TW201112487A - Systems and processes for operating fuel cell systems - Google Patents

Abstract

The present invention is directed to systems and processes of operating molten carbonate fuel cell systems. A process for operating the molten carbonate fuel cell includes providing a hydrogen-containing stream comprising molecular hydrogen from a high temperature hydrogen-separation device to a molten carbonate fuel cell, wherein the high temperature hydrogen-separation device comprises one or more high temperature hydrogen-separating membranes; mixing at least a portion of hydrocarbons to be provided to, or provided to, a first reformer with anode exhaust from the molten carbonate fuel cell; at least partially reforming some of the hydrocarbons in the first reformer to produce a steam reforming feed; and providing the steam reforming feed to a second reformer, wherein the second reformer comprises the high temperature hydrogen-separation device or the second reformer is operatively coupled to the high temperature hydrogen-separation device, and the high temperature hydrogen-separation device is configured to produce at least a portion of the stream comprising molecular hydrogen provided to the molten carbonate fuel cell.

Description

201112487 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fuel cell system and a method for operating the same. In particular, the present invention relates to systems and methods for operating a molten carbonate fuel cell system. [Prior Art] A molten carbonate fuel cell converts chemical energy into electrical energy. Molten carbonate fuel cells are useful because they deliver high quality, reliable electrical power to operate a clean and relatively compact generator. These features make the use of smelting carbonate fuel cells as power sources in urban areas, ships or remote areas where access to power sources is limited. A molten carbonate fuel cell is formed by an anode, a cathode, and an electrolytic layer sandwiched between the anode and the cathode. The electrolyte comprises an alkali metal carbonate, an alkaline earth metal carbonate, a molten alkali metal carbonate or a mixture thereof which can be suspended in a porous, insulating and chemically inert matrix. An oxidizable fuel gas or a gas recombinable in the fuel cell to an oxidizable fuel gas is fed to the anode. The oxidizable fuel gas fed to the anode is typically a mixture of a syngas-oxidizable component, molecular hydrogen, carbon dioxide, and carbon monoxide. An oxidant-containing gas, typically air and carbon dioxide, can be fed to the cathode to provide a chemical reactant that produces a carbonate anion. The carbonate anions are constantly being updated during operation of the fuel cell. Operating a molten carbonate fuel cell at a high temperature (typically from 55 (rc to 7 Torr (rC)) to react oxygen in the oxidant-containing gas with carbon dioxide to produce carbonate anions. The carbonate anions cross the electrolyte at the anode Reacts with hydrogen and/or carbon monoxide from fuel gas by 148979.doc 201112487. The electrical energy is generated by the conversion of oxygen and carbon dioxide at the cathode to carbonate ions and the chemical reaction of carbonate ions with hydrogen and/or carbon oxide at the anode. The following reaction illustrates the electrochemical reaction in a battery in the absence of carbon monoxide: Cathodic charge transport: CO2+0.5 02+2e-->(:03 = anode charge transport: C03=+H2-H20+C02+2e_ and total reaction : H2+0.5 02—·Η20 If carbon monoxide is present in the fuel gas, the following chemical reaction illustrates the electrochemical reaction in the battery. Cathodic charge transfer: C02+〇2+4e-->2 C03 = Anode charge transfer: C〇3=+H2—H20+C02+2e· and CO3 +CO—C〇2+2e Total reaction: h2+co+o2->h2o+co2 An electrical load or storage device can be connected to the anode and The midday current between the cathodes Flowing between the pole and the cathode. The current supplies power to the electrical load or provides electrical power to the storage device. The fuel gas is typically supplied to the anode by a steam reformer that recombines a low molecular weight hydrocarbon and steam into hydrogen And carbon oxides. For example, the decane in the natural gas is used to produce a preferred low molecular weight hydrocarbon for the fuel gas of the fuel cell. Alternatively, the fuel cell anode can be designed to be implemented internally. Recombination of one of the anodes supplied to the anode of the fuel cell: (for example, 曱炫) with steam of steam. The recombination of the smoldering gas provides a fuel gas containing hydrogen and carbon monoxide according to the following reaction: CH4+H2〇 t; C〇 + 3H2. Typically, the steam recombination reaction system 148979.doc 201112487 is carried out at a temperature effective for converting a large number of brothels to steam and 1 and carbon monoxide. It can be steamed in a steam reformer. Carbon monoxide is converted into hydrogen and carbon dioxide by a water gas conversion reaction: H^ + COSCOrfH2 is converted to hydrogen and carbon dioxide to achieve further hydrogen production. However, it is used to supply fuel gas to a melt. In a conventional operating steam reformer of a carbonate fuel cell, a small amount of hydrogen is produced by the water gas shift reaction because the steam reformer is energized at a temperature which is favorable for the production of carbon monoxide and hydrogen by steam recombination reaction. Operation at this temperature is not conducive to the production of carbon dioxide and hydrogen by the water gas shift reaction. Since carbon monoxide can be oxidized in the fuel cell to provide electrical energy and carbon dioxide cannot, it is beneficial to the recombination of hydrocarbons and steam to hydrogen and carbon monoxide. Performing the recombination reaction at a temperature is generally accepted as a preferred method of providing a fuel for the fuel cell. Since the fuel gas is usually supplied to the anode by external or internal steam recombination, it contains hydrogen, carbon monoxide and a small amount of carbon dioxide, unreacted methane, and water as steam. However, a fuel gas containing a non-hydrogen compound (e.g., carbon monoxide) is inefficient for producing a relatively pure hydrogen fuel gas stream in a molten carbonate fuel cell. At a given temperature, the electrical power that can be produced in a molten carbonate fuel cell increases as the hydrogen concentration increases. This is due to the electrochemical oxidation potential of molecular hydrogen relative to other compounds. For example, Watanabe et al., "Applicability 〇f molten carbonate fuel cells to various fuels" (J〇urnai 〇fp〇vver Sources, 2006, pp. 868-871) describes the use of 5% by mole of molecular hydrogen and 5% by weight. One of the water is fed and at a pressure of 9〇0/〇 fuel, one of the pressures of 〇·49 MPa, and one of the current densities of 1500 A/m2 148979.doc 201112487 Operation One of the 10 kW molten carbonate fuel cell stacks can be produced 〇 12 W/cm2 of one electric power density and 0.792 volts of one battery voltage, while using the same molten carbonate fuel cell stack operating under the same operating conditions with one of 50% carbon oxide and 50% water feed can produce only 1. 1 1 W/Cm2 electric power density and 0.763 volts one battery voltage. Therefore, a fuel gas stream containing a large amount of non-hydrogen compounds is not as good as most hydrogen-containing fuel gas in a smelting carbonate fuel cell. effective. However, molten carbonate fuel cells are typically commercially operated in a "hydrogen lean" mode in which the fuel gas is selected, for example, by steam recombination to limit the amount of hydrogen exiting the fuel cell in the fuel gas. This is done to balance the electrical potential of the hydrogen in the fuel gas with the potential energy (electrochemistry + heat) lost by the hydrogen exiting the cell without being converted to electrical energy. However, some measures have been taken to recapture the ability of hydrogen to exit the fuel cell. The energy efficiency of such hydrogen is significantly lower than in the case where hydrogen reacts electrochemically in the fuel cell. For example, the anode exhaust gas generated by electrochemical reaction of the fuel gas in the fuel cell has been burned to drive a turboexpander to generate electricity. However, the electrochemical potential of hydrogen in the fuel cell is significantly higher than that. Inefficient, due to many thermal energy losses in thermal energy rather than conversion to electrical energy by an expander. The fuel gas exiting the fuel cell has been combusted to provide thermal energy for various heat exchange applications. However, after combustion, almost 50% of the thermal energy is lost in these heat exchange applications. Hydrogen is used to ignite an expensive gas used in one of the burners used in inefficient energy recovery systems, and thus the amount of hydrogen used in a molten carbonate fuel cell is conventionally adjusted to utilize the hydrogen provided to the fuel cell. Most of this produces 148,979.doc 201112487 electrical power and minimizes the amount of hydrogen that exits the fuel cell in the fuel cell exhaust. Other measures have been taken to recycle more hydrogen from the fuel gas present in the anode exhaust and/or to recycle the hydrogen in the anode gas by providing the fuel gas to a post-recombiner and/or gas separation unit. The fuel gas present in the anode for recovery of hydrogen and/or carbon dioxide is recombined in a post-recombiner to concentrate hydrogen in the % polar gas stream and/or undergo a water gas shift reaction to form hydrogen and carbon dioxide. Heat can be supplied by the anode gas stream. The heat used to induce the methane vapor recombination reaction in a steam reformer and/or to convert the liquid fuel to the feed for the steam reformer has also been provided by the burner. A burner that combusts an oxygen-containing gas with a fuel, typically a hydrocarbon fuel such as natural gas, can be used to provide the required heat to the steam reformer. The fca burn has been used to drive the heat of the steam recombination reaction, wherein the flameless combustion is also driven by providing a hydrocarbon fuel and oxidant to a flameless combustion chamber by avoiding the relative amount of induced flaming combustion. The energy efficiency of such methods for providing the heat necessary to drive the steam recombination reaction and/or the water gas shift reaction is relatively low because the large amount of thermal energy provided by combustion is not captured and lost. The hydrogen and carbon dioxide in the reformed gas stream can be separated from the anode gas stream, for example by using a pressure swing adsorption unit and/or a membrane separation unit. The temperature of the anode exhaust is typically higher than the temperature required for commercial hydrogen and/or carbon dioxide separation units. For example, the stream can be cooled by a heat exchanger, although thermal energy can be lost during the cooling process. The separated hydrogen is fed to the anode portion of the fuel cell. Recirculation of nitrogen to 148979.doc -10- 201112487 to the anode allows the fuel gas entering the molten carbonate fuel cell to be enriched in hydrogen. The separated carbon dioxide is fed to the cathode portion of the fuel cell. Recirculating carbon dioxide to the cathode enriches the air entering the molten carbonate fuel cell with carbon dioxide. US Patent No. 7,097,925 provides a fuel cell power generation system comprising: a molten carbonate fuel cell; an anode gas separation soup unit that cooperates with a combustion chamber (which may include a catalyst to ensure complete combustion) Enriched with hydrogen for anode recirculation and transporting carbon dioxide from the anode side of the fuel cell to the cathode side; and an integrated gas turbine unit for gas compression and expansion. II is converted from a portion of the feed by internal recombination within the anode to produce hydrogen. The feed gas system is illustrated as natural gas. The anode gas mixture is discharged from the anode σ. Steam is added to the anode gas mixture and the mixture is introduced to an optional rear recombiner. The post-recombiner contains a steam recombination catalyst to perform an endothermic steam recombination reaction = H4 + H2 (^C〇 + 3H2A CH4 + 2H2 (^c〇 2+4H2. After the reaction in the post-recombiner, the anode is The gas mixture is delivered to an inlet of a first expander. After expansion in the expander, the post-recombined anode gas is reheated with heat from a combustion chamber and the anode gas is delivered to a second expander. The post-recombined anode gas stream is expanded in a second expander to substantially reduce the weigh pressure and then the anode gas stream is passed to a water gas shift reactor. The anode gas mixture is passed through a heat reflux heat exchanger for cooling From the water gas shift reactor to a condenser to remove water: and then to a pressure swing adsorption unit to separate gas from the anode gas present compound. Hydrogen-rich light product gas and fuel from a pressure swing adsorption unit Mixing and delivering 148979.doc 201112487 to a pretreatment unit' and then to the anode inlet of the fuel cell. Although combustion provides more efficiency than trapping heat, the method is relatively thermally inefficient. Multiple heating 'cooling and/or separation steps are required to produce hydrogen and/or carbon dioxide. Additionally, the reformer does not convert a liquid hydrocarbon feedstock to a lower molecular weight feed for the steam reformer and possibly from the tree material battery Insufficient heat is provided to carry out this. Improvements in the efficiency of operating a molten carbonate fuel cell system for generating electricity and enhancing the power density of the molten carbonate fuel cell may be desired. SUMMARY OF THE INVENTION A method of operating a molten carbonate fuel cell system, comprising: providing a stream comprising molecular hydrogen from a high temperature hydrogen separation unit to a molten carbonate fuel cell, wherein the high temperature hydrogen separation unit comprises one or more: high temperature a hydrogen separation membrane; heating, by a heat source, a portion of the hydrocarbon to be supplied to or supplied to a first reformer, the heat source comprising anode exhaust gas from the molten carbonate fuel cell and/or from the anode exhaust gas Heating at least partially recombining certain hydrocarbons of the hydrocarbons in the first reformer to produce a feed stream; and providing the feed stream to a second recombiner, wherein the second recombiner package: a high temperature hydrogen separation unit or the second recombiner is operatively coupled to the peri-hydrogen separation unit and the high temperature hydrogen separation unit is configured to generate an The molten carbonate fuel cell includes at least one portion of a molecular hydrogen stream 148979.doc 201112487. In another aspect of the invention, a molten carbonate fuel cell system includes: a molten carbonate fuel cell; a first recombiner coupled to the molten carbonate fuel cell, the first recombiner configured to receive anode exhaust gas and hydrocarbons from the molten carbonate fuel cell, and the first recombinator is configured to Allowing the anode exhaust or heat from the anode exhaust to be sufficiently mixed with the hydrocarbons to at least partially recombine certain hydrocarbons of the hydrocarbons to produce a feed stream; a second recombiner coupled to the a first recombiner configured to receive the feed stream from the first recombiner; and a high temperature hydrogen separation unit that is part of the second recombiner or coupled to S Xuan second Reorganizer Is operatively coupled to the molten carbonate fuel cell, wherein the temperature 咼 hydrogen separator comprises one or more high temperature hydrogen- separation film, and was configured to provide a ilk comprising molecular hydrogen to the molten carbonate fuel cell. [Embodiment] The invention as set forth herein provides an efficient method for operating a molten carbonate fuel cell to produce electricity at a high electrical power density and a system for performing the same. First, the methods described herein are more thermally and energy efficient than the methods disclosed in the prior art. The heat from the exhaust of a fuel cell is transferred directly to a first recombiner. A portion of the transferred thermal energy is then transferred from the first recombiner to a second recombiner. The heat is directly vented from the anode of the fuel cell to the first recombiner. The transmission is efficient 148979.doc -13 - 201112487, because the transmission is from the fuel cell by the first recombiner. & The anode exhaust stream is directly distributed with a hydrocarbon stream comprising fumes and steam. A hot feed is produced from the first reformer and subsequently fed to the first reformer. The transfer of thermal energy from the first recombiner to the second recombination is also efficient because the thermal energy is included in the feed from the first recombiner to the second recombiner. The method as set forth herein is also more thermally efficient than the methods disclosed in the art because the heat from the anode exhaust is used to produce hydrogen at temperatures below the typical steam recombination process. In the process of the present invention, hydrogen can be separated from the reformed product gas using a t-temperature hydrogen separation unit, wherein the high temperature gas knife separation device is a membrane separation device. The high temperature hydrogen separation unit is operatively coupled to the second reformer such that hydrogen can be separated from the reformed gas upon recombination reaction in the second reformer. The separation of hydrogen towards the hydrogen produces a drive equilibrium and reduces the temperature required to produce hydrogen. In addition, more hydrogen can be produced at lower recombination temperatures, which is due to the balance of the water gas shift reaction (H2〇+C〇t; C〇2+H2), which facilitates the production of hydrogen at lower recombination temperatures. Recombination reaction temperature is not conducive to it. The large amount or all of the molecular hydrogen produced from the second recombiner is supplied to the shale carbonate fuel cell. 0 The method as set forth herein allows for the use of liquid fuel. The heat supplied from the anode exhaust, the effluent stream from the oxidation unit, or a combination thereof allows the operating temperature of the first reformer to rise above the adiabatic condition. Increasing the temperature above the adiabatic condition allows for efficient cracking and/or recombination of the fuel having a carbon number greater than four. The use of liquid fuel allows one fuel to be used by more than one H8979.doc -14- 201112487 power supply. For example, diesel fuel can be used on board to power a refinery carbonate fuel cell and engine. Hydrogen is added to the first recombiner through the mixing of the anode exhaust and the (iv) feed. The recycling of hydrogen eliminates the need for a separate source of hydrogen for the thermal cracking of the liquid feed. Although some hydrogen is consumed, (iv) is produced after the recombination of the cracked hydrocarbon. The integration of the recombiner with the high temperature hydrogen separation unit allows the system to produce substantially all of the hydrogen required by the methods. Recombination and/or hydrocracking of liquid fuels produces more carbon dioxide per mole of hydrogen produced. This is because the hydrogen to carbon ratio of fuels with a carbon number greater than 6 (eg, oil and naphtha) is lower than A hydrogen to carbon ratio of a fuel having a carbon number of less than 6 (e.g., 'decane). The hydrogen produced per mole produces more carbon dioxide to allow substantially all or all of the carbon dioxide required to produce the shale carbonate fuel cell from the liquid fuel. Producing carbon dioxide in this manner eliminates or reduces the need to use the anode gas and/or a portion of the helium gas to be used as a fuel for the heat inefficient combustion burner to produce carbon dioxide. In the process set forth herein, 'excess hydrogen is produced' which allows hydrogen to be recycled through the system. Two places. Therefore, the fuel cell voltage is maximized. The method also utilizes the following steps to achieve higher electrical power density than in the prior art: using a carbon dioxide rich method in the method described herein to maintain the path length at the cathode electrode of the electrochemical reaction over the entire path length of the cathode The system disclosed in the electric power density and/or electricity described herein produces - more 'the oxidized carbon in a smelting carbonate fuel cell floods the cathode to make the available carbon dioxide concentration throughout the cathode 148979.doc - 15· 201112487 The flow of the oxidant gas and the partial pressure of the cathode portion of the fuel cell is higher than the partial pressure of the carbon monoxide of the molten carbonate fuel. Nine': the battery is made in the majority of the anode portion of the molten carbon dioxide pool or all of the partial carbon dioxide pools compared to the system disclosed in the prior art, ~ Le 藉 by the method described herein by utilizing - Changqi fuel and minimizing, rather than maximizing, the fuel consumption per pass of the fuel cell produces a more electrical power density in a molten carbonate fuel cell system. The minimization is achieved by catalyzing the separation and recirculation of hydrogen captured by the fuel exhaust of the fuel cell (eg, anode exhaust) and feeding the hydrogen from a feed and recirculation at a selected rate to minimize each Fuel utilization rate of the pass. In the method set forth herein, the anode is flooded with hydrogen over the i path length of the anode of the molten carbonate fuel cell so that the concentration of hydrogen available at the anode electrode of the electrochemical reversal is throughout the length of the anode path. Maintain at the high level. Therefore, the electric power density of the fuel cell is maximized. The use of primary hydrogen or preferably almost all nitrogen in the process maximizes the electrical power density of the fuel cell system because chlorine is commonly used in other oxidizable compounds in a smelting carbonate fuel cell system (eg, , carbon monoxide) has a significantly larger electrochemical potential. The methods set forth herein also maximize the electrical power density of the battery system by minimizing, rather than maximizing, the fuel utilization per fuel path of the fuel in the molten sulphonate fuel cell. Minimizing the fuel utilization per pass to reduce the concentration of carbon dioxide and oxidation products (specifically water) throughout the length of the anode path of the fuel cell such that the length throughout the anode path is maintained 148979.doc -16 - 201112487 One to the hydrogen concentration. The fuel cell provides a high electrical power density due to the presence of excess hydrogen along the entire anode path length of the fuel cell relative to the electrochemical reaction at the anode electrode. In one method for achieving a high fuel utilization per pass (eg, greater than 60% fuel utilization), the concentration of carbon dioxide and oxidation products may include greater than fuel before the fuel has traveled through even half of the fuel cell. 40% of the flow. In a fuel cell exhaust, the concentration of carbon dioxide and oxidation products can be a multiple of the hydrogen concentration such that the electrical power provided along the anode path can be significantly reduced by the amount of fuel supplied to the fuel cell as it passes through the anode. The inventive method allows a molten carbonate fuel cell to operate at a pressure of about 0.1 MPa (10 atm) or less than about 0.1 MPa (l atm) and provides a power density of at least 012 w/cm 2 and/or a battery of at least 800 mV Voltage. The methods described herein are also highly efficient because hydrogen and carbon dioxide that are not utilized in the fuel cell to produce electricity are continuously recirculated through the fuel cell system. This achieves a high electrical power density relative to the lowest heating value of the fuel by solving the problems associated with the loss of hydrogen and/or carbon dioxide energy from the battery that is not converted to electrical energy. The system set forth herein allows a hydrogen rich fuel stream and a carbon dioxide rich fuel stream to be provided to the molten carbonate fuel cell while minimizing the amount of hydrocarbons provided to the fuel cell, as compared to conventional systems. The system produces an argon-rich argon-containing stream that can be directly introduced into the anode portion of the molten carbonate fuel cell. The system does not require direct coupling to the anode of the molten carbonate fuel cell and/or a recombiner positioned in the anode to ensure sufficient hydrogen production as a fuel for the anode of the fuel cell, in the molten carbonic acid Salt 148979.doc 17 201112487 The removal or elimination of a recombiner or recombination zone in a fuel cell allows the molten carbonate fuel cell to be flooded with hydrogen while supplying a substantial portion of the heat from the anode exhaust to the first recombiner. Fuel cells that have been equipped with internal recombination zones can be used in combination with the systems described herein. Such fuel cells can operate more economically and efficiently than systems disclosed in the art. The use of the fuel cell system set forth in the present invention allows the molten carbonate fuel cell to be operated at a power of 〇i Mpa(i atm). Typically, a molten carbonate fuel cell operates at a pressure from atmospheric pressure to about i Μρ & (ι 〇 (4). Operation at pressures above atmospheric pressure can affect the life of the seal in various portions of the molten carbonate fuel cell. The operation of the molten carbonate fuel cell at or near atmospheric pressure extends the life of the seal in the smelting carbonate fuel cell while generating electricity at a high current density for a given cell voltage and/or power density. In the squares & described herein, each unit of electricity generated by the Yanhai method produces relatively small amounts of carbon dioxide - a first recombiner, a second recombiner, and a: a thermal product of a warm hydrogen separation device and a fuel cell. Reducing and preferably eliminating the need for: providing additional energy to the endothermic recombination reaction in one or both of the recombiners, by providing a hot anode exhaust stream from the fuel cell to the first weight, And the heat generated in the fuel cell is directly transferred to the first weight, and the product of the first recombiner is directly fed into the second/recombination benefit and then The product of the second recombiner is supplied to the high temperature hydrogen device such that the thermal product is reduced (e.g., by combustion) to provide additional energy so as to reduce the amount of oxidation that is produced when the energy is supplied to drive the recombination reaction. 148979.doc • 18· 201112487 By recirculating carbon dioxide from the reformed gas product and subsequently feeding a carbon dioxide containing gas stream to the fuel cell, recirculating the anode exhaust stream through the system and providing a carbon dioxide gas stream to the fuel cell is reduced The amount of carbon dioxide produced by the combustion is required. This recycling increases the electrical efficiency of the process and '= this reduces any carbon dioxide emissions. In addition, the gas stream is separated by self-recombining gas product and then fed to the hydrogen-containing stream to The fuel cell recirculates an anode exhaust stream through the system and provides a hydrogen-rich stream containing one of the molecular hydrogen to the fuel cell to reduce the amount of hydrogen required to be produced by the first recombiner. This recycling boosts the electrical efficiency of the method. In addition, the power density of the molten carbonate fuel cell is improved. The power of the amount can be generated using a fuel cell having a smaller size than a conventional fuel cell. As used herein, unless otherwise indicated, the term "chlorine" refers to molecular hydrogen. As used herein, "Air source" means a compound from which free chlorine can be produced, and t, the hydrogen source may be, for example, a hydrocarbon or a mixture of such compounds or a hydrocarbon-containing mixture such as natural gas. As used herein, when two Or more elements are described as being "operably connected" or "operably coupled", which are defined as being directly or indirectly connected to permit direct or indirect fluid flow between the elements. As used herein, the term "fluid flow" of a gas or a fluid flows as in "operating" "Indirect fluid flow" as used in the definition of "coupled by operation" means that the fluid may be entangled between two defined elements by one or more additional elements 148979.doc -19- 201112487 or one The flow of gas changes one or more aspects of the fluid or gas as it flows between the two defined elements. A state in which a fluid or a gas can be changed in an indirect fluid flow includes physical properties (e.g., temperature or pressure of a gas or a fluid) and or a composition of the gas or fluid. For example, the water is condensed by separating one of the gases or fluids or by a stream of one of the contained steam. As defined herein, "indirect fluid / 'IL activity" does not include a chemical reaction (eg, oxidation) or reduction of one or more elements of a smectic fluid or gas to change the relationship between the two defined elements. The composition of a gas or fluid. As used herein, the term "selectively permeable to hydrogen" is defined as being permeable to molecular hydrogen or elemental hydrogen and impermeable to other elements or compounds such that at most 1%, or at most, non-hydrogen elements or compounds 5% or up to 1% can penetrate substances that are permeable to molecular hydrogen or elemental hydrogen. As used herein, the term "high temperature hydrogen separation unit" is defined as being separated from a gas stream at a temperature of at least 25 Torr (for example, from 3 〇〇〇c to 65 〇β (at a temperature)). A device or device that is effective in the form of hydrogen in the form of a molecule or element. As used herein, the "utilization of hydrogen per pass" of the utilization of hydrogen in a fuel in a molten carbonate fuel cell is defined as relative to For the amount of hydrogen passing through the (four) carbonate fuel cell to the fuel in one of the fuel cells - the amount of hydrogen in the fuel used to generate electricity in the pass. Hydrogen per pass (4) Calculated by: measuring the amount of hydrogen fed to one of the anodes of a fuel cell; measuring the amount of hydrogen in the anode exhaust of the fuel cell; from the measured feed to the 148979.doc •20· 201112487 The amount of hydrogen in the fuel cell fuel minus the measured amount of hydrogen in the anode exhaust of the fuel cell to determine the amount of hydrogen used in the fuel cell; Hydrogen used in the fuel cell The amount is divided by the amount of hydrogen fed to the fuel of the fuel cell. The hydrogen utilization per pass can be expressed as a percentage by multiplying the calculated hydrogen utilization per pass by 1 。. 1 to 3 are schematic views of an embodiment of a system of the present invention for carrying out a method for operating a molten carbonate fuel cell to produce electricity according to the present invention. The fuel cell system 10 includes a molten carbonate fuel cell. 2. A first recombiner 14, a second recombiner 16, a high temperature hydrogen separation unit 18 and an oxidation unit 20. In a preferred embodiment, the second recombiner 丨6, the high temperature hydrogen separation unit 18 and the oxidation unit 20 In one embodiment, the oxidation unit 20 is a catalytic partial oxidation recombiner. In one embodiment, the high temperature hydrogen separation unit 18 is a molecular hydrogen membrane separation unit. In one embodiment, the second The recombiner 16 includes a recombination zone, a high temperature hydrogen separation unit 18, a catalytic partial oxidation recombiner 20, and a heat exchanger 22. The thermal integrated system provides sufficient hydrogen and carbon dioxide for continued operation of the molten carbonate fuel cell. The molten carbonate fuel cell 12 comprises an anode 24, a cathode 26 and an electrolyte 28. The electrolyte 28 is interposed between the anode 24 and the cathode 26 and contacts the anode and cathode. The molten carbonate fuel cell 12 can be a conventional smelting carbonate. The fuel cell and preferably may have a tubular or planar configuration. The molten carbonate fuel cell 12 may comprise a plurality of individual fuel cells stacked together. The individual fuel cells may be electrically connected by interconnection and operatively connected Having one or more gas streams flowing through the anode of the stacked fuel cell and an oxygen containing 148979.doc -21 - 201112 487 agent gas can flow through the cathode of the stacked fuel cell. As used herein, the term " A molten carbonate fuel cell is defined as a single molten carbonate fuel cell or a plurality of fused carbonate fuel cells that are operatively connected or stacked. The anode 24 of the molten carbonate fuel cell 12 can be formed from a porous sintered nickel compound, a nickel-chromium alloy, a lithium-chromium oxide-recorded and/or copper-recorded alloy, or any material suitable for use as an anode of a molten carbonate fuel cell. The cathode 26 of the molten carbonate fuel cell 12 can be formed of a porous sintered material (e.g., nickel oxide, lithium-nickel-iron oxide) or any material suitable for use as a cathode of a molten carbonate fuel cell. A gas stream is fed to the anode and cathode to provide the reactants necessary to produce electricity in the fuel cell stack. The hydrogen containing stream enters the anode 24 and contains an oxidant stream into the cathode 26. Electrolyte section 28 is positioned in the fuel cell to block the flow of hydrogen containing gas into the cathode and to prevent the flow of oxidant (oxygen and carbon dioxide) from entering the anode. The oxidant-containing gas stream comprises one or more streams containing oxygen and/or carbon dioxide. The electrolyte section 28 directs carbonate ions from the cathode to the anode to achieve oxidizable compounds (eg, hydrogen and, optionally, carbon monoxide) in the anode gas stream. An electrochemical reaction at one or more anode electrodes. Electrolyte section 28 can be formed from a molten salt of an alkali metal carbonate, an alkaline earth metal carbonate, or a combination thereof. Examples of the electrolyte material include a porous material formed of sodium lithium carbonate, lithium carbonate, sodium carbonate, sodium lithium carbonate, sodium lithium carbonate, and lithium potassium carbonate. The fuel cell 12 is configured to allow each of the _ >&&& Λ 干 dry δ nitrogen stream to flow from the anode inlet 30 through the anode 2 4 and out of the anode drain 萆屮 a . ^ J- ΙΛ AOT ^ potassium 矾 exports 32. The hydrogen-containing gas stream is contacted from the anode into the 148979.doc -22- 201112487 port 30 to the anode exhaust gas exit σ32 on the anode path length of one or more anode electrodes. In one embodiment, a gas stream containing molecular hydrogen (hereinafter referred to as "hydrogen" "IL") or a hydrogen source is fed through line 34 to the anode inlet 30. A throttle valve 36 can be used to select and control the flow rate of the hydrogen-containing stream to the anode inlet 30. In a preferred embodiment, the hydrogen is fed from the high temperature hydrogen separation unit 18 to the fuel cell at ▲ anode 24' λ. The high temperature hydrogen separation unit is a thin film unit, as explained in detail below. In one embodiment, the hydrogen-containing stream can comprise at least 〇6, or at least 0-7, or at least 〇.8, or at least 〇9, or at least 〇95 or at least 0.98 mole fraction hydrogen. Feed to the cathode - the gas contains an oxidant. As referred to herein, "oxidant" refers to a compound that can be reduced by reaction with molecular hydrogen. In certain embodiments, the oxidant-containing gas fed to the cathode comprises oxygen, carbon dioxide, an inert gas, or a mixture thereof. In one embodiment, the deuterium containing gas system - the oxygen containing stream is combined with one of the carbon dioxide containing gas streams or an oxygenated / oxidizing slave. In a preferred embodiment, the oxygen-containing gas fed to the cathode is an air or oxygen-rich line that has been mixed with sufficient carbon dioxide such that the molar ratio of carbon dioxide to oxygen is at least 2 or at least 2.5. 3 The oxidant gas may flow from the cathode inlet 38 through the cathode 26 and then out through the cathode exhaust outlet 4G. The oxidant-containing gas contacts one or more cathode electrodes from the cathode inlet 38 to the cathode exhaust outlet 4's cathode path length. In an implementation, the oxidizing body can flow convectively with respect to the flow of hydrogen containing gas to one of the anodes 24 of the fuel cell 12. In one embodiment, the oxidant-containing gas stream is passed through line 44 from the oxidant gas source 4848 to the cathode inlet 38. The throttle valve can be used to select and control the rate at which the gas stream is directed to the cathode 26. In some embodiments, the oxidant-containing gas is provided by an air compressor. The oxidant-containing gas stream can be air. In one embodiment, the oxidant-containing gas can be pure oxygen. In one embodiment, the oxidant gas stream may be oxygen and/or carbon dioxide-rich air containing at least 13% by weight oxygen and/or at least 26% carbon dioxide. The flow of air and/or carbon dioxide is controlled in a preferred manner such that the molar ratio of carbon dioxide to molecular oxygen in the air is at least about 2 or at least 2.5. In one embodiment, β is supplied to the oxidant-containing gas stream by a carbon dioxide-containing gas stream and an oxygen-containing gas stream. The carbon dioxide stream and the oxygen containing stream can come from two separate sources. In the preferred embodiment, most or substantially all of the carbon monoxide used to melt the carbonate fuel cell 12 is derived from k 〃 IL supplied to the first recombiner μ. The carbon dioxide containing gas stream is fed from the carbon dioxide source to the cathode human σ 38 through line 44. The carbon dioxide containing gas stream provided to fuel cell 12 may be fed to the same cathode inlet 38 as the oxygen containing stream, or may be mixed with the oxygen containing stream prior to feeding to cathode inlet 38. Alternatively, the carbon dioxide containing gas _L can be supplied to the cathode 26 through a separate cathode inlet. In the case of the vehicle, the carbon dioxide stream is supplied from the high/anolithic knife away from the unit 丨8 to the cathode % of the fuel cell 丨2 via lines 48 and 44. As explained herein, oxygen can be supplied via the official line 44 to Cathode 26 of fuel cell 12 » Prior to feeding to cathode 26 and/or anode 24, the gas fed to the cathode and/or anode (no flow - one or more streams) may be in a heat exchanger 22 or The heat is heated by other hot fathers, preferably by exchanging heat with the oxygen-depleted cathode exhaust stream exiting the cathode exhaust port 40 and connected to the hot parent exchanger 22 via line 50. 148979.doc • 24· 201112487 In the method of the month of the month, the helium-containing gas stream is mixed with the oxidant at one or more of the anode electrodes of the flash carbonate fuel cell 12 to generate electricity. Preferably, the oxidant is derived from the reaction of carbon dioxide and oxygen flowing through the cathode 26 and directed through the carbonate ions of the electrolyte of the fuel cell. The hydrogen-containing gas stream is mixed with the oxidant at one or more anode electrodes of the fuel cell by feeding a hydrogen-containing gas stream and/or an oxidant-containing stream 11 to the fuel cell 12 at a selected independent rate, as further detailed below Discussion. Preferably, the hydrogen-containing stream and the oxidant are mixed at one or more anode electrodes of the fuel cell to at least (M w/cm 2 , or at least 5l 5 w/cm 2 , or at least 0.2 W/cm 2 ) at 1 bar. , or at least 33 W/cm2 or at least 〇6 goods/(^2 one of the electrical power density produces electricity. It can be obtained at higher pressures and/or by using an oxidant-rich gas stream (eg, oxidant-rich air) High Power Density The molten carbonate fuel cell 12 is operated at a temperature that enables carbonate ions to be effective from the cathode 26 across the electrolyte portion 28 to the anode 24. It can be from 550t to 70 (TC or from 600t; to 65 ( The molten carbonate fuel cell 12 is operated at a temperature of rc. At one or more of the anode cells, hydrogen is exothermicly reacted with the oxidation of the carbonate ions. The heat of the reaction produces heat required to melt the carbonate fuel cell 12. The temperature at which the molten carbonate fuel cell is operated can be controlled by several factors including, but not limited to, adjusting the feed temperature and feed flow of the hydrogen-containing gas and the oxygen-containing gas. Excess hydrogen is minimized due to hydrogen utilization. Feed to the system and not Hydrogen may partially cool the smelting carbonate fuel cell by carrying excess heat to the first recombiner. Adjusting the flow of carbon dioxide and/or the flow of oxidant-containing stream to provide a molar ratio of carbon dioxide to molecular oxygen Maintained at 148979.doc •25· 201112487 About 2 places need sufficient oxidant gas to achieve about 13 to 2.0 times the amount of molecular oxygen required to react with the part of the hydrogen used by the anode. The excess of oxygen-depleted air or oxidant-containing emulsion exiting the cathode exhaust may carry a significant amount of heat from the molten carbonate fuel cell. A hydrogen-containing stream, as described below, is supplied from the high temperature hydrogen separation unit 18 to the melt. The carbonate, before the anode 24 of the battery 12, can be lowered by heat recovery (e.g., through the hot parent exchanger 22) to reduce the temperature of the hydrogen-containing stream supplied to the anode of the (iv) carbonate fuel cell. __High pressure: The oxidized carbon flow is supplied from the door/dish hydrogen knife off device 18 to the cathode 26 of the flash carbonate fuel cell 丨2, which can be reduced by heat recovery (for example, through the heat exchanger 22) Provided to The temperature of the high pressure carbon dioxide stream of the cathode of the carbonate fuel cell is provided by the heat recovery (eg, through the heat exchanger 22) prior to providing the effluent stream from the catalytic partial oxidation recombination (IV): the molten carbonate fuel cell cathode To reduce the temperature of the effluent stream. The waste heat from the fuel cell can be used to heat one or more of the streams utilized in the system. If necessary, it is known in the art for cooling molten carbonate fuel. Any supplemental system can be used to control the temperature of the molten carbonate fuel cell. In a consistent embodiment, 'the temperature of a hydrogen-containing gas stream is controlled to at most 55 Torr. One of the temperatures is to operate the molten carbonate fuel cell. It is maintained in a range from 550 ° C to 700 ° C, and is preferably maintained from 600 ° C to 65 ° C. (In one of the ranges. In one embodiment, the oxidant-containing gas stream fed to the cathode may be heated to at least 15 Torr or from 15 ° C to 350 before feeding to the cathode 26. (1: 148979.doc -26-

201112487 shirt degree. In one embodiment, when an oxygen-containing gas is used, the degree of a helium-containing gas is controlled to be from i50.匚 to a temperature of 35 〇艽. To initiate operation of the fuel cell 丨2, the fuel cell is heated to its operating level - sufficient to melt the electrolyte salt to allow the carbonate ion to flow at a temperature as shown in Figure 1, which can be oxidized by catalytic partial oxidation. A hydrogen-containing gas stream is produced in the vessel 2 and the hydrogen-containing stream is fed to the anode 24 of the molten slave brine fuel cell 12 through lines 52 and 34 to initiate operation of the molten carbonate fuel cell. In the presence of a conventional partial oxidation catalyst, one of the hydrocarbon streams described below, including a hydrocarbon stream, or a different hydrocarbon stream (eg, enriched in natural gas) is combusted in the catalytic partial oxidation reformer 20. One of the fuel streams) and an oxidant-containing gas to produce a hydrogen-containing _y in the catalytic partial oxidation reformer 2, and a quantity of oxygen in the oxidant-containing gas fed to the catalytic partial oxidation reformer 20 relative to Substoichiometry of the amount of one of the hydrocarbons in the hydrocarbon stream. The flow of the hydrogen containing stream can be controlled by valve 6〇. As shown in FIG. 2, the fuel cell is heated by generating a hydrogen-containing stream in the oxidation unit 2〇 and feeding the hydrogen-containing stream through the s-lines 96, 104, and 34 to the anode 24 of the molten carbonate fuel cell. To its operating temperature. The rate at which the hydrogen containing stream is fed from the oxidation unit 20 to the anode 24 via lines 96, 1 () 4 is controlled by a three-pass 1G2. The portion from the heat of the hydrogen containing stream may pass through the hot parent exchanger 98 via line 96 to provide heat to the first reformer &/or to the hydrocarbon stream comprising the hydrocarbon of the first reformer. Referring to Figures 1 and 2, the fuel fed to the catalytic partial oxidation reformer 2 can be a liquid or gaseous hydrocarbon or hydrocarbon mixture, and is preferably provided to the first recombination 148979.doc • 27-201112487. The hydrocarbon flow of the smoke is the same. Fuel can be fed via line 62 to catalytic partial oxidation reformer 20. In a practical example, the natural gas and/or hydrogen-rich feed from hydrogen source 64 is fed to the fuel that catalyzes partial oxidation of reformer 20. The oxidizing agent fed to the catalytic partial oxidation reformer 2G may be pure oxygen, air or oxygen-enriched air (hereinafter referred to as "oxidant-containing gas"). Preferably, the oxidant-containing gas is difficult to air. The oxygen butterfly should be fed to the catalytic partial oxidation reactor 20 such that the amount of oxygen in the oxidant is in a substoichiometric amount relative to the hydrocarbon fed to the catalytic partial oxidation recombination. In a preferred embodiment, the oxidant-containing gas is fed from oxidant source 42 to catalyzed 4-knife oxidative reformer 2 through line 56. The valve 58 controls the rate at which the oxidant-containing gas (air) is fed to the catalytic partial oxidation recombiner 2G and/or the cathode 26 of the fuel cell 12. In the example, the oxygen-depleted cathode row can be removed by exiting the cathode exhaust port. The gas stream exchanges heat to heat the oxidant-containing gas into the catalytic partial oxidation reformer 2 . In the valued partial oxidation recombination (IV), a hydrogen-containing stream is formed by burning a hydrocarbon and an oxidant in the presence of a conventional partial oxidation catalyst, wherein the oxidant is in a substoichiometric amount relative to the hydrocarbon. The hydrogen-containing stream formed by the contact of the hydrocarbon with the oxidant in the catalytic partial oxidation recombiner 2 is contained in the fuel cell anode 24 by contact with carbonate ions at one or more of the anode electrodes. Compound. The argon-containing gas stream from the catalytic partial oxidation reformer 20 preferably does not contain a compound which oxidizes one or more of the anode electrodes 24 of the fuel cell 12.

The hydrogen-containing gas stream formed in the catalytic partial oxidation reformer 20 is hot and may have at least 700 ° C, or from 700. (: to 1100. (or from 800 ° C to 1000 ° C 148979.doc -28 * 201112487 one of the temperatures. In the method of the invention, the hot hydrogen stream from the catalytic partial condensing recombiner 20 is used to initiate The firing of the molten carbonate fuel cell 丨2 is preferred because it allows the temperature of the fuel cell to rise almost instantaneously to the operating temperature of the fuel cell. In one embodiment, when the fuel cell is started In operation, heat may be exchanged between the hot hydrogen containing gas from the catalytic partial oxidation reformer 20 and one of the feed to the oxidant containing gas in the heat exchanger 22. Referring to Figure 1, the valve 60 can be used to adjust the catalysis. The heat of the partial oxidation recombiner 2 contains a flow of hydrogen into the fuel cell 12, while the hydrogen-containing stream is fed to the anode 24 by opening the %, and the hydrogen from the high-temperature hydrogen separation unit 18 is initially started. The flow of the stream can be followed by closing the valve 6 while reducing or stopping the flow of the hydrocarbon feed permeate line 62 and the oxidant feed permeate line 56 to the catalytic partial oxidation recombiner 20. Referring to Figure 2, the valve 102 can be used to adjust the hot hydrogen containing stream. By pipeline The autocatalytic partial oxidation recombiner 20 flows into the fuel cell 12 while feeding the hydrogen containing stream to the anode 24 by opening the valve 36. The valve can be closed after generating a hydrogen containing stream from the high temperature hydrogen separation unit 18. 1〇2, while reducing or stopping the flow of the hydrocarbon feed permeate line 62 and the oxidant feed through line 56 to the catalytic unit = 1 recombination (d). Then, the fuel cell can be operated in accordance with the method of the present invention. Λ Three-way throttle valve 1G2 controls the flow of the effluent autocatalytic partial oxidation recombiner to the anode 24 or cathode 26. During the start-up, the effluent from the catalytic partial oxidation group 20 is rich in hydrogen and therefore is worn through the pipeline. After passing through the heat exchanger 98, the effluent is directed to the anode (10) via line 1〇4. After the initiation of 148979.doc -29- 201112487 and if the catalytic partial oxidation recombiner 2G is used to generate carbon dioxide for the cathode The throttle valve 1〇2 controls the flow of the effluent from the catalytic partial oxidation recombiner 2 to the cathode 26 via line 96. In another embodiment, 'the introduction of the hydrogen-containing stream to the fuel line via line 66 Prior to 12, the operation of the fuel cell can be initiated by a hydrogen-generating gas stream from a hydrogen source 64 that can be passed through a generator (not shown) to bring the fuel cell to its operating temperature as shown in Figure 2. Hydrogen source M can be a storage tank capable of receiving hydrogen from the high temperature hydrogen separation unit 18. The hydrogen source can be operatively coupled to the fuel cell to permit introduction of a hydrogen-generating gas stream into the anode of the carbonate fuel cell. The generator heater indirectly heats the hydrogen-combustion gas stream from 750 Torr to 1 Torr (rc temperature). Alternatively, the generator heater can be supplied to the heater by hydrogen from the hydrogen source 64. It does not completely burn to provide hydrogen. The starting heater can be an electric heater or can be a combustion heater. After the operating temperature of the fuel cell is reached, the flow of hydrogen to the fuel cell can be shut off by the -valve, and the hydrogen-containing gas stream can be introduced by opening a valve from the hydrogen generator to the anode of the fuel cell. The fuel cell is used to start the operation of the fuel cell. In one embodiment, the first recombiner 14 comprises a catalytic partial oxidation recombination unit which is used to provide hydrogen to the molten carbonate fuel cell upon actuation. The first-recombiner 14 can include one or more catalyst beds that allow the first recombiner to be used for autothermal recombination and then for steam recombination when the (d) carbonate fuel cell has reached operating temperature. Once the fuel cell 12 has begun to operate, both the cathode 26 and the anode 24 dissipate the exhaust gas 1 from the exhaust of the cathode 26 and the anode 24 and are from the exhaust. • 30-148979.doc

The heat of 201112487 can be combined with other units to create a thermal integrated system that produces all of the fuel (hydrogen) and oxidant (carbonate ions) necessary for operation of the fuel cell. As shown in FIG. 1 and FIG. 2, the method described in the present invention utilizes a system-hydrogen separation and separation device, a molten carbonate fuel cell 12, a first recombiner 14, and a second recombiner. 16 and (in certain embodiments) catalyzing the partial oxidation recombiner 20. The high temperature ammonia separation unit 18 includes one or more high temperature hydrogen separation membranes 68 and is operatively coupled to the molten carbonate fuel cell 12. The high temperature hydrogen separation unit 18 supplies a hydrogen-containing stream mainly containing molecular hydrogen to the anode 24 of the fuel cell 12, and an exhaust system from the anode of the molten carbonate fuel cell 12 is supplied to the first reformer 14. The first recombiner 14 and the second recombiner 16 can be a unit or two operatively compliant units. The first-recombiner 14 and the second recombiner 16 may comprise one or more recombination zones. In one embodiment, the first recombiner 14 and the second recombiner 16 comprise a unit of a first recombination zone and a second recombination zone. A hydrocarbon stream comprising hydrocarbons is provided via line 62 to first reformer 14 and the anode exhaust is mixed with hydrocarbons. The method is a thermal assembly wherein the anode exhaust gas from the exothermic molten carbonate fuel cell 12 can be directly driven in the first recombiner and/or with the hydrocarbons supplied to the first recombiner hydrocarbon stream. The heat of the endothermic recombination reaction in a reformer 14. In one embodiment, a portion of the heat from the anode exhaust is mixed with a hydrocarbon in a heat exchanger, the heat exchanger being located in the first reformer or operatively coupled to the first recombination. As shown in Figure 2, the additional heat to the first reformer 14 can be provided from a hot effluent stream from one of the catalytic partial oxidation reformers 20. At least a portion of the hydrocarbons from the hydrocarbon stream are lysed and/or recombined in a first recombination 148,979.doc •31·201112487, to produce a feed stream to one of the second reformers 16 via line 70. The second recombiner 16 is operatively coupled to the high temperature hydrogen separation unit 18 and the high temperature hydrogen separation unit produces at least a portion, a majority, at least 75% by volume, or at least 90% by volume or substantially all of the anode entering the smelting carbonate fuel cell 12. 24 hydrogen-containing gas. The high temperature hydrogen separation unit can be positioned after the second reformer and before the molten carbonate fuel cell 12. In a preferred embodiment, the high temperature hydrogen separation unit 18 is a membrane separation unit that is part of the second reformer 16. The still temperature hydrogen separation unit 18 separates hydrogen from the recombined product. The separated hydrogen is supplied to the anode 24 of the molten carbonate fuel cell 12. In one embodiment of the method, the hydrocarbon stream contains one or more of any vaporizable hydrocarbons which are liquid at 2 atmospheres under atmospheric pressure (as appropriate for oxygenation) and up to 4 atmospheres at atmospheric pressure. Hey. (The temperature can be evaporated. These hydrocarbons can include, but are not limited to, 5 〇. 〇 to 36 〇. (: a fraction of the boiling point of petroleum, such as naphtha, diesel, jet fuel, gasoline and kerosene The hydrocarbon stream may optionally contain some hydrocarbons in the gaseous state, such as decane, ethane, propane or other compounds containing from one to four carbon atoms in a gaseous state at 251. In one example, the hydrocarbon stream contains hydrocarbons having a carbon number ranging from five to twenty-five. The hydrocarbon stream can be fed to the first recombiner Μ month j '.'I treatment and/or in a hot parent converter Heating in 7 2 to remove any material that can adversely affect any of the catalysts used to convert higher molecular weight hydrocarbons to lower molecular weight hydrocarbons in the first reformer. For example, the hydrocarbon stream can have been experienced a series of treatments to remove metal, sulfur and/or nitrogen compounds. Preferably, in the embodiment, the plume contains at least 〇5, or at least 〇6, 148979.doc

-32- 201112487 or a hydrocarbon containing at least five, or at least six or at least seven carbon atoms, at least 0.77 or at least 0.8 mole fraction. In one embodiment, the hydrocarbon stream is calcined. In a preferred embodiment, the hydrocarbon stream is a diesel fuel. In one embodiment of the method the hydrocarbon stream contains at least 2% by volume, or at least 50% by volume. Or a natural gas mixture of at least 80% by volume of carbon dioxide. If necessary, the natural gas has been treated to remove hydrogen sulfide. In one embodiment, a hydrocarbon stream having at least 20% by volume of carbon dioxide, at least 5% by volume of carbon dioxide, or at least 70% by volume of carbon dioxide can be used as a fuel source. In one embodiment, the hydrocarbon stream can be provided to the first reformer 14 at a temperature of at least 150 ° C, preferably from 2 ° C to 400 ° C, wherein the hydrocarbon stream can be in a heat exchanger Heat to a desired temperature as explained below. The temperature at which the hydrocarbon stream is fed to the first reformer 14 can be selected to be as high as possible to evaporate the hydrocarbons without producing coke. The temperature of the hydrocarbon stream may be from 15 (TC to 400. (the range of: another option is (but less preferred), and if the sulfur content of the hydrocarbon stream is low, it may be lower than, for example, 150 ° C. The hydrocarbon stream is fed directly to the first reformer 14 at a temperature without heating the hydrocarbon stream β as shown in Figure 1, which can be passed through one or more heat exchangers 72 to heat the feed. The hydrocarbon stream can be heated by exchanging heat with a cathode exhaust stream that is separated from the cathode 26 of the molten carbonate fuel cell 12 and fed to the heat exchanger via line 74. The throttle valves 76 and 78 can be adjusted by adjusting The rate at which the cathode exhaust stream is fed to the heat exchangers 72 and 22 is controlled. In a preferred embodiment, a separate anode exhaust stream is fed via line 8 to one or more recombinations of the first reformer 14. In the zone, the rate at which the anode exhaust stream is fed to the first recombiner 丨4 can be controlled by adjusting the section 148979.doc • 33· 201112487 flow valve 82. The anode exhaust gas temperature can be from about 500. (: to Approximately 70 (the range of TC, and preferably about 650.): The anode exhaust stream contains hydrogen, steam, and from the feed to the fuel cell 12. The oxidized reaction product of the fuel of the electrode 24 and the unreacted fuel. In one embodiment, the anode exhaust stream contains at least 0.5, or at least 〇6 or at least 莫7 mole fraction of hydrogen. Feed to the first recombiner 14. Or hydrogen in the anode exhaust stream of the recombination zone of one of the first reformers can help prevent coke from enthalpy in the first reformer. The anode exhaust stream contains self-destruction. 〇〇1 to about 〇.3, or from 0.001 to about 0.25 or from 〇〇1 to about 莫2 mole fraction of water (as steam). In addition to hydrogen, present in the feed to the first recombiner 14 or The vapor in the anode exhaust stream of the recombination zone of the first group can also help prevent the formation of coke in the first reformer. The anode exhaust stream can contain sufficient hydrogen to inhibit coking and is sufficient The steam is used to recombine a majority of the hydrocarbons in the to 15 , hydrogen and carbon monoxide. Therefore, less steam may be required in the first reformer and/or the second reformer to recombine the hydrocarbons. Line 84 feeds steam to the first recombiner 14 or a recombination zone of the first recombinator to The weight of the recombiner or the first recombiner, and the hydrocarbon stream in the zone is mixed. The steam may be fed to the first recombiner 14 or a recombination zone of the first recombiner to inhibit or prevent coke in the first a reconstitution benefit is formed and optionally used in the recombination reaction achieved in the first recombiner. In an embodiment, steam is fed to the recombination zone of the first recombiner 14 at a rate, The molar ratio of the total I 添加 added to the first recombiner is at least twice or at least three times that of the carbon 148979.doc -34· 201112487 added to the hydrocarbon stream of the first recombiner. The total steam to the first reformer can include steam from the anode exhaust, steam from an external source (e.g., through sound line 84), or a mixture thereof. Providing at least 2:1, or at least 25:1, or at least 3:ι or at least 3.5:1 in a recombination zone of the first recombiner 14 or the first recombinator, a steam to carbon molar ratio can be used to inhibit The formation of coke in the first recombiner. The throttle valve 86 can be used to control the rate at which the vapor is fed through the line 84 to the recombiner or one of the recombination zones of the first recombiner. Since the helium anode exhaust contains a large amount of hydrogen, less coking tends to occur during recombination. Thus, the amount of optional steam fed to the first reformer 14 can be significantly less than the amount of steam used in conventional recombination units. The steam can be at least 125. (:, preferably from 150 ° C to 3 〇〇. (: one at a temperature to the first recombiner 14, and may have a pressure from one 肘 1 肘 to 〇 5 Mpa ' preferably has equal to or low The pressure-pressure of the anode discharge U pressure fed to the first-recombiner is as described herein (4). The high-pressure water having a pressure of up to 1.0 MPa, preferably 1. 5 MPa to 2.0 MPa can be heated by heating. The steam is generated by transferring the high pressure water through the heat exchanger 9 through the official line 88 to be heated by exchanging heat with the cathode exhaust gas which has been fed through the heat exchanger 72 through the heat exchanger 72 at the cathode exhaust gas. The high pressure water is formed to form a high pressure steaming "" alternatively, the cathode exhaust gas can be directly fed to the heat exchanger column (not shown) or one or more heat exchangers. After exiting the heat exchanger 9 or the final heat exchanger, the high pressure steam can then be fed via line 92 to line 84. The squeezing pressure can be expanded by passing through an expander. The high pressure steam is depressurized to the desired pressure and then fed to the first recombiner. Alternatively, it can be passed through 148979.doc • 35- 201112487 - One or more heat exchangers 90 feed low pressure water and deliver the resulting steam to the first reformer 14 to produce steam for use in the first recombiner. The high pressure steam π that is not utilized in the vessel 14 or the second reformer 16 can be expanded by other power plants (e.g., a turbine (not shown)) with any unused pressurized carbon dioxide stream or, as the case may be, without the high pressure carbon dioxide stream. The power source can be used to generate electricity and/or electricity other than electricity generated by the fuel cell. The power generated by the power source and/or fuel cell can be used to power compressor 94 and/or any method used in the method of the present invention. Other compressor power supplies. The hydrocarbon stream, the optional steam, and the anode exhaust stream are at a first recombiner 14 or the first temperature at a temperature that is not effective for vaporizing any hydrocarbons in vapor form and cracking the hydrocarbons to form a feed. One of the recombiners is mixed and contacted with a recombination catalyst. The recombination catalyst can be a conventional recombination catalyst and can be any catalyst known in the art. Typical recombination catalysts that can be used include Restricted to the νπι group transition metal 'specifically nickel and one of the carriers or substrates which are inert under high temperature reaction conditions. Suitable inert compounds for use as a carrier for the temperature recombination/hydrocracking catalyst include, but are not limited to, α- Alumina and cerium oxide. In a preferred embodiment, the 'hydrocarbon stream, anode venting, and optional steam are from about 500 ° C to about 650 ° C or from about 550 ° C to 60 (at one TC temperature) A catalyst mixes and contacts 'all of the heat necessary for the recombination reaction to be supplied by the anode exhaust. In one embodiment, the hydrocarbon stream, optional steam and anode exhaust stream are at least 400 ° C, or from 450 ° C to 650 ° C or from 500 ° C to 600. (: at one of the ranges of temperature mixed with a catalyst and contact. 148979.doc • 36- 201112487 The anode exhaust stream fed from the exothermic molten carbonate fuel cell 12 is supplied to the first recombiner 14 or the heat of the recombination zone of the first recombiner to drive the endothermic heat in the recombiner Cleavage and heavier and react. The anode exhaust gas stream fed from the smelting carbonate fuel cell 12 to the first recombiner 14 and/or the recombination zone of the first recombiner is extremely hot, having a temperature of at least 5 Torr (Tc - usually having 55 (TC to 700. (or: from 60 (rCi65〇t temperature). The heat transfer from the molten carbonate fuel cell 12 to the first recombiner 14 or the recombination zone of one of the first recombiners is quite effective, This is because the thermal energy from the fuel cell is contained in the anode exhaust stream and is transferred to the first recombiner 14 or one of the first recombiners by directly mixing the anode exhaust stream with the hydrocarbon stream and steam. A mixture of a hydrocarbon stream, an optional vapor, and an anode exhaust stream. In one preferred embodiment of the method set forth herein, the anode exhaust stream is provided from a mixture of a hydrocarbon stream, an optional vapor, and an anode exhaust. Producing at least 99% or substantially all of the heat required for the feed. In a particularly preferred embodiment, no other heat source other than the anode exhaust stream is provided to the first reformer 14 to convert the hydrocarbon stream to feed. In an embodiment, the anode exhaust stream, hydrocarbon stream, and optional steam are in The pressure of a recombiner 14 in contact with the recombination catalyst may range from 0.07 MPa to 3. 〇 MPa. If high pressure steam is not fed to the first recombiner 14, then the anode exhaust stream, hydrocarbon The stream and optional low pressure steam may be contacted with the recombination catalyst in the first reformer at a pressure at the lower end of the range (typically from 0.07 MPa to 0.5 MPa or from 0.1 MPa to 〇_3 a). Steam '々-recombiner 14, the anode exhaust stream, hydrocarbon stream and steam may be at the higher end of the pressure range (typically from 1.0 MPa to 3.0 MPa or from 1.5 MPa to 148979.doc -37 to 201112487 2.0 MPa) Contact with the recombination catalyst. The second recombiner 14 of Figure 2 is heated to above 63 藉 by exchanging heat with the effluent from the catalytic partial oxidation recombiner 20 via line 96. 〇, or from 650 ° C To 900. (: or from 700. (: to 8 〇〇. 温度 temperature. Line % is operatively coupled to heat exchanger 98. Heat exchanger 98 may be part of line 96. Heat exchanger 98 may be located a recombiner 14 or connected to the first recombiner to allow heat exchange with the hydrocarbon stream entering the first recombiner. The throttle valve 100 and the two-way throttle valve 1 〇 2 are adjusted to control the rate at which the effluent is fed from the catalytic partial oxidation recombiner 20 to the first reformer 14. At least 500 ° C, or from 55 〇 to 950 ° C, or from 6 〇〇. (: to 80 (rc or from 65CTC to 750t: at one temperature in contact with the hydrocarbon stream in the first - recombiner 14, pyrolysis, catalyst and anode exhaust stream can be cracked and / or Recombining at least a portion of the hydrocarbons and forming a feed. The hydrocarbons in the cracked and/or reformed hydrocarbon stream reduce the number of carbon atoms in the hydrocarbon compound in the hydrocarbon stream, thereby producing a hydrocarbon compound having a reduced molecular weight. In one embodiment, the hydrocarbon stream may comprise a hydrocarbon containing at least 5, or at least 6 or at least 7 carbon atoms, which are converted to a maximum of 4, which may be used as a feed to the second reformer 16, Or hydrocarbons of up to 3 or up to 2 carbon atoms. In one embodiment, the hydrocarbons in the hydrocarbon stream may be reacted in the first recombiner 14 or a recombination zone of the first recombiner such that the feed produced from the first recombiner may be no more than 〇1. Or no more than 〇〇5 or not more than 0.01 mole fraction of a hydrocarbon having four or more carbon atoms. In one embodiment, the hydrocarbons in the hydrocarbon stream may be cracked and/or recombined such that at least 〇7, or at least 〇8, or at least 0·9 or at least 0.95 of the feed produced from the hydrocarbons in the hydrocarbon stream The resulting hydrocarbon is decane at the ear fraction. In one implementation -38- 148979.doc

In the case of S 201112487, the hydrocarbons in the cracked and/or recombined hydrocarbon stream produce hydrocarbons having a feed having at most 1.3, at most 1. 2 or at most 1.1 one of the average carbon numbers. As noted above, the hydrogen and vapor from the anode exhaust stream and the additional steam added to the first reformer 14 inhibit the formation of coke in the first reformer as it is cracked to form a feed. In a preferred embodiment, the relative rates of anode exhaust stream, hydrocarbon stream, and steam feed to first reformer 14 are selected such that hydrogen and vapor in the anode exhaust stream are added to the first recombination via line 84. The steam of the device prevents the formation of coke in the first reformer. In one embodiment, at least 500t:, or from 55〇. (: to 70 (TC or from 6 ° ° C to 65 ° t at a temperature in the first recombiner 14 in the hydrocarbon reactor, steam and anode exhaust gas and the recombination catalyst can also achieve hydrocarbons in the hydrocarbon stream Hydrogen and carbon oxides (specifically, carbon monoxide) are produced by recombination with at least some of the feed produced in the first reformer 14. The amount of recombination can be substantial in the first-recombiner 14 or the first recombination The feed resulting from both cracking and recombination in the recombination zone of the apparatus may contain at least G.G5, or at least 0'1 or at least 0.15 mole fraction of carbon monoxide. The first-recombiner 14 or the first-recombiner may be selected. - the temperature and pressure conditions in the recombination zone, so the first heavy and the residual % are the heaviest, and the feed produced in the benefit is included in the -I state, usually containing 1 to 4 carbon atoms. Light hydrocarbon. In a preferred embodiment, the smoke produced by the first reformer is hydrogen of at least -6, or at least °. 7, or at least two-pole exhaust gas, and if in the first-recombiner The medium implementation includes the reorganization of the process from the beginning to the end. The steam recombination feed also includes the anode from I48979.doc •39 - 201112487 Exhaust flow and, as the case may be, steam from the recombiner steam feed. If a large amount of recombination is achieved in one of the recombination zones of the Tiyi 14 or the βHai-recombiner, it is supplied to the second recombiner 16 from the first The steam produced by the reformer is recombined into (4) carbon monoxide other than carbon monoxide. In the process of the present invention, the 'steam recombination feed is supplied from the first-recombiner to the permeate line 70 to be operatively coupled to the first recombiner. The second recombiner 16. The steam recombination feed exiting the first recombiner 14 can have from 500 C to 650 C or from 550 C to 600. (: One temperature. Steam recombination at the first recombiner I4 will be withdrawn Before the feed is fed to the second reformer 16, the steam recombination exiting the first recombiner can be reduced by exchanging heat in one or more heat exchangers 9A prior to feeding to the second reformer 16. Temperature of the feed. Optionally, the vapor recombination feed is not cooled prior to entering the second reformer. The first recombiner 14 is passed from another source (e.g., as shown in Figure 2, from the catalytic partial oxidation recombiner 20). Steam and/or heat) In the embodiment, the steam recombination feed exiting the first reformer may have a flow rate from 65 CTC to 950 ° C, or from 700 ° C to 900 ° C or from 750 ° C to 800. (: one of the temperatures. The water exchange heat, cooled steam recombination feed to the system and produces steam that can be fed to the first reformer 14 to cool the steam recombination feed, as set forth above. If more than one heat exchanger is utilized 90, the steam recombination feed and water/steam may be fed successively to each of the heat exchangers, preferably in a one-stream flow to cool the steam recombination feed and heat the water/steam. The recombination feed is cooled to a temperature from 150 ° C to 650 ° C, or from 150 ° C to 300 ° C, or from 400 ° C to 650 ° C or from 450 ° C to 550 ° C. 148979.doc -40- 201112487 The cooled steam recombination feed may be fed from heat exchanger 90 to compressor 94, or in another embodiment may be fed directly to second reformer 16. Alternatively, the steam recombination feed, which is selected as (but less preferred) exiting the first recombiner 14 or a recombination zone of the first recombiner, can be fed to the compressor 94 or the second recombination thief 16 without cooling. The compressor 94 is capable of operating a compressor at a high temperature, and is preferably a commercially available StarRotor compressor. The steam reforming feed may have a pressure of at least one of 0.5 MPa and a temperature of from 400 ° C to 800 ° C, preferably from 4 ° C to 650 ° C. The feed may be compressed by compressor 94 to a pressure of at least 5 '5 MPa, or at least [ο MPa, or at least 5 MPa, or at least 2 MPa, or at least 2.5 MPa, or at least 3 MPa to maintain the second recombiner 16 Sufficient pressure in the recombination zone 108. In one embodiment, the steam recombination feed is compressed to a pressure from 0.5 MPa to 6_0 MPa prior to providing the feed stream to the second reformer. The feed, including hydrogen, light hydrocarbons, steam, and, as the case may be, carbon monoxide, is optionally fed to the second reformer 丨6. The steam recombination feed can have a pressure of at least 0 5 MPa and from 400. (: to 800. (:, preferably from one of 400 ° C to 650 ° C. In one embodiment, if necessary, J borrows after the steam recombination feed from the first reformer 14 exits the compressor 94 The temperature of the steam recombination feed from the first recombiner is increased by circulating the portion of the feed through the heat exchanger 9 and/or helium. If necessary, additional steam/fly can be added to the recombination zone 108 of the first recombiner 16 for mixing with the steam heavy feed. In the preferred embodiment, it can be passed through the line 11 The net pressurized water is injected from the water inlet official line 88 into the compressor 94 to add additional steam 148979.doc 201112487 for mixing with the feed when compressing the feed in the compressor. - Example (not shown) The high water may be injected into the feed by mixing the hot water with the feed in the heat exchanger. In another embodiment (not shown), the feed may be passed Pressing water injection in line 11 之前 before or after heat exchanger 90 or before or after transferring the feed to compressor 94 In an embodiment, high pressure water may be injected into: line 70 or injected into compressor 94 or injected into heat exchanger 9A, wherein the compressor or the heat exchanger is not included in the feed. In the system, the pressurized water is heated to form steam by mixing with the steam recombination feed, and the steam recombination feed is cooled by mixing with the water. By = water injected into the steam recombination feed Providing cooling thereto can eliminate the need for heat exchanger 90, preferably limiting the number of heat exchangers used to cool the steam recombination feed to at most one. ...Another option is (but less preferred) High pressure steam may be injected into the recombination zone 1〇8 of the second reformer 16 or injected into the line to the second reformer for mixing with the steam recombination feed. The high pressure steam may be passed through the heat exchanger The steam generated by the high pressure water injected into the system through the water inlet line 88 (by exchanging heat with the feed exiting the first reformer 14) is heated. The sorghum steam can be fed to the second reformer 16 through line U2. The throttle valve 114 can control the steam to the The flow of the second reformer. The high pressure steam may have a pressure similar to the pressure of the feed being fed to the second reformer. Alternatively, the high pressure steam may be fed to line 70 to feed the feed. The feed is mixed with the feed prior to feeding to the compressor 94 so that the mixture of steam and feed can be compressed together to a selected pressure. The high pressure steam can have from 2 〇〇 (: to 5 〇〇. (: • 42, 148979.doc

S 201112487 One of the temperatures. The rate at which high pressure water or high pressure steam is fed to the system can be selected and controlled to provide a quantity of steam effective to produce a hydrogen containing stream to the first reformer feed 14 and/or to optimize the reaction in the reformer. Or the second recombiner 16. By adjusting the throttle valves 116 and 118 (which control the rate at which water is fed to the system) or by adjusting the throttle valves 86, 120 and 114 (which control the steam feed to the first recombiner 14, The rate of the second reformer 16) controls the rate at which steam other than the vapor in the anode exhaust stream is supplied to the first reformer 14. Steam can be supplied to additional components in the system (eg, a turbine). If high pressure water is injected into the second recombiner 16, the throttle valve 120 and 120 can be adjusted to control the rate at which water is injected through the line 112 into the second recombiner. If high pressure steam is injected into the second reformer 16 or injected into line 7A, the throttle valves 114, 116, and 118 can be adjusted to control the rate at which steam is injected into the second reformer 16 or injected into the line 7〇. . The flow of steam can be adjusted to provide at least 2:1, or at least 2:5:1, or at least 31 or at least 3.5:1 molar ratio of steam to carbon. > The steam recombination feed produced by the first reformer and, as the case may be, additional steam is fed to the recombination zone 1G8 of the second recombination 11 16 . The recombination zone may, in fact, contain a recombination catalyst therein. The recombination catalyst can be a conventional & gas weight. and catalyst and can be known in the art. Typical steaming catalysts that can be used include, but are not limited to, transitional metals, specifically recorded. 4, it may be desirable to carry the recombination catalyst on a refractory substrate (or carrier), and the carrier (if used) is preferably an inert compound. The m compound used as a carrier contains elements of Groups III and IV of the periodic table, for example, U8979.doc •43· 201112487

Sl Tl, Mg, Ce & Zr oxide or carbide. The steam recombination feed and, optionally, additional steam are mixed with and contacted with the recombination catalyst in the recombination zone ι 8 at a temperature effective to form a hydrogen-containing and carbon dioxide-recombined product gas. The recombined product gas can be formed by steam reforming the hydrocarbons in the feed. The reformed product gas may also be formed by subjecting steam to a water gas shift reaction with one of the carbon oxides in the feed and/or by steam recombining the feed. In one embodiment, if a large amount of recombination is achieved in the recombination zone of the first recombiner 14 or the first recombiner and the steam recombination feed contains a large amount of carbon monoxide, the second recombiner 16 may serve as a water gas conversion. reactor. The recombined product gas comprises hydrogen and at least one slave oxide. In one embodiment, the reformed product gas comprises a gaseous hydrocarbon 'hydrogen and at least one carbon oxide. The carbon oxides that may be present in the reformed product gas comprise carbon monoxide and carbon dioxide. In one embodiment, the heat from the effluent from the catalytic partial oxidation reformer 2 can be heat exchanged with the steam reforming feed being provided to and/or in the reforming zone 丨〇8. The temperature of one of the effluents from the catalytic partial oxidation reformer 2 can range from 750 ° C to 1050. (:, or from 800 ° C to 1000. (: or from 850 ° C to

900 ° C range. The heat from the effluent heats the recombination zone 108 of the second recombiner 16 to about 500. (: to a temperature of about 850 ° C or from about 55 CTC to 700 ° C. One of the recombination zones 1 〇 8 of the second recombiner 16 may be sufficient to recombine substantially all or all of the feed from the first recombiner 14 To produce a recombined product gas comprising hydrogen and at least one carbon oxide. The recombined product gas can enter a high temperature hydrogen separation unit 18 operatively coupled to the second recombiner 16. As shown in Figures 1 and 2 , high temperature hydrogen concentration • 44 - 148979.doc

S 201112487 The device 18 is the part of the first configuration. As shown in FIG. 3, the hydrogen separation device 18 is first separated from the 'reservoir' 16 and is coupled to the second recombiner via line 122. The separation device 18 may include one or more The high temperature tubular hydrogen separation thin, film 68 can be located in the recombination zone 1〇8 of the second recombiner 16 and positioned such that the feed and recombined product gas can contact the film heart to pass through the film wall of the film 68 (not shown) ) to the hydrogen conduit 124 located in the membrane 68. The membrane wall of each individual membrane will direct the hydrogen conduit 124 from the recombined product gas in the recombination zone 108 of the second reformer 16 to the non-gas compound in the feed and steam. The gas is separated and the membrane wall is selectively permeable to hydrogen (elements and/or molecules) such that hydrogen in the recombination zone 1〇8 can pass through the membrane wall of the membrane crucible to the hydrogen conduit 124, while the rest of the recombination zone The gas is prevented from being transferred to the hydrogen conduit by the membrane wall. The hydrogen flux across the high temperature hydrogen separation unit 18 can be increased or decreased by adjusting the pressure in the second reformer 16. The pressure in the second reformer 16 can be The anode exhaust stream is fed to the first recombiner 14 Rate Control. Referring to Figure 3, the feed from the second reformer 16 is fed via line 122 to a high temperature hydrogen separation unit 18. The high temperature argon separation unit 18 can include selectively permeable to hydrogen (in molecular or halogen form). One member. In a preferred embodiment, the high temperature hydrogen separation device comprises a film that is selectively permeable to hydrogen. In one embodiment, the high temperature hydrogen separation device comprises a tubular film coated with hydrogen. The gas stream entering the high temperature hydrogen separation unit 18 via line 122 may comprise hydrogen, carbon oxides and hydrocarbons. The gas stream may contact the tubular hydrogen separation membrane 68 and the hydrogen may pass through 148979.doc -45 - 201112487 passes through a film wall to a hydrogen conduit 124 located within the membrane 68. The membrane wall separates the nitrogen conduit 124 from gas communication with the non-hydrogen compound and is selectively permeable to hydrogen (elements and/or molecules). Hydrogen entering the gas can pass through the membrane wall to the hydrogen conduit 124, while other gases are prevented from being transferred to the hydrogen conduit by the membrane wall. The high temperature tubular hydrogen separation membrane 68 of Figures 1 and 2 can comprise a Carrier The coating is coated with a thin layer of one of a metal or an alloy which is selectively permeable to hydrogen. The carrier may be formed of a ceramic or a metal material which is permeable to hydrogen. Porous stainless steel or porous oxide is preferably used for the carrier of the film 68. The hydrogen-selective metal or alloy coated on the support may be selected from the following Group VIII metals, including but not limited to Pd, Pt, Ni, Ag, Ta, V, Y, Nb, Ce, ln, Ho,

La, Au and RU (specifically in alloy form). Palladium and palladium alloys are preferred. A particularly preferred film 68 used in the method has a very thin palladium alloy film' which has a high surface area coated with a porous stainless steel support. A film of this type can be prepared by the method disclosed in U.S. Patent No. 6,152,987. A film of platinum or platinum alloy having a high surface area will also be suitable as a hydrogen selection material. The pressure in the recombination zone 1〇8 of the second recombiner 16 is maintained at a level significantly higher than the pressure within the hydrogen conduit 124 of the tubular membrane 68 such that the hydrogen is forced from the recombination zone 1 of the second recombiner 16. The crucible 8 passes through the wall of the membrane into the hydrogen conduit. In one embodiment, the hydrogen conduit 124 is maintained at or near atmospheric pressure and the recombination zone 108 is maintained at a pressure of at least M 5 Mpa, or at least 1 MPa, or at least 2 Mpa or at least 3 Mpa. As described above, the recombination zone can be recombined by injecting the feed from the first recombiner 14 with the compressor 94 and injecting the feed mixture at 148979.doc -46·201112487 high pressure into the recombination zone 1〇8. 8 Maintained under such increased pressure. Alternatively, the recombination zone 1〇8 can be maintained at such high pressures by mixing the high dust vapor with the feed as described above and injecting the high pressure mixture into the recombination zone 1〇8 of the second recombiner 16. under. Another option is to 'mix the high pressure steam with the hydrocarbon stream in the first recombiner 14 or one of the first recombiner recombination zones and direct the first recombination directly or through one or more hot parent exchangers 90 A high pressure feed produced in the reactor is injected into the second reformer 16 to maintain the recombination zone 1 〇 8 at such high pressures. The recombination zone 1〇8 of the second recombiner 16 can be maintained at a pressure of at least 55 MPa, or at least 1 MPa, or at least 2.0 MPa or at least 3_0 MPa. The steam recombination feed and (as appropriate) additional steam are mixed and contacted with the recombination catalyst in the recombination zone 108 of the second reformer 16 at a temperature of at least 400 ° C ' and preferably at 4 〇 (rc) To the range of 65 (rc, optimally in the range from 450 ° C to 55 (TC). A typical steam recombiner operates at 75 Torr or higher to achieve a sufficiently high equilibrium conversion. In this method The recombiner is at 4 〇〇〇 c to 65 藉 by continuously removing hydrogen from the recombination zone 1 〇 8 into the hydrogen conduit 124 of the membrane 68 (and thus removed from the second recombiner 16). In the manner of temperature, the reaction to hydrogen is driven to recombine. In this way, the method can obtain nearly complete conversion of the reactant to hydrogen without equilibrium limitation. 40 (rc to 650t: one operating temperature is also favorable) The reaction 2 is converted to convert carbon monoxide and steam to more a, and then the hydrogen is removed from the recombination zone 1〇8 through the membrane wall of the membrane into the hydrogen conduit 124. This can be achieved in the second recombinator 16. Recombination and water gas conversion reaction of smoke and carbon monoxide to hydrogen and carbon dioxide Full conversion, as the balance is never reached due to the continuous removal of hydrogen from the first recombiner from 148979.doc -47· 201112487. In one embodiment, from the first recombiner 14 and/or the first reorganization The recombination zone of the device provides feed heating to the second recombiner 丨6 to drive the reaction in the second recombiner. To the second recombiner 16 from the first recombiner 14 and, or the first recombiner The steam recombination feed produced by a recombination zone may contain sufficient thermal energy to drive the reaction in the second recombiner and may have a temperature from 400 C to 950 C. From the first recombiner 14 and/or the first The thermal energy of the steam reforming feed produced by one of the recombiner recombination zones may exceed the thermal energy required to drive the reaction in the second reformer 16, and as described above, the feed to the second recombiner 16 is fed. The feed may previously be cooled in the heat exchanger 9 and/or by injecting water into the feed to a temperature from 4 Torr to less than 600 C. with or near the second recombination One of the temperatures required for the device 16 may be preferred so that the second reorganization can be adjusted The temperature within 16 is to facilitate the production of hydrogen in the water gas shift reaction; 2) to extend the film 68; and 3) to improve the performance of the compressor 94. The heat energy from the first recombiner 14 to the second recombiner 16 The delivery system is quite efficient because the thermal energy from the first recombiner is included in the feed, which is closely related to the reaction in the second recombiner. In the commercial temperature hydrogen separation unit 18 by selectivity Hydrogen is passed through the membrane wall of the hydrogen separation membrane 68 to the hydrogen conduit 124 to separate the hydrogen-containing stream from the reformed product gas to form a hydrogen-containing stream from the reformed product gas. The argon-containing gas stream may contain a very high hydrogen concentration. And may contain at least 〇9, or at least 0 95 or at least 0.98 mole fraction of hydrogen. Due to the high throughput of hydrogen passing through the hydrogen separation membrane 68, the hydrogen containing stream can be separated from the recombined product gas at a relatively high rate of 148979.doc • 48-201112487. In one embodiment, the hydrogen separation membrane 68 is separated from the recombined product gas by a temperature of at least 300 ° C, or from about 350. (: to about 600. (: or from 400 ° C to 500 t. Since hydrogen is present in the second reformer 16 at a high partial pressure, hydrogen passes through the hydrogen separation membrane 68 at a high flux rate. Second recombination The high partial pressure of hydrogen in the unit 16 is due to 1) a large amount of hydrogen fed to the first reformer 14 and passed to the anode recirculating stream of the second reformer in the feed; 2) in the first reformer Hydrogen produced and fed to the second recombiner; and 3) hydrogen produced by the recombination and shift reaction in the second recombiner. Due to the high rate of hydrogen separation from the recombined product, no sweep gas is required to assist in the removal of hydrogen from the hydrogen conduit 124 and removal of the high temperature hydrogen separation unit 18. The warm hydrogen separation unit 18 enters the anode 24 of the smelting carbonate fuel cell 12 via a hydrogen conduit 124 through lines 126 and 34 to the anode inlet 3〇. Alternatively, the system is fed directly to the anode inlet 30 via line 126. The ammonia gas stream will: be supplied to the anode 24 to achieve an electrochemical reaction with the oxidant at one or more anode electrodes along the anode path of the fuel cell: the molecular nitrogen-partial pressure of the setter 16 is higher than the exit high temperature nitrogen separation Device 18: Gas separation device (4) The difference between the fraction of the gas stream ==16 and the withdrawal of the high temperature drive recombination reaction and/or the water gas transfer knife. In some embodiments, more hydrogen can be produced. In some (10) from the inner portion of the membrane wall member, the nuclear conduit can be separated from the recombination zone by a hydrogen separation membrane. [By this, M8979.doc -49·201112487 before feeding the hydrogen-containing stream to the anode 24 The hydrogen-containing gas stream or its portion can be fed to heat exchanger 72 via line 128 to force the hot hydrocarbon stream and cool the hydrogen stream. After exiting the high temperature hydrogen separation unit 8, the hydrogen containing stream may have a temperature from 400 C to 650 ° C (typically from 45 ° C to 55 〇 β (: one temperature). Exiting the high temperature hydrogen separation unit The pressure of the hydrogen-containing gas of 18 may have a pressure of about 0.1 MPa, or from 0.01 MPa to M5 Mpa' or from M2 Mpa to 〇4 MPa or from 0-3 to 0.1 MPa. In a preferred embodiment, The hydrogen-containing gas stream exiting the high-temperature hydrogen separation unit 18 has a temperature of about 45 〇t: one temperature and a pressure of about 1 MPa. The pressure and temperature of the hydrogen-containing gas stream exiting the high-temperature hydrogen separation unit 18 can be adapted to directly The hydrogen-containing stream is fed directly to the anode inlet 30 of the molten carbonate fuel cell 12. It is possible to heat the hydrocarbon stream by exchanging heat with the hydrogen stream in heat exchanger 72 and optionally by exchanging heat with the carbon monoxide gas stream as follows As explained, in combination with selecting and controlling the temperature of the oxidant-containing gas stream fed to the cathode 26 of the molten carbonate fuel cell 2, the hydrogen stream fed to the anode 24 of the molten carbonate fuel cell 12 can be cooled to at most 4 Torr. 〇. (:, or at most 30 0. (:, or up to 200 ° C, or up to 150 ° C temperature, or from 2 CTC to 400. (: or from 25 ° C to 250 ° C temperature to control the operating temperature of the molten carbonate fuel cell In a range from 600 ° C to 700 ° C. The hydrogen containing stream or a portion thereof can typically be cooled to a temperature from 200 ° C to 400 ° C by exchanging heat with the hydrocarbon stream in heat exchanger 72 . Optionally, the hydrogen stream or portion thereof may be transferred from the heat exchanger 72 to one or more additional heat exchangers (not shown) in each of the one or more additional heat exchangers. To further cool the hydrogen stream by exchanging heat with a hydrocarbon stream or with a stream of water or its components. 50-148979.doc

201112487 points. If an additional heat exchanger is employed in the system, the hydrogen stream or portion thereof may be cooled to a temperature from 20 ° C to 20 (TC, preferably from 25 t to loot. In one embodiment, the helium stream A portion may be cooled in heat exchanger 72 and, where appropriate, one or more additional heat exchangers, and a portion of the gas stream may be fed to molten carbonate fuel cell 1 2 without being cooled in a heat exchanger. The anode 24, wherein the combined portion of the hydrogen stream can be at most 400 ° C, or at most 30 (TC, or at most 200. (:, or at most one i50 ° c temperature, or from 2 (TC to 400 art or Feeding to the anode of the fuel cell from a temperature of 25 ° C to 100 ° C. The hydrogen stream or a portion thereof can be selected and controlled to the heat exchangers 7 2, 2 2 and (as appropriate) to one or more additional The flow rate of the heat exchanger controls the temperature of the hydrogen stream fed to the anode 24 of the molten carbonate fuel cell 12. The hydrogen flow or a portion thereof can be selected and controlled by adjusting the throttle valves 36, 130 and 132 to the hot parent. Change the flow rate of Is 2 2 and optional additional heat exchangers. Adjust throttle valves 3 6 and 13 0 to control The gas stream or a portion thereof flows through line 1 2 6 to the anode 24 of the smelting carbonate fuel cell 12 without cooling the hydrogen stream or a portion thereof. The throttle valve 130 can also control the hydrogen stream or a portion thereof to the heat exchanger 22 Flow. The throttle valve 132 can be adjusted to control the flow of the hydrogen stream or a portion thereof through the line 128 to the heat exchanger 72 and any optional additional heat exchanger. The throttle valves 130 and 132 can be coordinated to adjust hydrogen gas. The desired degree of cooling is provided to the hydrogen stream prior to flowing to the anode 24 of the molten carbonate fuel cell 12. In one embodiment, 'the anode exhaust stream and/or cathode row may be responsive to exiting the fuel cell stack 2 The throttles 130 and 132 are automatically and coordinatedly adjusted in response to the temperature feedback of the gas stream. The hydrogen stream provides hydrogen to the anode 24 to achieve one of the anode path lengths in the fuel cell 12 at 148979.doc -51 - 201112487. Or electrochemical reaction of the plurality of anode electrodes with the oxidant. The hydrogen stream can be selectively fed to the anode 24 of the molten carbonate fuel cell η by selecting the rate at which the feed is fed to the second weight > Rate, and The feed feed to the second recombiner rate can in turn be selected by the rate at which the hydrocarbon stream is fed to the first recombiner 14, and the rate at which the flue stream is fed to the first recombiner 14 can be adjusted by adjusting the flue gas flow. The inlet is wide (10) to control. The portion of the gas-containing gas stream fed to the heat exchanger 72 and (as appropriate) the additional heat exchanger may be from the heat exchanger or through the last used to cool the hydrogen-containing stream: an additional Heat exchanger feed, wherein any portion of the hydrogen stream is routed to the anode of the (iv) carbonate fuel cell. In one embodiment, the hydrogen may be compressed in a compressor (not shown) The combined portion of the stream or exits the hydrogen containing stream of the high temperature hydrogen separation unit 18 to increase the pressure of the hydrogen stream, and the hydrogen stream can then be fed to the anode. In one embodiment, the hydrogen stream can be compressed to the chamber from Gl5 Mp_5, or from. A pressure of two to 0.3 MPa, or a pressure of up to 0.7 MPa or up to 1 MPa, may be formed by expansion of a high pressure carbon dioxide stream and/or through high pressure steam of one or more turbines as set forth below. Provide all of the energy or part of that energy required to drive the compressor. The vertical selection is 'by controlling the throttle valve 36 and i 34 to select hydrogen in a coordinated manner. IL feeds to the anode of the molten carbonate fuel cell 12 at a rate that can be used to increase or decrease hydrogen gas. The flow to the anode 24 is y! The throttle valve 134 controls the flow of the throttle valves 36 and 134 in a coherent manner by increasing or decreasing the flow of hydrogen to the hydrogen source 64 so that a selected 148979.doc

-52· 201112487 The rate of hydrogen flow can be fed through line 34 to the anode 24' of the molten carbonate fuel cell 2, and a portion of the hydrogen stream that exceeds the amount of hydrogen flow required to provide the selected rate can be passed through line 136. Feed to a hydrogen source 64. A hydrogen depleted recombined product gas stream can be removed from high temperature hydrogen separation unit 18 via line 48, wherein the hydrogen depleted recombined product gas stream can comprise unreacted feed and gaseous non-hydrogen recombination in the reformed product gas. product. The non-hydrogen recombined product and unreacted feed may comprise carbon dioxide, water (as steam π), and a small amount of carbon monoxide and unreacted hydrocarbons. The hydrogen depleted reconstituted product stream may also contain a small amount of hydrogen. In one embodiment, the hydrogen depleted rectified product stream exiting the high temperature hydrogen separation unit 18 may comprise at least 〇8, or at least 〇9, or at least 0-95 or at least 〇98 kHz on a dry basis. Carbon dioxide gas stream of carbon dioxide. The carbon dioxide gas stream is a high pressure gas stream having a pressure of at least M 5 Mpa, or at least i Mb, or at least 2 MPa or at least 2.5 MPa. In the following, the hydrogen depleted recombined product gas will be referred to as a high pressure carbon dioxide gas stream. The temperature of the high pressure carbon dioxide gas stream exiting the A hydrogen separation unit 18 is at least 4 ° C or usually between 425 t and 60 (rc or 45 (rc and 55 〇. 。. High pressure carbon dioxide gas stream can exit high temperature hydrogen separation) Device 18 is fed purely to the cathode % of fuel cell 12 via line 48. As shown, high pressure dioxane = and gas passes through heat exchanger 22 and can be used to heat the oxidant gas stream. In an embodiment, the carbon dioxide stream The portion is directly mixed with the oxidant stream entering the cathode 26 via line 44. In the preferred embodiment, the high pressure carbon dioxide gas stream is passed via line 48 into 148979.doc • 53· 201112487 to oxidize the reformer 20 in the catalytic section. The oxidative recombiner 2〇, the remaining hydrocarbons in the oxidized carbon stream (eg, A7, Ethylene, Acrylate) are combusted in the presence of oxygen or air fed through the tube (4) from the oxidation_42 to form a via line 138 passes through heat exchanger 22 and is fed via line 44 to a hot effluent combustion stream of cathode 26. In one embodiment, the combustion stream is fed directly to cathode 26 via line 38 and 44 to catalytic partial oxidation recombination. 2G The amount of molecular oxygen contained in the oxidant stream is at least 0.9 times but not more than 1.1 times the stoichiometric amount required for complete combustion of the smoke in the carbon dioxide stream. The hot combustion stream may contain a large amount of carbon dioxide 'but may also contain nitrogen And water. The hot combustion stream exiting the catalytic partial oxidation recombiner can have a temperature ranging from at least 750 C to 1050 C, or from 800 ° C to 10 ° C or from 850 ° C to 900 ° C. The heat from the hot combustion gases can be exchanged with the hydrogen containing stream parent in the heat exchanger 22 and/or with the oxidant containing gas stream in the heat exchanger. As shown in Figure 2, from the exit catalytic partial oxidation recombination 2〇 At least a portion of the heat of the combustion stream can be exchanged with the first reformer 14 in heat exchanger % via line 96. In one embodiment, the hot combustion gases can be fed directly to the cathode exhaust inlet 38. Adjustable One temperature of the oxidant gas is such that the temperature of one of the cathode exhaust streams exiting the fuel cell is from 55 (TC to 700. (the range: can be oxidized by cooling and/or heating in the hot parent exchanger 22) Gas temperature adjusted to 150 The temperature of one of °C to 450 ° C. The flow of the oxidant-containing gas stream from the high temperature hydrogen separation unit 18 to the heat exchanger 22 and/or the catalytic partial oxidation reformer 20 can be controlled by adjusting the throttle valves 46, 58 and 140. I48979.doc -54- 201112487 When the hot combustion gas stream exits the catalytic partial oxidation recombination 20, it may contain Dali as the water of the Luoqi. In one embodiment, it may be in the heat exchanger 22 and/or in the heat exchange. The unit 72 and, if desired, one or more additional heat exchangers (not shown) cool the hot combustion gas stream and remove steam from the hot combustion gas stream from the steam condensate. The hydrocarbon stream is heated by a high pressure carbon dioxide gas stream from the high temperature hydrogen separation unit 18 by passing a carbon dioxide containing gas stream through line 142 to heat exchanger 72 while simultaneously feeding the hydrocarbon stream through gas stream line 62 to heat exchanger 72. The flow of the high pressure thermal oxidizing carbon stream from the high temperature hydrogen separation unit 18 to the heat exchanger 72 can be controlled by adjusting the throttle valve 144. A throttle valve 丨 44 can be adjusted to control the flow of carbon dioxide to the heat exchanger 72 to heat the hydrocarbon stream to a selected temperature. The stream can be heated to a temperature such that the stream has at least 15 Torr when the hydrocarbon stream is fed to the first recombiner 14.匚 or from 2〇〇. 〇 to 5〇〇. One of the temperatures. The throttle valves 46, 58 and 14〇 can be automatically adjusted by a feedback mechanism that measures the temperature of the cathode exhaust stream exiting the fuel cell 12 and/or the hydrocarbon stream entering the first recombiner 14. Temperature and adjusting the throttle valves 46, 58 and 140 to maintain the temperature of the cathode exhaust stream and/or the hydrocarbon stream entering the first reformer crucible 4 within the set limits while the second recombiner 16 and/or The internal pressure in the high temperature hydrogen separation unit 18 is maintained at a desired level. The hydrogen stream and the oxidant (carbonate ion) produced by the reaction of oxygen with carbon dioxide at the cathode are preferably 'closed (as set forth above) at one or more anode electrodes of the fuel cell 12 to be at least 0.1 W/ More preferably, cm2, at least 0.15 W/cm2, or at least 〇2 W/cm2 or at least 〇3 W/cm2, one of the electrical work 148979.doc -55-201112487 rate density peak often β-r π . Electricity is generated at such electrical power densities by selecting and controlling the rate at which the hydrogen stream is fed to the fuel cell anodes and 24 and the rate at which the oxidant-containing gas stream is fed to the cathodes 6 of the fuel cell 12. The flow rate of the oxidant stream to the cathode of the fuel cell 2 can be selected and controlled by adjusting the oxidant gas inlet valve 46. As explained above, the feed rate can be selected and controlled by selecting and controlling the rate at which the feed is fed to the second weight and the benefit 16 to control and control the flow of hydrogen to the anode 24 of the fuel cell 12. The rate to the second recombiner 16 can in turn be selected and controlled by the rate at which the work machine is fed to the first recombiner 14, and the rate at which the flue stream is fed to the first recombiner 14 can be adjusted by adjusting the hydrocarbons. The flow inlet valve 1〇6 is selected and controlled. Alternatively, as indicated above, the rate at which the nitrogen material is fed to the anode 24 of the fuel cell 12 can be selected and controlled by controlling the throttle valves 36, 13A, 132 and 134 in a coordinated manner. In an embodiment, the throttle valves %, 13〇, M2, and Μ# = can be automatically adjusted by a feedback mechanism to maintain the hydrogen flow to the anode 24, wherein the feedback mechanism can be based on the anode exhaust The hydrogen content of the stream, or the water content of the anode exhaust stream, or the ratio of the water formed in the fuel cell to the hydrogen in the anode exhaust stream is measured. In the method of the present invention, the hydrogen stream is mixed with the oxidant at one or more anode electrodes by being present in the feed to the fuel cell. One of the hydrogen is partially oxidized with the oxidant. It is emulsified in the machine to produce water (as steam). The water produced by the oxidation of hydrogen and the oxidant passes through the unreacted hydrogen stream through the anode (10) of the fuel f as part of the anode exhaust stream exiting the pole 24 . w 148979.doc -56- 201112487 In one embodiment of the method of the present invention, the flow rate of the hydrogen stream feed to the anode 24 is selected and controlled, so that each unit of water formed in the "fuel pool 12" The ratio of the amount to the amount of anode exhaust gas F 甲 per unit time is at most 1.0, or at most 0.75, or at most 067, 7 或 or at most 〇.43, or at most 〇25 or at most 0.11. In an embodiment In the above, J can measure the amount of water formed in the fuel cell stack 2 and the amount of 浒曰矾T in the anode exhaust gas so that the water formed in the fuel cell per unit time The ratio of the amount of hydrogen in the anode exhaust gas to the mother's early time is at most 1 〇, or at most 0.75 ” up to 0.67, or at most 0.70 per unit time. 〇43, or at most 〇25 or at most 0.11, in the palladium only case, the flow rate of the hydrogen stream feed to the anode 24 can be selected and controlled, so that the hydrogen utilization rate per pass in the fuel cell 12 is less than the view, or ^45% , or ^乡桃,❹彡娜, "up to 2〇% or up to 10%. In another embodiment of the method of the present invention, the flow rate of the hydrogen stream feed to the anode 24 can be selected and controlled, such that the anode exhaust stream contains at least 〇6, or at least 0.7, or at least 0.8 or at least 〇.9 Ear fraction hydrogen. In a further embodiment, the flow rate of the hydrogen stream fed to the anode 24 can be selected and controlled such that the anode exhaust stream contains greater than 50%, or at least 60, of the hydrogen in the hydrogen stream fed to the anode 24. %, or at least 70%, or at least 8%, or at least 90 〇/〇. Examples The following is a non-binding example. One of the combinations with the calculation of the battery potential UniSim® simulation program (Honeywell) is used to construct a detailed process simulation. The UniSim program is used to obtain material balance and energy balance data from 14S979.doc • 57- 201112487. The detailed process simulation is repeated for the same hydrogen utilization value and other related system parameters. This detailed process simulation output contains detailed information on all process flows entering and exiting the MCFC. For high temperature fuel cells, the startup loss is small and the battery potential can be obtained over the actual current density range by considering only ohmic and electrode losses. Thus, the cell potential (v) of a molten carbonate fuel cell is the difference between the open circuit voltage (E) and the loss (iR) as shown in the equation (丨).

V=E-/R ^ ^ (1) , where V and E have units of volts and millivolts, lanthanide current density and R(DCrn2) is an ohmic (Rohm), cathode (electrolyzed, cathode and anode combined) The combination of η.) and anode (仏) resistance, as shown in the equation. R=R〇hm+Tlc+r|a (7) E is obtained from the Nernst equation: E=E°+(RT/2F)ln(PH2PO20-5/PH2〇)+(RT/2F) ln(Pc02c/ Pc〇2a) (3) where E is the standard battery potential, the general gas constant of the ruler is 8 3i4472 jk_〗 mol 1, T is the absolute temperature, and 1? is the Faraday constant 9 64853399 χΐ〇 4 c mol · 1. As shown, the cell voltage of a molten carbonate fuel cell can be varied by varying the concentrations of carbon dioxide, hydrogen and oxygen. Example 1 uses the detailed process simulations set forth above to simulate cell voltage versus current density and power density formation for the molten carbonate fuel cell system set forth herein, wherein the first recombiner is heated by the anode exhaust without additional heating . For example, the system illustrated in FIG. The heat for the second recombiner is heated by exchange with a hot effluent from a oxidizing recombiner that is catalyzed by I48979.doc • 58 · 201112487. The output temperature of the effluent from the catalytic partial oxidation recombiner is increased by using a cathode exhaust gas to preheat the catalytic oxidation of the reformer air. Example 2 uses the simulations set forth above to simulate cell voltage versus current density and power density formation for the molten carbonate fuel cell system set forth herein, with anode venting and heat from a catalytic partial oxidation recombiner. Heat the first recombinator. For example, the system depicted in Figure 2. For Examples 1 and 2, the molten carbonate fuel cell was operated at a pressure of 1 bar (about (M MPa or about i atm) and at a temperature of 650 ° C. Feed to the cathode of the molten carbonate fuel cell The flow is convective with the flow to the feed to the anode. Air is used as the source of oxygen. The value of air is used to produce a molar ratio of carbon dioxide to molecular oxygen at various hydrogen utilization rates. Listed in Table i The percent hydrogen utilization of the molten carbonate fuel cell simulated in Examples 1 and 2, the operating conditions of the first and second reformers, the steam to carbon ratio, and the percent conversion of benzene to hydrogen. From jp〇wer Sources 2〇 〇 2,112, pp. 509-5 18, obtain r in Equation 2 and assume that it is equal to 〇75 Qcm2. The data used for the simulations of Examples 1 and 2 will be used by Larmine et al.

Cell Systems Explained" (2003, Wiley & Sons, p. 199) compares the literature values of the battery voltage, current density and power density of current state of the art molten carbonate fuel cells. I48979.doc -59- 201112487 Table 1 h2 utilization, % temperature, first recombiner, °C temperature, second recombinator, °C pressure, second recombiner, Ba steam/carbon ratio, first recombiner steam /carbon ratio, % conversion of benzene to hydrogen in the second reformer 20 619 500 15 2.5 3 94 30 591 500 15 2.5 3 95 40 569 500 15 2.5 3 96 50 551 500 15 2.5 3 96 60 536 500 15 2.5 3 97 4 For the molten carbonate fuel cell system simulated in Examples 1 and 2, the battery voltage (mV) versus current density (mA/cm2) and the literature of a molten carbonate fuel cell having one of the reconstituted oils as one feed are shown. value. The molten carbonate fuel cells were operated at a hydrogen utilization rate of 2% and 30%. Data line 160 is shown for one of the melt carbonate fuel cell systems of Examples 1 and 2 at a battery voltage (mV) versus current density (mA/cm2) at 20% hydrogen utilization. Data line 162 is shown for Examples 1 and 2 for battery voltage (mV) versus current density (mA/cm2) at 30% hydrogen utilization. The data line 164 is directed to

Larmine et al. at "Fuei Cell Systems Explained" (2003,

The state of the art molten carbonate fuel cell system set forth in Wiley &Sons' page 199 shows cell voltage (mV) vs. current density (mA/cm2). As shown in Figure 4, for a given current density, the battery voltage of the molten carbonate fuel cell system set forth herein is higher than that of a molten carbonate fuel cell having the state of the art as a feedstock of reconstituted oil gas. battery voltage. Figure 5 shows the power density (W/em2) vs. 148979.doc -60 - 201112487 current density for the molten carbonate fuel cell system simulated in Examples 1 and 2 operating at 20% and 30% hydrogen utilization ( mA/cm2) and literature values for a molten carbonate fuel cell having one of the reconstituted oil gases as a feed. Information line! 66 shows power density (w/cm2) versus current density (mA/cm2) at 20% hydrogen utilization for Examples i and 2. Data line 168 plots power density (W/cm2) versus current density (mA/cm2) at a hydrogen utilization rate of 3% for Examples} and 2. The data line 丨7〇 shows the power density of the current state of the art 'melt sulphonate fuel cell system as described by Larmine et al. in "Fuel Cell Systems Explained" (2003, Wiley & Sons, p. 199). (w/cm2) vs. current density (mA/cm2). As shown in Figure 5, for a given current density, the power density of the molten carbonate fuel cell system set forth herein is higher than the power density of a molten carbonate fuel cell having a reconstituted oil gas as a feed. Example 3 is directed to a molten carbonic acid fuel cell system (eg, the system depicted in FIG. 1) comprising a first recombiner heated by anode exhaust gas using a simulation as set forth above to determine at 7 bar (about 〇· The current density, cell voltage and power density of a molten carbonate fuel cell operating at 7 Mpa or about 7 atm) is 2 Torr at a pressure of 7 bar and a temperature of 650 C. /. Or 3〇〇/. The hydrogen utilization rate operates the molten carbonate fuel cell. The first recombiner has a vapor-to-carbon ratio of 2.5. Allow the temperature of the first-recombiner to change. The second recombiner in combination with the high temperature hydrogen separation unit has 5 Torr. One of the temperature and the pressure of the bar. Use air as the source of oxygen. The value of air is used such that the ratio of carbon dioxide to molecular oxygen in the cathode feed is stoichiometric, thus minimizing the concentration of the cathode side. In all cases, the combined carbon conversion value of the system using benzene as the feed is between 93% and 95%. By the system 148979.doc -61 · 201112487

The inner heat product supplies the heat of reaction for the second reformer. By CY

The method described in Yuh and J.R. Selman in J. Electrochem. Soc. (Vol. 138, No. 12', December 1991) separately calculates the individual terms in Equation 2 above to calculate R. For Example 3, the slide rule is 〇57 Q.cm2. Figure ό shows the cell voltage (mV) vs. current density (mA/cm2) for a molten carbonate fuel cell as depicted in Figure 1. The data line 18〇 shows the cell voltage (mV) versus current density (mA/crn2) at 20% hydrogen utilization. The data line 1 82 is shown at 30°/. The battery voltage (mV) versus current density (mA/cm2) under hydrogen utilization. Comparing Figure 4 with Figure 8, at a given current density, 'with the cell voltage of the molten carbonate fuel cell system operating at 1 bar, than the molten carbonate fuel operating at a pressure of about 7 bar. A higher battery voltage was observed in the battery system. Figure 7 illustrates power density (W/cm2) versus current density and one of the states of the molten carbonate fuel cell for a molten carbonate fuel cell system as illustrated in Figure 1. Data line 184 plots power density (W/cm2) versus current density (mA/cm2) at 20% hydrogen utilization. Data line 186 plots the power density (W/cm2) versus current density (mA/cm2) at 30% hydrogen utilization. Data Point 188 shows power density (W/cm2) pairs for a state of the art molten carbonate fuel cell system as described by J. R. Selman in the Journal of Power Sources (2006 'pp. 852-857). Current density (mA/cm2). As shown in Figure 9, the power density of the molten carbonate fuel cell system set forth herein at a current density of about 300 mA/cm2 is higher than the power density of the state of the art molten carbonate fuel cell. 148979.doc -62·

201112487 As shown in example (1), systems and methods for operating a molten carbonate fuel cell as described herein produce a higher current density at a given battery voltage compared to current state of the art molten carbonate fuel cell systems. And producing a higher power density at a given current density, the systems and methods: providing a -molecular hydrogen flow - part of the high temperature hydrogen separation unit to a smelting carbonate fuel cell; using - heat source heating to provide Or provided to a first weight; and to the J; - portion, the heat source comprising anode exhaust gas from the molten carbonate fuel cell and / or heat from the anode exhaust; at least partially reconstituting Certain hydrocarbons of the hydrocarbons in the first reformer to produce a feed stream; and providing the feed stream to a second reformer. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a consistent embodiment of a system for high temperature hydrogen separation apparatus comprising a first recombiner=and-second recombiner in combination with one of the methods described herein. . 2 is a schematic diagram of one of the embodiments of a system comprising one of a first recombiner having a heat exchanger and a high temperature hydrogen separation unit in combination with a second recombiner, for practicing one of the methods set forth herein. . Figure 3 is a schematic illustration of one embodiment of a portion of a system in which a high temperature hydrogen separation unit is external to the second reformer. Figure 4 shows green cell voltage (mV) vs. current density (mA/cm2) for an embodiment of a molten carbonate fuel cell system operating at 1 bar. Figure 5 depicts power density (W/cm2) vs. current density for an embodiment of a molten carbonate fuel cell system operating at 1 bar. Figure 6 shows the implementation of a molten carbonate fuel cell system operating at 7 bar 148979.doc -63 - 201112487. The battery voltage (mV) vs. current density (mA/cm2) is illustrated. Figure 7 illustrates power density (W/cm2) versus current density (mA/cm2) for an embodiment of a flash carbonate fuel cell system operating at 7 bar. [Main component symbol description] 10 Fuel cell system 12 Flash carbonate fuel cell 14 First recombiner 16 Second recombiner 18 High temperature hydrogen separation device 20 Oxidation unit 22 Heat exchanger 24 Anode 26 Cathode 28 Electrolyte 30 Anode inlet 32 Anode Exhaust outlet 34 line 36 throttle valve 38 cathode inlet 40 cathode exhaust outlet 42 oxidant gas source 44 line 46 throttle valve 48 line 148979.doc • 64·

S 201112487 50 Line 52 Line 56 Line 58 Valve 60 Valve 62 Line 64 Hydrogen Source 66 Line 68 Temperature Temperature Mouse Separation Membrane 70 Line 72 Heat Exchanger 74 Line 76 Throttle Valve 78 Throttle Valve 80 Line 82 Throttle Valve 84 Line 86 Throttle 88 Line 90 Heat exchanger 92 Line 94 Compressor 96 Line 98 Heat exchanger 148979.doc - 65 - 201112487 100 Throttle valve 103 Three-way throttle valve 104 Line 106 Hydrocarbon flow inlet valve 108 Recombination zone 110 Pipeline 112 Line 114 throttle valve 116 throttle valve 118 throttle valve 120 throttle valve 122 line 124 hydrogen line 126 line 128 line 130 throttle valve 132 throttle valve 134 throttle valve 136 line 138 line 140 throttle valve 142 line 144 section Flow valve -66 148979.doc

Claims (1)

201112487 VII. Patent Application Range: 1 . A method for operating a molten carbonate fuel cell, comprising: providing a hydrogen-containing stream comprising molecular hydrogen from a high temperature hydrogen separation unit to a molten carbonate fuel cell, wherein the high temperature The hydrogen separation device includes one or more high temperature hydrogen separation membranes; mixing at least a portion of the hydrocarbons to be supplied to or supplied to a first reformer with an anode exhaust gas from the molten carbonate fuel cell; at least partially recombining Certain hydrocarbons of the first recombiner to produce a vapor recombination feed; and the steam recombination feed is provided to a second reformer, wherein the second recombiner includes the helium temperature hydrogen separation unit Or the second recombiner is operatively coupled to the high temperature hydrogen separation unit, and the high temperature hydrogen separation unit is configured to generate at least a portion of the stream comprising molecular hydrogen supplied to the molten carbonate fuel cell. 2. The method of claim 1, wherein the molecular hydrogen of the hydrogen-containing stream from the high temperature hydrogen separation unit has a molar fraction of at least about 6 or at least about 0.95. 3 ’ruth. The method of claim 2, wherein the steam recombination feed comprises one or more gaseous hydrocarbons, molecular hydrogen, and at least one carbon oxide, and the method further comprises reconstituting at least a portion of the steam recombination feed with the second recombination The catalyst is contacted to produce a recombined product gas comprising molecular hydrogen and carbon dioxide. 4 · The method of claim 1 5 ‘If the method of claim 1 3 The sensitizer is a water-gas conversion catalyst. And further comprising controlling the flow rate of the hydrogen-containing stream to the melted carbonate fuel cell such that the molar ratio of water to molecular hydrogen in the anode exhaust stream is at most 1.0. 6. The method of claim 1, further comprising the step of separating at least a portion of the helium-depleted stream comprising one or more gaseous hydrocarbons and at least / species of stone anti-oxidation from the high temperature hydrogen knife-off device At least a portion of the separated hydrogen depleted stream is contacted with an oxidant to produce a hot effluent stream comprising carbon dioxide, and at least a portion of the heat from the hot effluent stream is provided to the first recombiner. 7. The method of claim 1 wherein at least one of the hydrocarbons mixed with the anode exhaust has a carbon number of at least four. 8. As requested! a method, wherein at least some of the hydrocarbons recombined in the first reformer are obtained from a hydrogen source comprising at least 1% by volume, or at least 5% by volume or at least 80% by volume of at least one carbon oxide hydrocarbon. 9. The method of claim 1 , further comprising: mixing at least a portion of the hydrogen-containing stream comprising molecular hydrogen with the oxidant at one or more anode electrodes of one of the anodes of the molten carbonate fuel cell, and At least one of the electric power densities of 〇i W/cm2 generates electricity from the molten carbonate fuel cell. 1〇_ A molten carbonate fuel cell system comprising: a molten carbonate fuel cell; a first recombiner coupled to the molten carbonate fuel cell, the first recombinator configured to receive from the melt An anode exhaust of a carbonate fuel cell and a hydrocarbon' and the first recombiner is configured to allow the anode exhaust to be sufficiently mixed with the hydrocarbons to at least partially recombine some of the gases in the 148979.doc 201112487 To generate a steam recombination feed; a second recombiner coupled to the first recombiner, the second recombiner configured to receive the steam recombination feed from the first recombiner; and a high temperature hydrogen a separation device coupled to or coupled to the second recombiner and operatively coupled to the molten carbonate fuel cell, wherein the high temperature hydrogen separation device comprises one or more high temperature hydrogen separation membranes A configuration is provided to provide a hydrogen-containing stream comprising molecular hydrogen to the molten carbonate fuel cell. 148979.doc