WO2008093292A1 - Pile à combustible à oxyde solide combiné - Google Patents

Pile à combustible à oxyde solide combiné Download PDF

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Publication number
WO2008093292A1
WO2008093292A1 PCT/IB2008/050359 IB2008050359W WO2008093292A1 WO 2008093292 A1 WO2008093292 A1 WO 2008093292A1 IB 2008050359 W IB2008050359 W IB 2008050359W WO 2008093292 A1 WO2008093292 A1 WO 2008093292A1
Authority
WO
WIPO (PCT)
Prior art keywords
reformer
fuel cell
solid oxide
hydrogen
catalyst
Prior art date
Application number
PCT/IB2008/050359
Other languages
English (en)
Inventor
Sadig Kuliyev
Beycan Ibrahimoglu
Rafig Alibeyli
Ibrahim Pamuk
Yalçin SEZEN
Deniz Kozlu
Original Assignee
Vestel Elektronik Sanayi Ve Ticaret A.S.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vestel Elektronik Sanayi Ve Ticaret A.S. filed Critical Vestel Elektronik Sanayi Ve Ticaret A.S.
Publication of WO2008093292A1 publication Critical patent/WO2008093292A1/fr

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Classifications

    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • 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
    • 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
    • H01M8/0625—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 in a modular combined reactor/fuel cell structure
    • 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
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • 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

  • the present invention relates to a Solid Oxide Fuel Cell (SOFC) designed in a combined manner.
  • SOFC Solid Oxide Fuel Cell
  • Such combined solid oxide fuel cell designed to convert the hydrogen generated by decomposing hydrocarbon gases and fossil fuels into electrical energy by means of an electrochemical method is characterized in that the fuel cell and the gas conversion reformer are designed together as a single unit.
  • PAFC Phosphoric acid fuel cells
  • Fuel cells may provide low-, medium-, and large-capacity electrical power production. They have the following advantages over conventional power producing systems:
  • SOFC Solid Oxide Fuel Cells for utilization in military and civil fields such as houses, vehicles, submarines, and other equipments and industrial fields, etc.
  • SOFC of varying sizes have already been manufactured [3, A].
  • SOFCs operate with hydrogen obtained as a result of cracking fossil fuels at high temperatures [4].
  • High-temperature fuel cells are classified as Molten Carbonate Fuel Cells (MCFC) and Solid Oxide Fuel Cells (SOFC) according to the electrolytes they employ.
  • Hydrogen gas (H 2 ) is required to operate all fuel cells. Hydrogen gas is produced by various means and supplied to fuel cells.
  • the H 2 gas required for SOFCs is obtained by various catalytic methods from coal, diesel oil, gasoline, natural gas, methane, LPG, etc. [1 ,3].
  • the hydrogen gas generation process is conducted by means of the following catalytic methods at 650-850 0 C temperatures:
  • the significant advantage of the conversion method of methane with water vapor is based on that even the one hydrogen molecule in water resulting from the reaction is made use of, so as to enhance the efficiency.
  • the carbon produced from the reaction covers the catalyst's surface so that the hydrogen generation rate is gradually lowered and after a certain period of time, it renders the catalyst completely inoperable. In order to avoid this process, it becomes indispensable to regenerate the catalyst with oxygen at high temperatures after a certain period of time.
  • two reformers are required to continuously run the fuel cell. Periodically, in one of said reformers the catalyst is activated, while in the other the hydrogen is converted. As known, extra system developments are required in order to conduct all such processes.
  • the reformer is built separately from the cell [1 , 2, 3].
  • the fuel is supplied to the reformer and is converted to hydrogen at high temperatures.
  • the obtained hydrogen gas is fed to the fuel cell at high temperature.
  • Tubular solid oxide fuel cells 2. Planar solid oxide fuel cells
  • tubular solid oxide fuel cells allow for simple cell stacking and do not require gaskets.
  • manufacturing of such fuel cells are difficult, expensive, and labor- intense. Since it also involves a long current collector path, it presents a lower power density as compared to other type of fuel cells.
  • planar solid oxide fuel cells whilst they have the advantage of being proper to be cast in the form of stripes, they present "thermal shock resistance” due to high temperatures.
  • Solid oxide fuel cells need to be operated at around 1000 0 C to have a low internal electrical resistance.
  • the operating temperature of solid oxide fuel cells is in principle at an adequate level for vapor reforming within the solid oxide stacks for hydrocarbon fuels.
  • the internal vapor reforming shall simplify the balance of the solid oxide fuel cell's power system and enhance the operation efficiency.
  • hydrocarbon fuel within the stack many problems emerge.
  • the decomposition of methane is conducted out of the fuel cell for hydrogen generation.
  • the remaining processes are conducted within the fuel cell.
  • the methane converter i.e. reformer
  • SOFC Solid Oxide Fuel Cell
  • the methane converter i.e. reformer
  • the methane converter to generate hydrogen is not designed as a separate unit, instead, it is devised as a single unit together with the fuel cell. Differing from conventional methods, all processes in this design are conducted concurrently and in sequence within a single unit comprising the fuel cell and reformer, as illustrated below.
  • the conversion reactions of methane and carbon with water vapor are conducted in parallel.
  • the water required for the latter two reactions is generated at the surface of anode as a result of ongoing reactions within the solid oxide fuel cell, and the water is converted to steam with the high temperature in the cell.
  • a further significant feature of the combined solid oxide fuel cell according to the present invention is that no extra oxidative regenerator is required in converting the coke (carbon) formed on the catalyst's surface in the direct decomposition process of methane with water vapor, in other words, in eliminating the coke formed this way.
  • Figure 2 illustrates the basic elements of the fuel cell and the operation principle thereof.
  • the reference numbers of parts in Figure 2 are as following: 1- Fuel,
  • a SOF cell is composed of two electrodes separated by an electrolyte membrane. Oxygen supplied from air or by direct means is reduced to oxygen ion at the cathode region.
  • the electrolyte ensures the transfer of oxygen ions from the cathode to the anode.
  • hydrogen and carbon monoxide are oxidized with the O "2 ions coming from the cathode.
  • a different SOFC is designed based on the reactions occurring at the cathode and anode.
  • the direct decomposition approach of methane is envisaged for the Combined Solid Oxide Fuel Cell according to the present invention.
  • the cell design is simple, its efficiency is high, and the coke formation on the catalyst, along with other problems are avoided without necessitating additional equipments and devices.
  • the subject SOFC is also more compact and is run at a relatively higher efficiency.
  • the reformer required for the fuel cell is not designed out of the cell, but is designed in the form of a plate at the lower section of the cell.
  • the reference numbers of parts in Figure 3 are as following: 1- Catalyst, 2- Catalyst slot,
  • the combined solid oxide fuel cell according to the present invention differs from other solid oxide fuel cells with respect to design and operation procedure.
  • Figure 4 illustrates a stack of combined fuel cell.
  • Figure 5 gives a cross-section of a combined fuel cell stack.
  • the reference numbers of parts in Figure 5 are as following: 1- Membrane,
  • a plurality of cylindrical tubes (6) are provided within the reformer (8) located at the lower section of the fuel cell, and the interior of said tubes are filled with catalyst (7).
  • the catalyst (7) is accurately filled so as to occupy the two third of the volume of cylindrical tubes (6), leaving a space for the enlargement of catalyst (7) in use.
  • Methane gas supplied externally to the reformer (8) is collected at the lower tank (9) and is transferred by means of channels (5) to cylindrical tubes (6) containing the catalyst (7).
  • the methane gas undergoes the decomposition reaction here on the catalyst (7):
  • the hydrogen gas generated in cylindrical tubes (6) filled with catalyst contacts the anode surface of the membrane (1) assembled on the tubes. Oxygen supplied from air or by direct means is reduced to oxygen ion on the cathode surface.
  • the electrolyte membrane group provides the transfer of oxygen ions from the cathode to the anode. At the anode region, hydrogen and carbon monoxide are oxidized with the O "2 ions coming from the cathode.
  • the hydrogen generated at the reformer section is transferred to serially-connected fuel cells by means of inlet (4) and outlet (5) channels at the anode side, so that hydrogen (3) and oxygen (2) gases are uniformly distributed along the entire area by helical channels formed on the gas distributor plate (10).
  • the hydrogen requirement to operate the fuel cell is met.
  • various hydrocarbon gases such as C 1 -C 4 and their mixtures can be used as fuel.

Abstract

L'invention concerne une pile à combustible à oxyde solide combiné qui est conçue pour convertir l'hydrogène généré par la décomposition du méthane, du gaz naturel ou d'autre gaz d'hydrocarbure, en énergie électrique au moyen d'un procédé électrochimique, la pile à combustible et le reformeur de recyclage de gaz étant conçus ensemble en une seule unité. Dans le mode de réalisation de l'invention, le reformeur (8) est conçu au niveau de la section inférieure de la pile à combustible, un catalyseur (7) est fourni dans le reformeur et des membranes (1) sont placées sur le reformeur. L'hydrogène généré par les gaz de décomposition dans le reformeur génère un courant à la surface d'anode des membranes, forme de l'eau avec des ions d'oxygène provenant de la région de cathode (2), et une telle eau générée entre en contact avec le catalyseur de reformeur sous la forme de vapeur. La vapeur d'eau générée au niveau de la région d'anode (3) réagit avec le coke (carbone) formé sur la surface du catalyseur de reformeur, produisant du monoxyde de carbone et de l'hydrogène. Grâce à cette caractéristique, la carbonisation du catalyseur est évitée de façon à prolonger sa durée de fonctionnement et à générer un courant supplémentaire à partir d'un tel hydrogène généré.
PCT/IB2008/050359 2007-02-02 2008-01-31 Pile à combustible à oxyde solide combiné WO2008093292A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2007/00587 2007-02-02
TR2007/00587A TR200700587A2 (tr) 2007-02-02 2007-02-02 Kombine katı oksit yakıt pili

Publications (1)

Publication Number Publication Date
WO2008093292A1 true WO2008093292A1 (fr) 2008-08-07

Family

ID=39345203

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2008/050359 WO2008093292A1 (fr) 2007-02-02 2008-01-31 Pile à combustible à oxyde solide combiné

Country Status (2)

Country Link
TR (1) TR200700587A2 (fr)
WO (1) WO2008093292A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3796442A4 (fr) * 2018-05-18 2022-03-02 Kabushiki Kaisha F.C.C. Système de pile à combustible

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297483A (en) * 1965-04-07 1967-01-10 Air Prod & Chem Method for generating electrical energy from light gaseous fuel
WO2003075388A1 (fr) * 2002-03-04 2003-09-12 Ceramic Fuel Cells Limited Pile a combustible a oxyde solide
US20030175565A1 (en) * 2002-02-19 2003-09-18 Aisin Seiki Kabushiki Kaisha Solid oxide fuel cell system and a method for controlling the same
US6653005B1 (en) * 2000-05-10 2003-11-25 University Of Central Florida Portable hydrogen generator-fuel cell apparatus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297483A (en) * 1965-04-07 1967-01-10 Air Prod & Chem Method for generating electrical energy from light gaseous fuel
US6653005B1 (en) * 2000-05-10 2003-11-25 University Of Central Florida Portable hydrogen generator-fuel cell apparatus
US20030175565A1 (en) * 2002-02-19 2003-09-18 Aisin Seiki Kabushiki Kaisha Solid oxide fuel cell system and a method for controlling the same
WO2003075388A1 (fr) * 2002-03-04 2003-09-12 Ceramic Fuel Cells Limited Pile a combustible a oxyde solide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3796442A4 (fr) * 2018-05-18 2022-03-02 Kabushiki Kaisha F.C.C. Système de pile à combustible

Also Published As

Publication number Publication date
TR200700587A2 (tr) 2008-06-23

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