.
  • the invention is well suited to provide hydrogen-rich reformate fuel for fuel cells, it may be used in refineries for desulfurization of all types of hydrocarbon fuels, such as natural gas, liquified petroleum gas, gasoline, diesel (including JP-8), kerosene, and other fuels generated from biomass and the like.
  • hydrocarbon fuels such as natural gas, liquified petroleum gas, gasoline, diesel (including JP-8), kerosene, and other fuels generated from biomass and the like.
  • the embodiment described herein is used in the desulfurization of natural gas, it may also be used in the desulfurization of other hydrocarbon feeds such as liquified petroleum gas, gasoline, diesel fuel, methane, and the like.

Abstract

A hydrogen-rich reformate gas generator (36), such as a mini-CPO, POX, ATR or other hydrogen generator provides warm, dry, hydrogen-rich reformate gas to a hydrogen desulfurizer (17) which provides desulfurized feedstock gas to a major reformer (14) (such as a CPO) which, after processing in a water-gas shift reactor (26) and preferential CO oxidizer (27) produces hydrogencontaining reformate in a line (31) for use, for instance, as fuel for a fuel cell power plant. The expensive prior art hydrogen blower (30) is thereby eliminated, thus reducing parasitic power losses in the power plant. The drier reformate provided by the small hydrogen generator to the hydrogen desulfurizer favors hydrogen sulfide adsorption on zinc oxide and helps to reduce sulfur to the parts per billion level.

Description

HYDROGEN GENERATOR FOR HYDROGEN DESULFURIZATION OF HYDROCARBON FEEDS
Technical Field
This invention relates to using a hydrogen generator, such as a small catalytic partial oxidizer
(mini-CPO) , a homogeneous, non-catalytic partial oxidizer (POX) , an auto-thermal reformer (ATR) , a catalytic steam reformer, or a small water hydrolyzer, to generate hydrogen-containing reformate as an input, along with natural gas, liquified petroleum gas, or other hydrocarbon fuels, for hydrogen desulfurization (HDS) in the production of hydrogen from hydrocarbon fuels, for use, for instance, in fuel cell power plants, refineries, or other processes.
Background Art
Fuel cell power plants use hydrogen as the fuel. Current technology includes conversion of hydrocarbon feeds to hydrogen by passing natural gas through a desulfurizer, a catalytic partial oxidizer (or other reformer), a water-gas shift reactor, and' a preferential carbon monoxide oxidizer for the generation of significant hydrogen for use as a fuel in a fuel cell, in which hydrogen and oxygen on opposite sides of the electrolyte are converted to electricity and water, in the known fashion.
Referring to Fig. 1, hydrogen reformate is generated in a line 13 by a major reformer 14, such as a catalytic partial oxidizer (CPO) , an auto-thermal reformer or a steam reformer, which in turn receives desulfurized hydrocarbon fuel, such as natural gas, over a line 16 from a hydrogen desulfurizer 17. The hydrogen desulfurizer 17 receives hydrocarbon fuel over a line 19. The CPO 14 also receives humidified air, from a suitable source such as an enthalpy recovery device, over a line 23. In the CPO 14, the hydrocarbons in the fuel react with the humidified air on a catalyst, such as rhodium, iridium or zirconia, to produce in the line 13 reformate which, for methane feedstock, is roughly 37% hydrogen,
14% CO, 4% C02 and traces of other gases, which is further processed with water from a line 24 in a water-gas shift reactor 26 and a preferential CO oxidizer 27 to make it suitable for use as fuel in a line 31, such as for a fuel cell.
However, the hydrogen desulfurizer requires hydrogen enrichment in order to convert sulfur compounds, such as thiophene, into hydrogen sulfide, which is captured on adsorbents, such as zinc oxide. This hydrogen is provided by a hydrogen recycle blower 30 which pressurizes hydrogen from a line 31 and applies it over a line 32 to the hydrogen desulfurizer 17. A plurality of valves 34 allow adjustment of the processes, all as is known. Problems with this system include the fact that the hydrogen blower 30 is expensive, and it consumes on the order of 2 k of the power generated by the fuel cell for a 150 kW fuel cell power plant. Additionally, there is a significant amount of steam present in the hydrogen recycle stream 32 which has a negative impact on the hydrogen sulfide adsorption on zinc oxide in the hydrogen desulfurizer 17.' This can impair the reduction of the level of sulfur, which must reach the parts-per-billion (pbb) level for fuel cell applications and to avoid rapid deactivation of catalysts used in the process.
Disclosure of Invention
Objects of the invention include providing hydrogen to a hydrogen desulfurizing unit: which has less "humidity in it than is provided by hydrogen recycled from a reformate stream, which does not require equipment costing several thousand dollars, and which requires substantially no energy for operation; and provision of: improved hydrogen generation, such as for fuel in a fuel cell; a lower cost source of hydrogen-containing reformate; and reduced parasitic power in a fuel cell power plant utilizing hydrogen-containing reformate.
This invention is predicated on the discovery that the higher temperature in a hydrogen desulfurizer, which results from using hydrogen generated in a mini-reformer, prevents the carbon monoxide in the reformer product from having any significant adverse effect on the precious metal catalyst (such as platinum) or the adsorption material (such as zinc oxide) in a hydrogen desulfurizer. According to the present invention, hydrocarbon feed (such as natural gas) and air are fed to a small hydrogen generator to generate hydrogen rich reformate to be fed to a hydrogen desulfurizer, thereby eliminating the need for a hydrogen recycle blower. The invention reduces cost, power consumption and moisture in the hydrogen gas provided to a hydrogen desulfurizer.
According to the invention further, the small hydrogen generator is run in a nearly steady state condition, obviating the need for controls; any excess hydrogen that is generated simply becoming part of the fuel stream, which is economically utilized.
By providing dry reformate to the hydrogen desulfurizer, the adsorption of sulfur on the zinc oxide is enhanced, reducing sulfur to the parts per billion level, which is significant. The invention also provides a certain amount of heat which raises the desulfurizing process from about 260°C (500°F) to about 350°C (662°F), thereby to aid in the desulfurizing process.
According to the invention, the hydrogen generator may be a small catalytic partial oxidizer (mini-CPO) , a homogeneous ' non-catalytic partial oxidizer (mini-POX) , a small auto-thermal reformer (mini-ATR) , a small catalytic steam reformer, a small water electrolyzer, or any other unit that produces hydrogen suitable for use in hydrogen desulfurization, particularly any unit that produces dry hydrogen at an elevated temperature with no parasitic cost or loss of efficiency.
Brief Description of the Drawings
Fig. 1 is a simplified schematic illustration of a hydrogen desulfurizer feeding a major reformer, with recycled hydrogen gas being provided through a hydrogen blower to the hydrogen desulfurizer, as known in the prior art.
Fig. 2 is a simplified schematic diagram of a hydrogen desulfurizer being supplied hydrogen rich ' reformate generated by a mini-CPO, in accordance with the present invention.
Figs. 3 and 4 are partial, simplified schematic diagrams of the embodiment of Fig. 2 except using a mini- POX and a mini-ATR, respectively.
Mode(s) for Carrying Out the Invention
Referring to Fig. 2, a mini-reformer, such as a mini-CPO 36, about the size of a 12 ounce beverage can, receives humidified air through a valve 37 and receives hydrocarbon fuel, such as natural gas, through a fixed orifice 38. The multiplicity of valves and the fixed orifice allows adjusting the correct flows to the mini- CPO, the hydrogen desulfurizer and the major reformer. In the mini-CPO, the fuel, which for natural gas, is typically more than 99% methane with traces of sulfur compounds, nitrogen and other hydrocarbons, is converted, along with the humidified air, to reformate, which may comprise roughly 30% hydrogen, 12% CO, and small amounts of other gases such as C02 and H20, nitrogen from the humidifier, and unconverted hydrocarbons. The reformate produced by the mini-CPO 36 in a line 38 is mixed with the fuel at the inlet to the hydrogen desulfurizer 17. Since no water is applied to the mini- CPO, the reformate is much drier than the reformate generated in the line 31 by the water-shift reactor 26 and preferential CO oxidizer 27 which provides significant humidity in the reformate in the line 31. Thus, a drier reformate is provided (about 2.8 mol % steam from the mini-CPO compared with about 8.8 mol % steam in the prior art) to the hydrogen desulfurizer, which enhances the adsorption on zinc oxide and helps to reduce the sulfur to the parts per billion level. Although there is carbon monoxide in the CPO reformate, the heat input from the mini-CPO helps the hydrogen desulfurizer to run at between 650°F (343°C) and 750°F (400°C) ; these temperatures are high enough so that the carbon monoxide has only a relatively small negative effect on the desulfurizer catalyst. Thus, a further benefit of the present invention is that it provides some heat to enhance the desulfurization process.
The small hydrogen generator in the embodiment of Fig. 2 is a mini-CPO. However, the small hydrogen generator may be a mini-POX 36a as illustrated in Fig. 3, a mini-ATR 36b as illustrated in Fig. 4, or it may be a small catalytic steam reformer, a small water electrolyzer, or any other type of hydrogen generator that will produce hydrogen. The small hydrogen generator may operate with dry air, if desired, although humidified air is presently thought to be preferable. The major reformer 14 may be a CPO, a catalytic steam reformer, or an autothermal reformer. The invention may be used in desulfurization processes for other than fuel cell power plants, such as in a refinery, or even in futuristic fuel (e.g., gasoline) stations.
Because the use of the small hydrogen generator will increase the temperature at the inlet to the hydrogen desulfurizer, the hydrogen generator may be configured with several layers of adsorbent material interspersed with several layers of precious metal hydrogen desulfurizing catalyst material so that the adsorbent may be replaced regularly, without either discarding or sorting through the catalyst to reclaim it, as is disclosed in copending U.S. patent application Serial No. 10/386,317, filed March 11, 2003.
Although the invention is well suited to provide hydrogen-rich reformate fuel for fuel cells, it may be used in refineries for desulfurization of all types of hydrocarbon fuels, such as natural gas, liquified petroleum gas, gasoline, diesel (including JP-8), kerosene, and other fuels generated from biomass and the like. Although the embodiment described herein is used in the desulfurization of natural gas, it may also be used in the desulfurization of other hydrocarbon feeds such as liquified petroleum gas, gasoline, diesel fuel, methane, and the like.

Claims

Claims
1. A method of providing desulfurized hydrocarbon feed, comprising: producing hydrogen-rich reformate from hydrocarbon feed in a small hydrogen generator; and feeding said hydrogen-rich reformate along with the hydrocarbon feed to a hydrogen desulfurizer.
2. A method according to claim 1 wherein said producing step comprises: producing hydrogen-rich reformate from the hydrocarbon feed and humidified air.
3. Apparatus for providing desulfurized hydrocarbon feed, comprising: means including a small hydrogen generator for producing hydrogen-rich reformate from hydrocarbon feed; a hydrogen desulfurizer; and means for feeding said hydrogen-rich reformate along with the hydrocarbon feed to said hydrogen desulfurizer.
4. A system for desulfurizing hydrocarbon feeds, comprising: a source of hydrocarbon feed; a small hydrogen generator receiving said hydrocarbon feed from said source and providing hydrogencontaining reformate gas; and a hydrogen desulfurizer receiving said hydrocarbon feed from said source of hydrocarbon feed and receiving said hydrogen-containing gas from said small hydrogen generator.
5. A system according to claim 4 further comprising: a source of humidified air; and wherein said small hydrogen generator receives humidified air from the corresponding source to produce said reformate gas from said fuel and said air.
6. A system according to claim 4 wherein: said small hydrogen generator is a mini-CPO
(catalytic partial oxidizer) .
7. A system according to claim 4 wherein: said small hydrogen generator is a mini-POX (non- catalytic partial oxidizer) .
8. A system according to claim 4 wherein: said small hydrogen generator is a mini-ATR (auto- thermal reformer) .
9. A system for producing hydrogen-rich reformate from hydrocarbon feeds, comprising: a source of hydrocarbon feed; a source of water; a small hydrogen generator receiving hydrocarbon feed from said source to produce hydrogen-containing reformate gas; a hydrogen desulfurizer receiving hydrocarbon feed from said source of hydrocarbon feed and hydrogen- containing reformate gas from said small hydrogen generator, and providing desulfurized hydrocarbon feed; and a fuel processor including a major reformer receiving said desulfurized hydrocarbon feed and said humidified air and producing hydrogen-containing reformate, a water-gas shift reactor receiving said hydrogen-containing reformate and water and feeding the resultant gas into a preferential CO oxidizer, for producing hydrogen-containing reformate for use as fuel, whereby recycled hydrogen gas from the output of said fuel processor is not required for said desulfurizer, thereby (a) eliminating the need for an expensive, power consuming hydrogen blower and (b) reducing the steam fed into said hydrogen desulfurizer.
10. A system according to claim 9 further comprising: a source of humidified air; and wherein said small hydrogen generator receives humidified air from the corresponding source to produce said reformate gas from said fuel and said air.
11. A system according to claim 10 wherein: said small hydrogen generator is a mini-CPO
(catalytic partial oxidizer) .
12. A system according to claim 10 wherein: said small hydrogen generator is a mini-POX (non- catalytic partial oxidizer) .
13. A system according to claim 9 wherein: said small hydrogen generator is a mini-ATR (auto- thermal reformer) .
14. A method of providing desulfurized hydrocarbon feed, characterized by: producing hydrogen-rich reformate from the hydrocarbon feed and air in a mini-catalytic partial oxidizer (36) ; and feeding said hydrogen-rich reformate along with the hydrocarbon feed to a hydrogen desulfurizer (17) .
15. A method according to claim 14 wherein said producing step comprises: producing hydrogen-rich reformate from the hydrocarbon feed and humidified air.
16. Apparatus for providing desulfurized hydrocarbon feed, comprising: a hydrogen desulfurizer (17); characterized by: means including a mini-catalytic partial oxidizer (36) for producing hydrogen from the hydrocarbon feed and humidified air; and means (19) for feeding said hydrogen along with the hydrocarbon feed to said hydrogen desulfurizer.
17. A system for desulfurizing hydrocarbon feeds, comprising: a source of hydrocarbon feed; a source of air; and a hydrogen desulfurizer (17); characterized by: a mini-catalytic partial oxidizer (36) (mini-CPO) receiving said hydrocarbon feed and said humidified air from said sources and providing hydrogen-containing reformate gas; said hydrogen desulfurizer (17) receiving said hydrocarbon feed from said source of hydrocarbon feed and receiving said hydrogen-containing gas from said mini- CPO.
18. A system according to claim 14 wherein: said source of air is a source of humidified air.
19. A system for producing hydrogen-rich reformate from hydrocarbon feeds, comprising: a source of hydrocarbon feed; a source of air; a source of water; and a hydrogen desulfurizer (17); characterized by: a mini-catalytic partial oxidizer (36) (mini-CPO) receiving hydrocarbon feed and said humidified air from said sources to produce hydrogen-containing reformate gas; said hydrogen desulfurizer receiving (19) hydrocarbon feed from said source of hydrocarbon feed and hydrogen-containing reformate gas from said mini-CPO, and providing (16) desulfurized hydrocarbon feed; -and a fuel processor including a major reformer (14) receiving said desulfurized hydrocarbon feed and said humidified air and producing hydrogen-containing reformate, a water-gas shift reactor (26) receiving said hydrogen-containing reformate and water and feeding the resultant gas into a preferential CO oxidizer (27), for producing hydrogen-containing reformate for use as fuel, whereby recycled hydrogen gas from the output of said fuel processor is not required for said desulfurizer, thereby (a) eliminating the need for an expensive, power consuming hydrogen blower and (b) reducing the steam fed into said hydrogen desulfurizer.
20. A system according to claim 19 wherein: said source of air is a source of humidified air.
PCT/US2004/005183 2003-02-18 2004-02-18 Hydrogen generator for hydrogen desulfurization of hydrocarbon feeds WO2004074405A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE112004000293T DE112004000293T5 (en) 2003-02-18 2004-02-18 Hydrogen generator for hydrogen desulfurization for hydrocarbon pipe materials
JP2006503773A JP4800923B2 (en) 2003-02-18 2004-02-18 Hydrogen generator for hydrodesulfurization of hydrocarbon feed

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Application Number Priority Date Filing Date Title
US10/369,359 US20040159584A1 (en) 2003-02-18 2003-02-18 Mini-CPO providing hydrogen for hydrogen desulfurization of hydrocarbon feeds
US10/369,359 2003-02-18
US10/731,291 US7128768B2 (en) 2003-02-18 2003-12-09 Hydrogen generator for hydrogen desulfurization of hydrocarbon feeds
US10/731,291 2003-12-09

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WO2014079492A1 (en) * 2012-11-21 2014-05-30 Topsøe Fuel Cell A/S Fuel cell system comprising a combined fuel processing apparatus and a fuel cell unit

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US3898153A (en) * 1973-11-23 1975-08-05 Sun Oil Co Pennsylvania Catalytic reforming process with sulfur removal
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WO2014079492A1 (en) * 2012-11-21 2014-05-30 Topsøe Fuel Cell A/S Fuel cell system comprising a combined fuel processing apparatus and a fuel cell unit

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