Fuel cell system having biogas desulfurizer assembly with manganese oxide desulfurizer material

• US 9,847,543 B2
• Filed: 03/06/2013
• Issued: 12/19/2017
• Est. Priority Date: 03/06/2013
• Status: Active Grant

• Current Assignee: Fuelcell Energy Ltd.
• Original Assignee: Fuelcell Energy Ltd.
• Inventors: Wang, Jin-Yun, Farooque, Mohammad, Xu, David, Sanders, Zachary
• Primary Examiner(s): Slifka, Sarah A
• Assistant Examiner(s): Ohara, Brian
• Application Number:
  US13/786,571
• Publication Number:
  US 20140255805A1
• Time in Patent Office: 1,749 Days
• Field of Search: 429410, 423700, 252184
• CPC Class Codes: B01D 2251/602 Oxides
• CPC Class Codes: B01D 2253/1124 Metal oxides
• CPC Class Codes: B01D 2255/2073 Manganese
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/306 Organic sulfur compounds, e.g. mercaptans
• CPC Class Codes: B01D 2257/553 Compounds comprising hydrogen, e.g. silanes
• CPC Class Codes: B01D 2257/80 Water
• CPC Class Codes: B01D 2258/05 Biogas
• CPC Class Codes: B01D 53/48 Sulfur compounds
• CPC Class Codes: B01D 53/8603 Removing sulfur compounds
• CPC Class Codes: B01J 43/00 Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties ion-exchange chromatography processes B01D15/36
• CPC Class Codes: C12M 47/18 Gas cleaning, e.g. scrubbers; Separation of different gases separating dispersed particles from gases or vapours B01D45/00; separation of gases or vapours B01D53/00; gas washing apparatus for laboratory uses B01L5/04
• CPC Class Codes: H01M 8/04014 Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
• CPC Class Codes: H01M 8/0675 Removal of sulfur
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A desulfurizer material for desulfurizing fuel supplied to a fuel cell system, the desulfurizer material comprising one or more manganese oxide materials having an octahedral molecular sieve (OMS) structure, and the desulfurizer material being resistant to moisture and being capable of removing organic sulfur containing compounds and H₂S. The desulfurizer material is used in a desulfurizer assembly which is used as part of a fuel cell system.

Claims

1. A fuel cell system comprising:

a biogas fuel supply assembly;

a desulfurizer assembly configured to receive biogas fuel from the biogas fuel supply assembly and to desulfurize the biogas fuel, the desulfurizer assembly comprising one or more desulfurizer beds; and

a fuel cell stack including an anode side and a cathode side, the anode side of the fuel cell stack receiving the desulfurized biogas fuel from the desulfurizer assembly;

wherein each of the one or more desulfurizer beds comprises a desulfurizer material configured to desulfurize biogas fuel conveyed through said one or more desulfurizer beds, and

wherein the desulfurizer material in at least one of the one or more desulfurizer beds comprises a manganese oxide material that has an octahedral molecular sieve (OMS) structure and is doped with Fe,

wherein the manganese oxide material comprises OMS-2 having a 2×

2 tunnel structure, and

wherein an amount of the Fe in the desulfurizer material is greater than 0% (mole) and less than 50% (mole) of a total metal content of the desulfurizer material.

2. The fuel cell system in accordance with claim 1, wherein:

the desulfurizer assembly comprises a plurality of desulfurizer beds, including a first desulfurizer bed and a second desulfurizer bed, and

the first desulfurizer bed and the second desulfurizer bed comprises different desulfurizer materials.

3. The fuel cell system in accordance with claim 1, further comprising a cleanup assembly configured to process the biogas fuel before the biogas fuel is conveyed to the fuel cell assembly, the cleanup assembly comprising an H₂S removal unit for removing H₂S from the biogas fuel.

4. The fuel cell system in accordance with claim 3, wherein:

the biogas fuel supply comprises a biogas digester; and

the fuel cell system further comprises a heating assembly configured to heat the biogas digester using waste heat from the fuel cell stack.

5. The fuel cell system in accordance with claim 4, wherein the heating assembly is configured to pre-heat the desulfurized fuel using one of anode exhaust and cathode exhaust, and the heating assembly is further configured to receive water and to humidify the desulfurized fuel with the received water.

6. The fuel cell system in accordance with claim 3, wherein the fuel cell system is configured to operate on two or more fuels of different compositions and the fuel cell system further comprises:

a second fuel supply assembly for supplying a second fuel, having a different composition from the first fuel, to the desulfurizer assembly,

wherein the second fuel is not conveyed through the cleanup assembly.

7. The fuel cell system in accordance with claim 6, wherein the biogas fuel supply assembly comprises a biogas digester and the fuel cell system further comprises a heating assembly configured to heat the biogas digester so as to maintain the temperature in the biogas digester at a predetermined temperature.

8. The fuel cell system according to claim 6, further comprising a control assembly for controlling at least one of:

(a) flow rates of first fuel and second fuel through the biogas fuel supply assembly and the second supply assembly, respectively; and

(b) flow of the biogas fuel and the second fuel through the one or more desulfurizer beds in the desulfurizer assembly.

9. The fuel cell system in accordance with claim 3, wherein the cleanup assembly further comprises a moisture conditioning unit for removing moisture from the biogas fuel.

10. The fuel cell system in accordance with claim 9, wherein the cleanup assembly further comprises a siloxane removal unit for removing siloxanes from the biogas fuel.

11. The fuel cell system in accordance with claim 6, wherein the second fuel is natural gas.

12. The fuel cell system in accordance with claim 1, wherein the manganese oxide material of the desulfurizer material in said at least one of the one or more desulfurizer beds is further doped with a second doping metal selected from the group consisting of K, Mg, Co, Ag, Cu, Zn, Ni, and mixtures thereof.

13. The fuel cell system in accordance with claim 1, wherein the manganese oxide material is resistant to moisture and capable of removing organic sulfur containing compounds and H₂S.

14. The fuel cell system in accordance with claim 1, wherein the OMS-2 has a tunnel size of about 4.6 Å

.

15. The fuel cell system in accordance with claim 1, wherein the biogas fuel supply assembly is configured to supply biogas fuel having a relative humidity of at least 10% to the desulfurizer assembly.

16. The fuel cell system in accordance with claim 1, wherein the biogas fuel supply assembly is configured to supply biogas fuel having a relative humidity of at least 30% to the desulfurizer assembly.