WO2012057727A1 - Ensemble adsorbeur - Google Patents

Ensemble adsorbeur Download PDF

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Publication number
WO2012057727A1
WO2012057727A1 PCT/US2010/053921 US2010053921W WO2012057727A1 WO 2012057727 A1 WO2012057727 A1 WO 2012057727A1 US 2010053921 W US2010053921 W US 2010053921W WO 2012057727 A1 WO2012057727 A1 WO 2012057727A1
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WIPO (PCT)
Prior art keywords
adsorber
oxide
reformate gas
fuel cell
hydrogen sulfide
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Application number
PCT/US2010/053921
Other languages
English (en)
Inventor
Jean Yamanis
David E. Tew
Sven Tobias Junker
Justin R. Hawkes
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Utc Power Corporation
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Publication date
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Priority to PCT/US2010/053921 priority Critical patent/WO2012057727A1/fr
Publication of WO2012057727A1 publication Critical patent/WO2012057727A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/02—Separation 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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation 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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This disclosure relates generally to treating reformate gas and, more particularly, to removing hydrogen sulfide from reformate gas supplied to a fuel cell stack.
  • ATR reactors may supply the reformate gas.
  • the ATR reactors use a supply of fuel and oxygen to generate the reformate gas, which may include sulfur in the form of hydrogen sulfide.
  • sulfur can poison electrodes within a fuel cell stack, such as the anode electrodes within individual solid oxide fuel cells.
  • the reformate gas is typically treated to remove some of the sulfur before the reformate gas enters the fuel cell stack.
  • the reformate gas must contain less than 100 parts per billion by volume of hydrogen sulfide to avoid poisoning the electrodes.
  • Zinc oxide is often used as an adsorbent to remove sulfur from the reformate gas.
  • the effectiveness of the zinc oxide as an adsorbent varies with temperature. Zinc oxide is most effective at temperatures below about 400°C, which is lower than the temperature of the reformate gas exiting the autothermal reformer and higher than the desired temperature of the reformate gas entering the fuel cell stack. Using zinc oxide at lower temperatures may result in coke deposition that can decrease efficiency of the overall system.
  • the reformate gas is cooled and then reheated before entering the fuel cell stack. Cooling and reheating the reformate gas requires multiple heat exchangers.
  • An example adsorber assembly includes an adsorber and a housing.
  • the housing extends between an inlet and an outlet.
  • the housing is configured to communicate a reformate gas through at least a portion of the adsorber.
  • the adsorber includes a material coating selected from a group consisting of cerium oxide, a rare earth oxide, manganese oxide, and combinations of these.
  • the material coating having a thickness and being configured to react with hydrogen sulfide throughout the thickness.
  • the adsorber includes a material coating selected from a group consisting of cerium oxide, lanthanum oxide, and combinations of these in the form of (Ce0 2 , La 2 0 3 ).
  • the adsorber includes a material coating selected from a group consisting of cerium oxide, lanthanum oxide, manganese oxide and combinations of these in the form of (Ce0 2 , La 2 0 3 , MnO).
  • the adsorber includes a material coating selected from a group consisting of cerium oxide, a rare earth oxide (REO) selected from the group of lanthanum, praseodymium, neodymium, samarium, and gadolinium and combinations of these.
  • the material coating is comprised of cerium oxide, a rare earth oxide selected from the group of lanthanum, praseodymium, neodymium, samarium, and gadolinium, manganese oxide and combinations of these in the form of (Ce0 2 , REO, MnO).
  • An example fuel cell adsorber arrangement includes a reformer and a fuel cell stack.
  • An adsorber includes a material selected from a group consisting of cerium oxide, lanthanum oxide, and combinations of these.
  • the reformate gas communicates between the reformer and the fuel cell stack through the adsorber.
  • the reformate gas communicated from the trap has less hydrogen sulfide than the reformate gas communicated to the adsorber.
  • the layer of material has a thickness and is configured to react with hydrogen sulfide throughout the thickness.
  • An example method of conditioning a reformate gas stream includes communicating a reformate gas stream through an adsorber and adsorbing material from the reformate gas stream using a material within the adsorber.
  • the material is selected from a group consisting of cerium oxide, a rare earth oxide, and combinations of these.
  • the adsorber is configured such that the entire thickness of the layer of material is able to absorb hydrogen sulfide.
  • the method then communicates the reformate gas to a fuel cell stack.
  • the rare earth oxide is lanthanum oxide in one example.
  • Figure 1 shows a schematic view of an example fuel cell adsorber arrangement.
  • Figure 2 shows a partial cutaway view perspective view of the Figure 1 adsorber assembly.
  • Figure 2A shows an end view of a portion of the Figure 2 adsorber assembly.
  • Figure 2B shows a partial section view at line 2-2 in Figure 2.
  • Figure 3 shows a perspective view of a portion of the adsorber in the Figure 2 adsorber assembly.
  • an example adsorber assembly 10 includes a reformer 14 and an adsorber 18 housed within a housing 22.
  • An inlet gas stream 26 enters the housing 22 at an inlet 30 and flows through the reformer 14.
  • the inlet gas stream 26 is treated within the reformer 14.
  • a reformate gas stream 34 or syngas flows from the reformer 14 to the adsorber 18.
  • the adsorber 18 removes hydrogen sulfide from the reformate gas stream 34.
  • An outlet gas stream 38 then flows from the adsorber 18 through an outlet 42 in the housing 22 to a fuel cell stack 44.
  • the example fuel cell stack 44 includes a plurality of individual solid oxide fuel cells that provide power in a known manner.
  • the fuel cell stack 44 utilizes the outlet gas stream 38 to support the chemical reactions that provide electrical power.
  • the inlet gas steam 26 includes a hydrocarbon fuel, steam and air.
  • the outlet gas stream 38 includes hydrogen, carbon monoxide, carbon dioxide, nitrogen, methane, water, and trace compounds.
  • the outlet gas stream 38 includes less hydrogen sulfide than the reformate gas stream 34.
  • the outlet gas stream 38 includes less than 100 parts per billion by volume of hydrogen sulfide, and the reformate gas stream 34 includes about 648 parts per billion by volume of hydrogen sulfide or higher concentrations of hydrogen sulfide.
  • the example adsorber 18 (or trap) includes a base 46 that is washcoated with a layer 48 of adsorber material.
  • the adsorber material is a single rare earth oxide, e.g., Ce0 2 or Ce 2 0 3 or La 2 0 3 , a binary oxide, e.g., (Ce02, La203), a ternary oxide, e.g., (Ce02, La203, MnO) or a multi-metal oxide, e.g., (Ce0 2 , REO, MnO) wherein the binary, ternary, or multi-metal oxide materials are formed as a compound oxide or a finely inter-dispersed mixture of the constituent oxides, in this example.
  • These single, binary, ternary or multi-metal oxide materials are prepared by well established processes to prepare powders that have high surface area and high sintering reactivity.
  • the example layer 48 covers each surface of the base 46 with the adsorber material. Other examples cover less of the base 46 leaving some of the base 46 exposed.
  • the example base 46 is made of a cordierite material or another ceramic material.
  • the base 46 includes multiple pores 50 each having a rectangular or near square cross- section.
  • the pores are oftentimes referred to as channels or cells, and have macroscale dimensions, i.e., widths greater than about 50 micrometers. These pores or channels or cells are inherently different from the microscopic pores fo the adsorber material layer 48 as will be discussed hereandbelow.
  • the pores 50 extend longitudinally through the adsorber 18 along an axis A aligned with the direction of flow through the adsorber 18.
  • the base 46 includes a plurality of walls 52 that establish the pores 50.
  • the pores 50 have a honeycomb or hexagonal cross-section.
  • the pores 50 have a circular cross- section.
  • the example base 46 ceramic is known in the art as a honeycomb or ceramic monolith or ceramic monolith substrate. These monoliths are widely used in the automotive business as a support for the catalyst washcoatings of the catalytic converter used in exhaust gas clean-up.
  • the high open flow area of these honeycomb substrates ensure that gas can flow through the ceramic with minimum resistance to flow, i.e., low pressure drop, at high gas velocities.
  • the example base 46 with the washcoating adsorber material for the removal of hydrogen sulfide from reformate gas is projected to lead to pressure drops of less than 3 kPa, and most preferably less than 1 kPa.
  • the example pores 50 have a width X of about 1 millimeter and a height Y of about 1 millimeter.
  • the thickness Ti of cordierite in the walls 52 is about 100 micrometers.
  • the layer 48 has a thickness T 2 that is less than 50 micrometers.
  • the layer 48 is washcoated to each side of the walls 52.
  • the total thickness ⁇ of the example walls 52 is equal to T 2 + T + T 2 , which is less than 200 micrometers.
  • the layer 48 thickness needs to be as large as possible in order to increase the sulfur capacity of the adsorber material.
  • the layer 48 thickness is limited by spallation, which tends to occur with increasing layer 48 thickness.
  • the optimum layer 48 thickness is a compromise, or tradeoff, between these two opposing effects.
  • the adsorber material layer 48 needs to be sufficiently porous so as to promote the diffusional transport of hydrogen sulfide in the pore gas space to the interior surfaces of the adsorber material and ensure as complete reaction as possible of the adsorber material.
  • the porosity of the layer 48 should be as high as possible, preferably up to about 50%, but it should not compromise the structural stability of the coating.
  • the pore size distribution should be tailored so as to promote the hydrogen sulfide diffusional transport rates, in other words, have large enough pores so that the transport of H 2 S occurs in the pore gas space under bulk or molecular diffusion, yet provide high enough surface area to promote the reaction of H 2 S with the adsorbent material.
  • the latter implies the need to have some pores of small size, in which diffusional transport may be controlled by Knudsen diffusion.
  • a combination of large and small pores is desirable, and this combination of pore sizes is usually referred to as a bimodal distribution of the pores in the adsorber material 48 in some examples.
  • the large pores of the adsorber material may have a diameters in the range of 0.5 to 5 micrometers whereas the small pores may have a diameter of 0.05 to 0.5 micrometers.
  • the layer 48 is applied to the honeycomb by wash-coating and sintering and the formation of the larger pores is achieved by incorporating pore former materials, i.e., organic or carbon based solids which burn off during the heat treatment and sintering process in air leaving behind larger voids and pores.
  • pore former materials i.e., organic or carbon based solids which burn off during the heat treatment and sintering process in air leaving behind larger voids and pores.
  • the layer 48 of the rare earth oxide adsorbs hydrogen sulfide from the reformate gas stream 34 as the reformate gas stream 34 flows through the adsorber 18.
  • the areas Ai of the walls 52 closest to the inlet 30 have reacted with the hydrogen sulfide.
  • the area of the walls 52 that have reacted with the hydrogen sulfide increases (e.g., to area A 2 ) as more hydrogen sulfide within the reformate gas stream 34 has moved through the adsorber 18 and more of the layer 48 reacts with the hydrogen sulfide.
  • the layer 48 is a cerium oxide that reduces to Ce 2 0 3 in reformate gas.
  • the layer 48 is a lanthanum oxide La 2 0 3 .
  • Other examples use binary or ternary alloys of cerium oxide or lanthanum oxide, multi-metal oxide adsorber material referred to earlier.
  • the layer 48 is a cerium-lanthanum-manganese oxide, this is another multi-metal oxide adsorber material in one other example.
  • the layer 48 is comprised of a multi-metal oxide based on cerium oxide, a rare earth oxide (REO) selected from the group of lanthanum, praseodymium, neodymium, samarium, and gadolinium and combinations of these which may be represented by the simplified formula (Ce0 2 , REO, MnO).
  • REO rare earth oxide
  • the solid phase of the entire thickness T 2 of the layer is configured to react with hydrogen sulfide within the reformate gas stream 34.
  • the sulfur adsorption capacity of these example oxides ranges from a high of about 115 mg/g at 600 C with no steam present in the gas to about 1 mg/g in gas streams containing 10 mol steam at residence times of about 2 milliseconds.
  • the example housing 22 is a cylindrical housing extending from the inlet 30 to the outlet 42.
  • the housing 22 has a frustoconical shape near the inlet 30, to promote near uniform flow distribution across the reformer 14 and reduce pressure losses.
  • a radiation shield 72 is disposed against the reformer 14.
  • the inlet gas stream 26 passes through the radiation shield 72 before entering the reformer 14.
  • the radiation shield in this example is a perforated metal or ceramic disk. In other instances, the radiation shield is made of a high porosity metal or ceramic foam.
  • the example reformer 14 is a catalytic autothermal reformer.
  • the reformer 14 is a catalytic partial oxidation reformer or a catalytic steam reformer.
  • the example reformer 14 is a porous ceramic with a catalyst and has a diameter D of about 12.065 cm.
  • the catalysts used in the autothermal reformer, partial oxidation reformer, and steam reformer are well known in the art and may be comprised of a combination of noble and base metals on inert ceramic supports, with or without promoters, that optimize selectivity and reforming efficiency, mitigate carbon formation and impart resistance to sulfur poisoning.
  • a spacer 76 is disposed between the adsorber 18 and the reformer 14.
  • the reformate gas stream 34 flows though an aperture 78 in the spacer 76.
  • a seal 80 surrounds a radially outer surface of the adsorber 18 such that the adsorber 18 is radially spaced from the housing 22.
  • the housing 22 is a metallic material in this example.
  • the housing 22 expands and contracts with temperature changes at a different rate than the adsorber 18.
  • the seal 80 ensures that no gaps form between the adsorber 18 and the housing 22 so that the reformate gas stream 34 is forced to move through the adsorber 18 rather than moving through the gaps.
  • the seal 80 is an interam intumescent mount seal.
  • a maintenance cap 84 connects to the adsorber 18 and the seal 80 with a plurality of pins 88.
  • the maintenance cap 84 enables a user to remove the adsorber 18 from the housing 22 by pulling the maintenance cap 84 in a direction Z. Once removed, the user can replace the adsorber 18 with a different or fresh or unreacted or virgin adsorber. Replacing the adsorber 18 may be necessary when substantially all the material in the layer 48 has reacted with reacted with hydrogen sulfide and the adsorber 18 is no longer effectively removes hydrogen sulfide.
  • the example adsorber 18 is thus disposable and replaceable.
  • Another example of the adsorber assembly 10 uses a rare earth element in a granular form to remove hydrogen sulfide from the reformate gas stream 34.
  • the granular form is uses instead of the layer 48 on the base 46.
  • the granular form may be held within a container (not shown) in the housing 22.
  • the granular form of the rare earth element may induce a significant pressure drop within an adsorber assembly due to the granular form blocking flow through the adsorber assembly 10.
  • features of the disclosed examples include using a rare earth oxide to remove hydrogen sulfide from reformate gas.
  • the example rare earth oxides are chemically stable for hydrogen sulfide adsorption at temperatures near 800°C and these adsorber materials can be used for reformate gas clean-up at temperatures higher than about 500°C.
  • another feature of the disclosed examples includes removing hydrogen sulfide from reformate gas without requiring significant temperature changes to the reformate gas.
  • Still other features of the disclosed examples include eliminating the need for heat exchangers or complicated piping and fittings when moving reformate gas to a fuel cell.
  • Another feature is substantially eliminating the possibility of coke formation and deposition using a low weight and low volume assembly which minimizes heat losses and essentially maintains the gas stream temperature near constant at the desired temperature level to eliminate the possibility of coke formation.

Abstract

L'invention concerne un ensemble adsorbeur donné à titre d'exemple qui comprend un adsorbeur et un logement. Le logement s'étend entre une entrée et une sortie. Le logement est configuré pour communiquer un gaz de reformage à travers au moins une partie de l'adsorbeur. L'adsorbeur comprend un revêtement de matériau choisi dans un groupe constitué par l'oxyde de cérium, un oxyde de terres rares, et leurs combinaisons. Le revêtement de matériau a une épaisseur et est configuré pour réagir avec du sulfure d'hydrogène à travers toute l'épaisseur.
PCT/US2010/053921 2010-10-25 2010-10-25 Ensemble adsorbeur WO2012057727A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020136936A1 (en) * 2001-02-12 2002-09-26 Grieve Malcolm James Trapping method and system for energy conversion devices
US20050032640A1 (en) * 2003-08-07 2005-02-10 He Huang Method and structure for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant
US20070012028A1 (en) * 2005-07-12 2007-01-18 Walter Weissman Sulfur oxide/nitrogen oxide trap system and method for the protection of nitrogen oxide storage reduction catalyst from sulfur poisoning
US20080210090A1 (en) * 2006-08-31 2008-09-04 Geo2 Technologies, Inc. Extruded Porous Ceramic Fuel Cell Reformer Cleanup Substrate
US20080267848A1 (en) * 2004-11-08 2008-10-30 Trustees Of Tufts College Apparatus and Methods for Non-Regenerative and Regenerative Hot Gas Sulfurization

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020136936A1 (en) * 2001-02-12 2002-09-26 Grieve Malcolm James Trapping method and system for energy conversion devices
US20050032640A1 (en) * 2003-08-07 2005-02-10 He Huang Method and structure for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant
US20080267848A1 (en) * 2004-11-08 2008-10-30 Trustees Of Tufts College Apparatus and Methods for Non-Regenerative and Regenerative Hot Gas Sulfurization
US20070012028A1 (en) * 2005-07-12 2007-01-18 Walter Weissman Sulfur oxide/nitrogen oxide trap system and method for the protection of nitrogen oxide storage reduction catalyst from sulfur poisoning
US20080210090A1 (en) * 2006-08-31 2008-09-04 Geo2 Technologies, Inc. Extruded Porous Ceramic Fuel Cell Reformer Cleanup Substrate

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