CN102804471A - Systems And Processes Of Operating Fuel Cell Systems - Google Patents

Systems And Processes Of Operating Fuel Cell Systems Download PDF

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CN102804471A
CN102804471A CN2010800271501A CN201080027150A CN102804471A CN 102804471 A CN102804471 A CN 102804471A CN 2010800271501 A CN2010800271501 A CN 2010800271501A CN 201080027150 A CN201080027150 A CN 201080027150A CN 102804471 A CN102804471 A CN 102804471A
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hydrogen
fuel cell
reformer
anode
molten carbonate
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崔晶瑜
E·E·恩沃尔
J·W·约翰斯顿
M·L·乔施
S·L·惠灵顿
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Shell Internationale Research Maatschappij BV
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Abstract

Processes and systems for operating molNISSAN CHEMICAL IND LTD ten carbonate fuel cell systems are described herein. A process for operating a molten carbonate fuel cell system includes providing a hydrogen-containing stream comprising molecular hydrogen to an anode portion of a molten carbonate fuel cell; controlling a flow rate of the hydrogen-containing stream to the anode such that molecular hydrogen utilization in the anode is less than 50%; mixing anode exhaust comprising molecular hydrogen from the molten carbonate fuel cell with a hydrocarbon stream comprising hydrocarbons, contacting at least a portion of the mixture of anode exhaust and the hydrocarbon stream with a catalyst to produce a steam reforming feed; separating at least a portion of molecular hydrogen from the steam reforming feed; and providing at least a portion of the separated molecular hydrogen to the molten carbonate fuel cell anode.

Description

Fuel cell system and method for operation thereof
Technical field
The present invention relates to the method for fuel cell system and operation of fuel cells.Specifically, the present invention relates to the system and method for operating molten carbonate fuel cells system.
Background technology
Molten carbonate fuel cell is converted into electric energy with chemical energy.Molten carbonate fuel cell is useful, is because it is sent the reliable electrical power of high-quality, cleanliness of operation and is the generator of relative compact.These characteristics make the use in urban area, boats and ships or the remote areas that molten carbonate fuel cell is restricted in the supply of electric power source as power supply have much attraction.
Molten carbonate fuel cell is formed by anode, negative electrode and the dielectric substrate that is clipped between said anode and the negative electrode.Said electrolyte comprises alkali carbonate, alkaline earth metal carbonate, molten alkali metal carbonate or its mixture that can be suspended in porous, insulation and the chemically inert matrix.With the oxidable fuel gas or gas delivery to the said anode that can in fuel cell, be restructured as oxidable fuel gas.The oxidable fuel gas that is transported to said anode is generally synthesis gas---the mixture of oxidable component, molecular hydrogen, carbon dioxide and carbon monoxide.Can the gas that contain oxidant (being generally air and carbon dioxide) be delivered to negative electrode so that the chemical reactant that produces carbonate anion to be provided.In the operating process of said fuel cell, bring in constant renewal in said carbonate anion.
At the following operating molten carbonate fuel cells of high temperature (being generally 550 ℃ to 700 ℃), so that contain oxygen and carbon dioxide reaction in the body of oxidant with the generation carbonate anion.Said carbonate anion is crossed over electrolyte with at anode place and hydrogen and/or reaction of carbon monoxide from fuel gas.Be converted into carbanion and carbanion and hydrogen and/or carbon monoxide chemical reaction at the negative electrode place through oxygen and carbon dioxide and produce electrical power at the anode place.Below the electric electrochemical reaction in the battery when not having carbon monoxide is described in reaction:
Negative electrode charge transfer: CO 2+ 0.5O 2+ 2e -→ CO 3 =
Anode charge transfer: CO 3 =+ H 2→ H 2O+CO 2+ 2e -With
Overall reaction: H 2+ 0.5O 2→ H 2O
If carbon monoxide is present in the said fuel gas, then following chemical reaction is described the electrochemical reaction in the said battery.
Negative electrode charge transfer: CO 2+ O 2+ 4e -→ 2CO 3 =
Anode charge transfer: CO 3 =+ H 2→ H 2O+CO 2+ 2e -With
CO 3 ＝+CO→2CO 2+2e -
Overall reaction: H 2+ CO+O 2→ H 2O+CO 2
Electric loading or storage device can be connected between said anode and the said negative electrode to allow electric current between said anode and negative electrode, to flow.Said electric current maybe will provide electrical power to said storage device for said electric loading power supply.
Usually through steam reformer fuel gas is supplied to anode, said reformer is hydrogen and oxycarbide with low molecular weight hydrocarbon and steam reformation.For example, the methane in the natural gas is a kind of preferred low molecular weight hydrocarbon that is used to produce the fuel gas that is used for said fuel cell.Selectively, said anode of fuel cell can be designed to realize in inside to the low molecular weight hydrocarbon (for example methane) of the anode that is supplied to said fuel cell and the steam reforming reaction of steam.
Methane steam reforming provides the fuel gas that contains hydrogen and carbon monoxide according to following reaction:
Figure BPA00001481538800021
usually, said steam reforming reaction is being to carry out under hydrogen and the carbon monoxide efficient temperature to a large amount of methane and steam-reforming.Can be in steam reformer through steam and carbon monoxide through water gas shift reaction:
Figure BPA00001481538800022
is converted into hydrogen and carbon dioxide realizes that further hydrogen produces.
Yet; At the steam reformer that is used for fuel gas is supplied to the traditional operation of molten carbonate fuel cell; Minute quantity hydrogen is produced by said water gas shift reaction, and this is because said steam reformer is operated under the temperature that helps on the energy through steam reforming reaction generation carbon monoxide and hydrogen.Operation is unfavorable for producing carbon dioxide and hydrogen through water gas shift reaction under this temperature.
Since carbon monoxide can be in said fuel cell oxidized with provide the electric energy carbon dioxide then can not, therefore helping carrying out under the temperature that hydrocarbon and steam reformation are hydrogen and carbon monoxide the method for optimizing that said reforming reaction is considered to be provided for the fuel of said fuel cell usually.Therefore, usually through externally or steam inside reforms that the said fuel gas that is supplied to anode contains hydrogen, carbon monoxide and amounts of carbon dioxide, unreacted methane and as the water of steam.
Yet the fuel gas that contains non-hydrogen compound (for example carbon monoxide) produces the electrical power poor efficiency in molten carbonate fuel cell, comparing in purer hydrogen fuel air-flow.To under the fixed temperature, producible electrical power increases with hydrogen concentration in the molten carbonate fuel cell.This is because of the electrochemical oxidation current potential of molecular hydrogen with respect to other compound.For example; People such as Watanabe are at " Applicability of molten carbonate fuel cells to various fuels " (Journal of Power Sources; 2006, the 868 to 871 pages) in be described in pressure, the 1500A/m of 90% fuel availability, 0.49MPa 2Current density under the 10kW molten carbonate fuel cell group of operating produce the 0.12W/cm under 0.792 volt the voltage with 50% molecular hydrogen and 50% water charging 2Electrical power density, and 50% carbon monoxide and the 50% water charging that are under the same operation condition only produce the 0.11W/cm under 0.763 volt 2Electrical power density.Therefore, it is effective not as the fuel gas appearance that major part contains hydrogen that the fuel gas stream that contains a large amount of non-hydrogen compounds is to produce the electrical power aspect in the molten carbonate fuel cell.
Yet molten carbonate fuel cell is operated with " hydrogen is poor " pattern commercial usually, and the condition (for example passing through steam reformation) of wherein selecting the fuel gas generation is to limit the amount of leaving the hydrogen of said fuel cell in the said fuel gas.It is unconverted to electrical potential energy (electrochemistry+heat) that electric energy was lost with leaving said battery through hydrogen with the electric energy current potential of the hydrogen in the said fuel gas of balance to implement this.
Yet, taked some measure to catch the energy of the hydrogen that leaves said fuel cell more, the energy efficiency of these hydrogen significantly is lower than the situation that electrochemical reaction takes place hydrogen in said fuel cell.For example, the anode exhaust that the fuel gas generation electrochemical reaction in the said fuel cell is produced has been burnt and has been produced to drive turbo-expander.Yet, so do than catch the remarkable poor efficiency of electrochemical potentials of the hydrogen in the said fuel cell, this is because many heat-energy losses in the heat energy but not be converted into electric energy through decompressor.The fuel gas that leaves said fuel cell is burnt to be provided for the heat energy of various heat exchange applications.Yet after burning, almost 50% heat-energy losses is in these heat exchange applications.Hydrogen is a kind of very expensive gas that is used for lighting the burner that utilized in the poor efficiency energy-recuperation system, and the amount of therefore adjusting employed hydrogen in the molten carbonate fuel cell traditionally provides the major part to the hydrogen of said fuel cell to produce electrical power and be minimized in the amount of leaving the hydrogen of said fuel cell in the fuel cell exhaust with utilization.
Taked other measure with the more hydrogen of generation of the fuel gas from be present in said anode exhaust and/or through said fuel gas being provided to afterwards reformer and/or gas separation unit come the hydrogen in the said anodic gas of recirculation.Be to reclaim hydrogen and/or carbon dioxide, the fuel gas that is present in the anode is being reformed in the reformer of back, so that the hydrogen enrichment in the anode gas flow and/or stand water gas shift reaction to form hydrogen and carbon dioxide.Heat can be provided by anode gas flow.
Be used for inducing the methane steam reforming reaction of steam reformer and/or the heat that liquid fuel is converted into the charging that is used for steam reformer is also provided by burner.The burner of burning oxygen-containing gas and fuel (being generally the for example hydrocarbon fuel of natural gas) can be used for required heat is provided to steam reformer.Utilized flameless combustion to provide heat to be used to drive steam reforming reaction, wherein also driven flameless combustion through hydrocarbon fuel and oxidant being provided to Flameless combuster with the relative quantity of avoiding inducing flaming combustion.Be used to provide the energy efficiency of these methods that drive steam reforming reaction and/or the necessary heat of water gas shift reaction low relatively, this is to obtain and lose because of the great amount of heat energy that provides through burning is at large.
Hydrogen in the air-flow of reforming can separate with anode exhaust with carbon dioxide, for example through using psa unit and/or film separative element.The temperature of anode exhaust is usually above the required temperature of commercial hydrogen and/or carbon dioxide separation unit.For example, can pass through the said stream of cools down, yet heat energy can lose in said cooling procedure.
The hydrogen that separates is transported to the anode part of said fuel cell.Hydrogen is recycled to anode can make the fuel gas that gets into molten carbonate fuel cell be rich in hydrogen.The carbon dioxide that separates is delivered to the cathode portion of said fuel cell.Carbon dioxide is recycled to negative electrode can make the air that gets into molten carbonate fuel cell be rich in carbon dioxide.
The cell potential of molten carbonate fuel cell (V) is provided by the difference between open circuit voltage (E) and the loss.For high-temperature fuel cell, activation loss is minimum, and can in the actual current density range, obtain cell potential through only considering ohmic loss.Therefore, cell potential V=E-iR, wherein V and E have the unit of volt or millivolt, and i is current density (mA/cm 2), and total Ohmic resistance (the Ω cm of R for electrolyte, negative electrode and anode groups are lumped together 2).Open circuit voltage is the dominant term in the cell potential.Can use nernst equation E=E o+ (RT/2F) ln (P H2P O2 .5/ P H2OThe ln of)+(RT/2F) (P CO2 c/ P CO2 a) expression molten carbonate fuel cell total voltage (electromotive force), wherein E is the standard cell current potential, R is conventional gas constant 8.314472JK -1Mol -1, T is an absolute temperature, and F is a Faraday constant 9.64853399 * 10 4C mol -1As shown in, can change the cell voltage of molten carbonate fuel cell through the concentration change that makes carbon dioxide, hydrogen and oxygen.
Taked concentration of carbon dioxide that some measure provides hydrogen to said fuel cell, oxygen with adjustment with maximize battery voltage.United States Patent (USP) the 7th, 097, No. 925 (' 925 patent) are rich in hydrogen through the stream that makes the anode that is delivered to molten carbonate fuel cell makes the stream that is delivered to negative electrode be rich in the denominator that oxygen and carbon dioxide maximizes following ratio simultaneously:
Figure BPA00001481538800051
The stream that is rich in hydrogen and is rich in oxygen and carbon dioxide is provided by psa unit.
Although prior art is providing hydrogen, oxygen and carbon dioxide to effective aspect the fuel cell with variable concentrations, said method is relative poor efficiency aspect generation hydrogen, carbon dioxide and oxygen flow.Said method also underground heat poor efficiency relatively in the generation of gas and thermal process, this is because cooling anodes gas anhydrates to remove before getting into psa unit.In addition, reformer is not converted into the lower molecular weight charging that is used for steam reformer with liquid hydrocarbons feedstocks yet, and possibly provide insufficient heat to carry out this work from said fuel cell.
Operation be can be desirably in and the molten carbonate fuel cell system of electricity and the further improvement of the efficient aspect of the power density that strengthens said molten carbonate fuel cell are used to produce.
Summary of the invention
The present invention relates to the method for a kind of operating molten carbonate fuel cells system, it comprises:
The hydrogeneous stream that will comprise molecular hydrogen provides the anode part to molten carbonate fuel cell;
Control the said hydrogeneous flow velocity that flow to said anode so that the molecular hydrogen utilance in the said anode less than 50%;
To comprise from the anode exhaust of the molecular hydrogen of said molten carbonate fuel cell and mixing that the said anode exhaust of wherein mixing with said hydrocarbon stream has 500 ℃ to 700 ℃ temperature with the hydrocarbon stream that comprises hydrocarbon;
At least a portion of the mixture of said anode exhaust and said hydrocarbon stream is contacted with catalyst, comprise the steam reformation charging of one or more gaseous hydrocarbons, molecular hydrogen and at least a oxycarbide with generation;
At least a portion of separating said molecular hydrogen from said steam reformation charging; With
At least a portion of the molecular hydrogen of said separation is provided to said fused carbonate fuel battery anode as the said at least a portion of the hydrogeneous stream of molecular hydrogen that comprises.
On the other hand, the present invention relates to a kind of molten carbonate fuel cell system, it comprises:
Molten carbonate fuel cell, it is set to receive the hydrogeneous stream that comprises molecular hydrogen with certain flow rate, so that the hydrogen utilance in the anode of said molten carbonate fuel cell is less than 50%;
One or more reformers; It operationally is coupled to said molten carbonate fuel cell; At least one reformer is configured to receive hydrocarbon and from the anode exhaust of said molten carbonate fuel cell; And be configured to allow said anode exhaust and said hydrocarbon to mix fully with some hydrocarbon in the said hydrocarbon of reforming at least in part and flow to produce the product of reforming, the product stream of wherein said reformation comprises molecular hydrogen and at least a oxycarbide; With
The high temperature hydrogen separator; Its in the said reformer at least one part or be coupled at least one in the said reformer; And operationally be coupled to said molten carbonate fuel cell, wherein said high temperature hydrogen separator comprises one or more high temperature hydrogen separating films and is configured to receive the product stream of reformation and will comprises that the stream of at least a portion of molecular hydrogen provides to said molten carbonate fuel cell.
Description of drawings
Fig. 1 be used to put into practice method described herein comprise first reformer and with the sketch map of the system implementation mode of the high temperature hydrogen separator of second reformer combination.
Fig. 2 be used to put into practice first reformer that has heat exchanger comprising of method described herein and with the sketch map of the system implementation mode of the high temperature hydrogen separator of second reformer combination.
Fig. 3 is positioned at the sketch map of execution mode of the part of the outside system of second reformer for high temperature hydrogen separator wherein.
Fig. 4 describes cell voltage (mV) to current density (mA/cm to the execution mode of the molten carbonate fuel cell system of operating down in 1 crust (bara) (absolute pressure) 2).
Fig. 5 describes power density (W/cm to the execution mode of the molten carbonate fuel cell system of operation under 1 crust 2) to current density.
Fig. 6 describes cell voltage (mV) to current density (mA/cm to the execution mode of the molten carbonate fuel cell system of operation under 7 crust 2).
Fig. 7 describes power density (W/cm to the execution mode of the molten carbonate fuel cell system of operation under 7 crust 2) to current density (mA/cm 2).
Fig. 8 is under given hydrogen utilance, using the execution mode of the excess air operating molten carbonate fuel cells of various amounts to describe percentage hydrogen utilance to Δ P CO2(crust).
Fig. 9 is to using methane or benzene to describe percentage hydrogen utilance to Δ P as the execution mode of feed source operating molten carbonate fuel cells CO2(crust).
Figure 10 describes cell voltage (mV) to current density (mA/cm to the execution mode of the molten carbonate fuel cell system that uses various fuels sources 2).
Figure 11 describes average excess carbon dioxide (Δ P to the execution mode of the molten carbonate fuel cell system that uses various fuels sources CO2 (avg)) to percentage hydrogen utilance.
Embodiment
The present invention described herein is provided for operating molten carbonate fuel cells with high efficiency method that produces electricity with high electrical power density and the system that is used to carry out said method.At first, like method described herein through minimizing but not maximize the electrical power density that the whenever logical journey fuel availability of fuel in said molten carbonate fuel cell maximizes said fuel cell system.Minimize said whenever logical journey fuel availability with the carbon dioxide of the anode path that reduces to spread all over said fuel cell and the concentration of oxidation product (specifically being water), so that keep the high hydrogen concentration that spreads all over said anode path.Because the whole anode path existence along said fuel cell is excessive hydrogen for anode electrode place electrochemical reaction, therefore said fuel cell provides high electrical power density.In about the method that realizes the whenever logical journey fuel availability (for example) of height greater than 60% fuel availability, the concentration of carbon dioxide and oxidation product can fuel advance pass said fuel cell in addition half the before comprise greater than fuel flow 40%.The concentration of carbon dioxide and oxidation product can be the several times of the concentration of the hydrogen in the said fuel cell exhaust, so that the electrical power that provides along said anode path can be passed said anode and significantly reduces with providing to advance to the fuel of said fuel cell.
In method described herein, on the entire path length of the anode of molten carbonate fuel cell, flood said anode with hydrogen, on whole anode path, maintain high level so that can be used for the concentration of hydrogen at the anode electrode place of electrochemical reaction.Therefore, maximize the electrical power density of said fuel cell.
In said method, use main hydrogen or the preferred almost fuel that is rich in hydrogen of perhydro to maximize the electrical power density of said fuel cell system; This is because hydrogen has significantly bigger electrochemical potentials than other the oxidable compound (for example, carbon monoxide) that is generally used in the molten carbonate fuel cell system.
Method described herein is rich in hydrogen fuel through utilization and minimizes but not the whenever logical journey fuel availability of maximize fuel cell produces higher electrical power density in molten carbonate fuel cell system.Said minimizing through following steps realized: separate and hydrogen that recirculation is caught from the fuel vent (for example, anode exhaust) of said fuel cell, and carry hydrogen whenever to lead to the journey fuel availability to minimize with selected speed from charging and recirculation flow.
Compare with conventional system, the stream that system described herein allows to be rich in hydrogen provides to said molten carbonate fuel cell, minimizes the amount that provides to the hydrocarbon of said fuel cell simultaneously.Said system produces the stream that is rich in hydrogen in the anode part that can directly be introduced into said molten carbonate fuel cell.
Said system need not couple directly to the said anode of said molten carbonate fuel cell and/or be positioned at reformer in the said anode and guarantee to produce as the sufficient hydrogen of the fuel of the said anode that is used for said fuel cell.In said molten carbonate fuel cell, remove or eliminate reformer or reformer section, allow to flood said molten carbonate fuel cell, will be supplied to said first reformer from the major part of the heat of said anode exhaust simultaneously with hydrogen.The fuel cell that has been equipped with the inside reforming district can use with system in combination described herein.More economical and the more effectively operation of disclosed system in the comparable prior art of these fuel cells.
In method described herein; On the entire path length of the negative electrode of molten carbonate fuel cell, flood said negative electrode, on whole negative electrode path, maintain high level so that can be used for the concentration of carbon dioxide at the cathode electrode place of electrochemical reaction with carbon dioxide.Therefore, maximize the electrical power density and/or the cell voltage of said fuel cell.
Therefore method utilization described herein contains the stream of carbon dioxide enriched oxidant gas, allows the operation of fuel cell so that the partial pressure of carbon dioxide in the major part of the cathode portion of molten carbonate fuel cell is higher than the partial pressure of carbon dioxide in the major part of anode part of molten carbonate fuel cell.Operation of fuel cells produces higher electrical power density than disclosed system in the prior art in this way.
Utilize the voltage of carbon dioxide enriched oxidant gas rising molten carbonate fuel cell, and suppress the carbon dioxide deficiency of molten carbonate fuel cell." carbon dioxide not enough " refers to leave the dividing potential drop (P of the carbon dioxide of negative electrode CO2 c) less than the dividing potential drop (P of the carbon dioxide that leaves anode CO2 a).Under minimum hydrogen utilance, excess carbon dioxide provided to molten carbonate fuel cell allow to obtain high voltage and/or current density from molten carbonate fuel cell.
Compare with conventional system, system described herein allows carbon dioxide enriched stream by providing the hydrocarbon to molten carbonate fuel cell to provide to fuel cell.Can directly be introduced in the cathode portion of molten carbonate fuel cell by the carbon dioxide that system produces.System does not need the external source of carbon dioxide to guarantee the sufficient carbon dioxide as the charging of the negative electrode that is used for fuel cell.
Method described herein also is efficiently, and this is not pass said fuel cell system because be used to produce the hydrogen and the continuous recirculation of carbon dioxide of electricity in the said fuel cell.This through solve with by unconverted be that electric energy promptly leaves the hydrogen of said battery and/or problem that the carbon dioxide loss energy is associated realizes producing high electrical power density with respect to the minimum heat value of fuel.
Said system allows the air of appropriate amount or the negative electrode that molecular oxygen is delivered to said fuel cell simultaneously, so that minimize the concentration polarization of the electrode of said fuel cell at the molar ratio of carbon dioxide to the charging of said negative electrode and molecular oxygen.Said system does not need oxygen-enriched air.Method of the present invention allows to flood anode and flood negative electrode with carbon dioxide simultaneously with hydrogen, controls the amount of molecular oxygen simultaneously so that the carbon dioxide to the charging of said negative electrode and the molar ratio of molecular oxygen are at least 2 or at least 2.5.
Fuel cell system described in use the present invention allows under 0.1MPa (1atm) with the said molten carbonate fuel cell of high power density operation.Usually, molten carbonate fuel cell operation under atmospheric pressure to the pressure of about 1MPa (10atm).Can influence the life-span of the sealing in the various piece at said molten carbonate fuel cell being higher than operation under the atmospheric pressure.Said molten carbonate fuel cell can prolong the life-span of the sealing in said molten carbonate fuel cell under atmospheric pressure or near operation under the atmospheric pressure, produce with high current density to given cell voltage and/or power density simultaneously.
In method described herein, the per unit electricity that said method produced produces few relatively carbon dioxide.The hot integrated minimizing of first reformer, second reformer and high temperature hydrogen separator and fuel cell and preferred the elimination provide to drive the required additional energy of heat absorption reforming reaction in one or two reformer; Wherein through providing the heat that is produced in said fuel cell to said first reformer directly to be transmitted in said first reformer from said fuel cell hot anode exhaust stream; And subsequently the product of said first reformer is directly carried in said second reformer, and then the product of said second reformer is directly provided to said high temperature hydrogen separator.This hot integrated minimizing provides the demand of (for example, through burning) additional energy.Therefore, reduce the amount of the carbon dioxide that is produced when energy is provided with the driving reforming reaction.
Through the gaseous product separating carbon dioxide of reforming certainly; Subsequently with carbonated gas delivery to said fuel cell, make anode exhaust stream recirculation pass said system and with carbon dioxide gas stream provide to said fuel cell minimizings need be by the amount of the carbon dioxide of burning generation.This recirculation increases the electrical efficiency of said method, and therefore reduces any emission of carbon-dioxide.
In addition; Separate hydrogen-containing gas streams and subsequently said hydrogen-containing gas streams is delivered to said fuel cell through the gaseous product of reforming certainly; The hydrogen-containing gas streams that makes anode exhaust stream recirculation pass said system and will be rich in molecular hydrogen provides to said fuel cell, has reduced the amount of the hydrogen that need be produced by said second reformer.This recirculation of said anode exhaust increases the electrical efficiency of said method.Therefore in addition, the power density of said molten carbonate fuel cell is able to improvement, for producing the power of same amount, can use the fuel cell that has a smaller szie than conventional fuel battery to produce power.
Method described herein than in the prior art disclosed method have more heat and energy efficiency.Heat energy from the fuel cell exhaust directly is passed in first reformer.The part of the heat energy that is transmitted in some embodiments, is passed in second reformer from said first reformer subsequently.Heat energy is efficiently from the transmission of the anode exhaust of said fuel cell to said first reformer directly, and this is because said transmission realize through in said first reformer, will directly mixing with a minute submode with hydrocarbon stream that comprises hydrocarbon and steam from the hot anode exhaust stream of said fuel cell.Hot feed produces and is delivered to subsequently second reformer from said first reformer.Heat energy also is efficiently from the transmission of said first reformer to said second reformer, and this is because said heat energy is comprised in from said first reformer and is delivered in the charging of said second reformer.
Method described herein also than in the prior art disclosed method have more the heat efficiency, this is because be used for producing hydrogen being lower than under the temperature of typical steam reforming method from the heat of anode exhaust.In the method for the invention, can use the high temperature hydrogen separator from the product gas separation of hydrogen of reforming, wherein said high temperature hydrogen separator is a membrane separation device.Said high temperature hydrogen separator can operationally be coupled to said second reformer so that can in said second reformer reforming reaction take place the time from the gas separations hydrogen of reforming.The separation driven equilibrium of hydrogen is towards the generation of hydrogen, and reduction produces the required temperature of hydrogen.In addition; Can under low reformation temperature, produce more hydrogen; This is because the balance of water gas shift reaction helps under low reformation temperature, producing hydrogen, and under low reformation temperature, is producing hydrogen in conventional reforming reaction temperature next being unfavorable for.A large amount of or all molecular hydrogens and the carbon dioxide that produce from said second reformer are provided to said molten carbonate fuel cell.
Method described herein allows to utilize liquid fuel.Use liquid fuel to allow a kind of fuel to supply to use more than a power supply.For example, can use diesel fuel to give the power supply of molten carbonate fuel cell and engine aboard ship.Through anode exhaust and mixing of liquid charging hydrogen being added into said first reformer.The demand to the independent hydrogen source of the thermal cracking that is used for the liquid charging is eliminated in the recirculation of hydrogen.Although consumed some hydrogen, hydrogen is producing after the reformation of the hydrocarbon of cracking.The said system of integrated permission of reformer and high temperature hydrogen separator produces required all hydrogen basically of said method.
Every mole of hydrogen that is produced of the reformation of liquid fuel and/or hydrocracking produces more carbon dioxide; This is because greater than the fuel of 6 carbon number (for example have; Diesel oil and naphtha) hydrogen carbon ratio is lower than the hydrogen that has less than the fuel (for example, methane) of 6 carbon number to carbon ratio.Every mole of hydrogen that is produced produces more carbon dioxide and allows to produce required all or all carbon dioxide basically of said molten carbonate fuel cell from said liquid fuel.Produce carbon dioxide in this way and can eliminate or reduce the demand that the part of anodic gas and/or feed gas is produced carbon dioxide with the fuel that acts on hot inefficient combustion burner.In method described herein, produce excessive hydrogen and carbon dioxide, this allows hydrogen and carbon dioxide recirculation to pass said system.
Method of the present invention allows molten carbonate fuel cell under 0.1MPa (1atm) or the pressure less than 0.1MPa (1atm), to operate and provide 0.12W/cm at least 2Power density and/or the cell voltage of 800mV at least.In some embodiments, method of the present invention allows molten carbonate fuel cell under 0.1MPa (1atm) or the pressure less than 0.1MPa (1atm), to operate and provide 0.12W/cm at least 2Power density and/or the cell voltage of 800mV at least.
As used herein, only if point out in addition, term " hydrogen " refers to molecular hydrogen.
As used herein, term " hydrogen source " refers to can be produced by it compound of free hydrogen.For example, hydrogen source can be the mixture or the hydrocarbon-containing mixture of natural gas for example of hydrocarbon or these compounds of methane for example.
As used herein, when two or more component descriptions were " being operably connected " or " operationally coupling ", said component definition was for connect to allow the direct or indirect fluid between the said assembly to flow directly or indirectly.As used herein, term " fluid flows " refers to flowing of gas or fluid.Such as in the definition of " being operably connected " or " operationally coupling " use; Term " indirectly fluid flow " refers to and can guide two fluid or gas flow between definitions component through one or more additional assemblies, between definitions component, to change when mobile aspect said fluid or gas one or more at said two at said fluid or gas.Fluid or gas can be in indirectly fluid flows change aspect comprise the composition of physical characteristic (the for example temperature of gas or fluid or pressure) and/or said gas or fluid.For example, the component through separating said gas or fluid or through by vapoury condensation water.Such as among this paper definition, " indirectly fluid flow " do not comprise chemical reaction (for example, oxidation or reduction) through one or more elements of said fluid or gas and changes said two said gas or compositions of fluid between definitions component.
As used herein; Term " optionally permeable to hydrogen " is defined as molecular hydrogen or element hydrogen is permeable and impermeable to other elements or compound, makes the 10% or at the most 5% or at the most 1% permeable to molecular hydrogen or the permeable material of element hydrogen at the most of non-protium or compound.
As used herein, term " high temperature hydrogen separator " is defined as effectively installing or equipment from the hydrogen that flow separation is molecule or element form in (for example, under 300 ℃ to 650 ℃ temperature) under at least 250 ℃ the temperature.
As used herein, refer to that " the whenever logical Cheng Qing utilance " of the utilance of hydrogen in molten carbonate fuel cell in the fuel is defined as with respect to be used in the total amount of fuel that inputs to the hydrogen in the fuel in the said fuel cell to the single pass of passing said molten carbonate fuel cell said through producing the amount of electric hydrogen.Whenever logical Cheng Qing utilance can be calculated through following steps: the amount of measuring the hydrogen in the anode fuel that is delivered to fuel cell; Measure the amount of the hydrogen in the anode exhaust of said fuel cell; The amount of the hydrogen in the measured fuel that is delivered to said fuel cell deducts the amount of the hydrogen in the anode exhaust of measured said fuel cell to confirm the amount of employed hydrogen in the said fuel cell; And with the amount of employed hydrogen in the said fuel cell that is calculated amount divided by the hydrogen in the measured fuel that is delivered to said fuel cell.Whenever logical Cheng Qing utilance can be expressed as percentage through the whenever logical Cheng Qing utilance of being calculated multiply by 100.
As used herein, " excess carbon dioxide " refers to value (the Δ P of partial pressure difference of carbon dioxide of anode and the negative electrode of said molten carbonate fuel cell CO2)." excess carbon dioxide " (Δ P CO2) calculate through following steps: the dividing potential drop of the carbon dioxide in anode and cathode outlet place measurement anode exhaust and cathode exhaust gas respectively; Deduct partial pressure of carbon dioxide value (for example, the Δ P of measured anode with partial pressure of carbon dioxide value from measured negative electrode CO2=(P CO2 c)-(P CO2 a)).For the extremely convection current of the charging of said anode and negative electrode, " excess carbon dioxide " calculated through following steps: the dividing potential drop of the carbon dioxide in anode export and cathode inlet place measurement anode exhaust and cathode exhaust gas; Deduct partial pressure of carbon dioxide value (for example, the Δ P of measured anode with partial pressure of carbon dioxide value from measured negative electrode CO2=(P CO2 Cinlet)-(P CO2 Aoutlet)).
Average excess carbon dioxide is calculated through following equation.
ΔP CO2(avg)＝[{P CO2 cinlet+P CO2 coutlet}-{P CO2 ainlet+P CO2 aoutlet}]/2
" local excess carbon dioxide " refers at value (the Δ P of supposition along the partial pressure difference of the carbon dioxide of the said molten carbonate fuel cell of the standardization last every percentage hydrogen utilance of distance of y direction (width) symmetry CO2 (local)).Local excess carbon dioxide is through Δ P CO2(x)=(P CO2 c) (x)-(P CO2 a) (x) calculate, wherein x is the standardization distance along the length of anode septal area.
Fig. 1 to Fig. 3 describes to be used to carry out the sketch map that is used for operating molten carbonate fuel cells with the system implementation mode of the present invention of the method that produces electricity of the present invention.Fuel cell system 10 comprises fusion carbon carbonate fuel battery 12, first reformer 14, second reformer 16, high temperature hydrogen separator 18 and oxidation unit 20.One preferred embodiment in, second reformer 16, high temperature hydrogen separator 18 and oxidation unit 20 are a unit.One preferred embodiment in, the reformer of oxidation unit 20 catalyzing part oxidations.In one embodiment, high temperature hydrogen separator 18 molecular hydrogen membrane separation devices.In one embodiment, second reformer 16 comprises reformer section, high temperature hydrogen separator 18, catalyzing part oxidation reformer 20 and heat exchanger 22.Hot integrated form system is that the continuation operation of molten carbonate fuel cell provides sufficient hydrogen and carbon dioxide to produce.
Molten carbonate fuel cell 12 comprises anode 24, negative electrode 26 and electrolyte 28.Electrolyte 28 inserts between anodes 24 and the negative electrode 26 and contacts said anode and negative electrode.Molten carbonate fuel cell 12 can be conventional molten carbonate fuel cell, and preferably can have tubulose or plane configuration.Molten carbonate fuel cell 12 can comprise a plurality of independent fuel cell that is stacked.Said independent fuel cell can and be operably connected and electrical coupling through interconnection, make one or more air-flows to flow and pass the anode of the fuel cell that piles up, and the gas that contains oxidant can flow and passes the negative electrode of the fuel cell that piles up.As used herein, term " molten carbonate fuel cell " is defined as single molten carbonate fuel cell or a plurality of molten carbonate fuel cell that is operably connected or piles up.The anode 24 of molten carbonate fuel cell 12 can be formed through nickel compound, the nichrome of sintering, the nickel with lithium chromated oxide and/or monel or the material of appointing that is suitable as the anode of molten carbonate fuel cell by porous.The negative electrode 26 of molten carbonate fuel cell 12 can be formed through the agglomerated material (for example nickel oxide, lithium-Ni-Fe oxide) or the material of appointing that is suitable as the negative electrode of molten carbonate fuel cell by porous.
Gas delivery to said anode and negative electrode are produced electric necessary reactant to be provided in the fuel cell 12.Hydrogeneously flow into anode 24, and contain oxidizer flow and get into negative electrode 26.Electrolyte part 28 is positioned to get into anode with the air-flow (oxygen and carbon dioxide stream) that stops hydrogen-containing gas streams entering negative electrode and prevention to contain oxidant in the said fuel cell.The air-flow that contains oxidant comprises the one or more streams that contain aerobic and/or carbon dioxide.
Electrolyte part 28 with carbanion from cathode guide to anode, with realize with anode gas flow in oxidizable compounds (for example, hydrogen and optional carbon monoxide) in the electrochemical reaction at one or more anode electrodes place.Electrolyte part 28 can be formed by the fuse salt of alkali carbonate, alkaline earth metal carbonate or its combination.The execution mode of electrolyte comprises the porous material that is formed by lithium carbonate sodium, lithium carbonate, sodium carbonate, lithium carbonate sodium barium, lithium carbonate sodium calcium and lithium carbonate potassium.
Fuel cell 12 is set to allow hydrogeneous air-flow to flow to pass anode 24 and flow out anode exhaust from anode inlet 30 and exports 32.One or more anode electrodes on the anode path of hydrogen-containing gas streams contact anode inlet 30 to anode air exit 32.
The air-flow (hereinafter referred to as " hydrogeneous stream ") or the hydrogen source that in one embodiment, will contain molecular hydrogen through pipeline 34 are delivered to anode inlet 30.Metering valve 36 can be used for selecting and controls the said hydrogeneous flow velocity that flow to anode inlet 30.One preferred embodiment in, hydrogen is delivered to the anode 24 of fuel cell 12 from high temperature hydrogen separator 18, wherein said high temperature hydrogen separator is a film unit, such as hereinafter detailed description.In one embodiment, said hydrogen-containing gas streams can comprise the hydrogen of at least 0.6 or at least 0.7 or at least 0.8 or at least 0.9 or at least 0.95 or at least 0.98 molfraction.
The gas that is transported to said negative electrode comprises oxidant.As mentioned among this paper, " oxidant " refers to can be through the compound that reacts to each other and reduce with molecular hydrogen.In some embodiments, the gas that contains oxidant that is delivered to negative electrode comprises oxygen, carbon dioxide, inert gas or its mixture.In one embodiment, the gas that contains oxidant is the combination of oxygen flow and carbonated air-flow or the stream that contains oxygen/carbon dioxide.One preferred embodiment in, the oxygen-containing gas that is delivered to negative electrode for the air or the oxygen-enriched air of the carbon dioxide mix of abundance, make carbon dioxide be at least 2 or at least 2.5 to the molar ratio of oxygen.
The gas that contains oxidant can flow to pass negative electrode 26 and export 40 through cathode exhaust gas subsequently and flow out from cathode inlet 38.The said one or more cathode electrodes of gas contact on the negative electrode path of cathode inlet 38 to negative electrode air exit 40 that contain oxidant.In one embodiment, containing the gas of oxidant can be with respect to the mobile convective flow of the hydrogen-containing gas of the anode that flows to fuel cell 12 24.
In one embodiment, contain the gas source 42 of oxidizer flow through pipeline 44 self-contained oxidants and be delivered to cathode inlet 38.Metering valve 46 can be used for selecting and controlling the speed of said gas delivery to negative electrode 26.In some embodiments, by air compressor the said gas that contains oxidant is provided.The said air-flow that contains oxidant can be air.In one embodiment, the said gas that contains oxidant can be pure oxygen.In one embodiment, the said air-flow that contains oxidant can be the air that is rich in oxygen and/or carbon dioxide of the carbon dioxide of the oxygen that contains at least 13 weight % and/or at least 26 weight %.One preferred embodiment in, the flowing of control air and/carbon dioxide so that Carbon Dioxide in Air is at least 2 or at least 2.5 to the molar ratio of molecular oxygen.
In one embodiment, through carbonated air-flow and oxygen containing air-flow the said air-flow that contains oxidant is provided.Carbon-dioxide flow and oxygen flow can be from two independent sources.One preferred embodiment in, be used for the most of of molten carbonate fuel cell 12 or basically all carbon dioxide be derived from the hydrocarbon stream that comprises hydrocarbon that provides to first reformer 14.Carbonated air communication is crossed pipeline 44 and is delivered to cathode inlet 38 from carbon dioxide source.Provide to the carbonated air-flow of fuel cell 12 and can be delivered to identical cathode inlet 38, or can before being delivered to cathode inlet 38, mix with oxygen flow with oxygen flow.Selectively, carbonated air-flow can provide to negative electrode 26 through independent cathode inlet.
One preferred embodiment in, said carbon-dioxide flow provides the negative electrode 26 to fuel cell 12 via pipeline 48 and 44 from high temperature hydrogen separator 18, such as this paper description.Oxygen can provide the negative electrode 26 to fuel cell 12 via pipeline 44.
Before being delivered to negative electrode 26 and/or anode 24; The gas (no matter one stream or a plurality of stream) that is delivered to negative electrode and/or anode can heat in heat exchanger 22 or other heat exchanger, preferably through with leave cathode exhaust vent 40 and be connected to the oxygen depletion cathode exhaust stream exchanged heat of heat exchanger 22 through pipeline 50.
In the method for the invention, mix to produce with oxidant a place or the many places of hydrogen-containing gas streams in the anode electrode of molten carbonate fuel cell 12.Said oxidant is preferably carbon dioxide and the reaction of oxygen and the electrolytical carbanion that said fuel cell is crossed in the warp guiding that being derived from flows passes negative electrode 26.Through hydrogen-containing gas streams and/or gas delivery to the fuel cell 12 that contains oxidant being mixed said hydrogen-containing gas streams and said oxidant at one or more anode electrodes place of said fuel cell, like the further argumentation in detail of hereinafter institute with selected independent rate.Said hydrogen-containing gas streams and said oxidant preferably mix at one or more anode electrodes place of said fuel cell with under 1 crust with 0.1W/cm at least 2, or 0.15W/cm at least 2, or 0.2W/cm at least 2, or 0.3W/cm at least 2Or 0.6W/cm at least 2Electrical power density produce.Can under elevated pressures and/or through use, be rich in air-flow (for example, the air of rich oxidant) the acquisition higher power density of oxidant.
To making carbanion cross operating molten carbonate fuel cells 12 under electrolyte part 28 to anode 24 efficient temperature from negative electrode 26.Can be under the temperature of 550 ℃ to 700 ℃ or 600 ℃ to 650 ℃ operating molten carbonate fuel cells 12.The exothermic reaction that is oxidized at one or more anode cells place's hydrogen and carbanion.The heat of said reaction produces the required heat of operating molten carbonate fuel cells 12.Residing temperature can receive several controlling factors during operating molten carbonate fuel cells, comprises but is not limited to regulate hydrogen-containing gas and contains the feeding temperature and the feed flow of the gas of oxidant.Because the hydrogen utilance minimizes, so excessive hydrogen is transported to said system, and unreacted hydrogen can partly cool off said molten carbonate fuel cell through excessive heat being carried to said first reformer.Regulate carbon-dioxide flow and/or contain the gas that contains oxidant that flowing of oxidant stream maintain about 2 place's needs abundances with the molar ratio with carbon dioxide and molecular oxygen realize being about need be with 1.3 to 2.0 times molecular oxygen of the amount of the partial reaction of the hydrogen that utilized in the anode excessive.The air of the oxygen depletion that therefore, in cathode exhaust gas, leaves or the excessive of gas that contains oxidant can carry big calorimetric from said molten carbonate fuel cell.In that described hydrogeneous stream provides to the anode 24 of molten carbonate fuel cell 12 from high temperature hydrogen separator 18 with hereinafter; Can reduce the temperature that provides to the said hydrogeneous stream of said fused carbonate fuel battery anode through recuperation of heat (for example, through heat exchanger 22).In that described high-pressure carbon dioxide stream provides to the negative electrode 26 of molten carbonate fuel cell 12 from high temperature hydrogen separator 18 with hereinafter; Can reduce the temperature that provides to the said high-pressure carbon dioxide stream of said fused carbonate fuel battery cathode through recuperation of heat (for example, through heat exchanger 22).Provide to the said fused carbonate fuel battery cathode in the outflow logistics of self-catalysis in future partial oxidation reformer 20, can reduce the temperature of said outflow logistics through recuperation of heat (for example, through heat exchanger 22).Can be used for heating one or more in the stream that is utilized in the said system from the used heat of said fuel cell.If necessary, any replenishment system that is used to cool off fused carbonate fuel then well known in the prior art can be used for controlling the temperature of said molten carbonate fuel cell.
The air-flow that contains oxidant that in one embodiment, can before being delivered to negative electrode 26, will be delivered to said negative electrode is heated to the temperature of at least 150 ℃ or 150 ℃ to 350 ℃.In one embodiment, when using oxygen-containing gas, the temperature of oxygen flow is controlled to 150 ℃ to 350 ℃ temperature.
Be the operation of beginning fuel cell 12, with said fuel cell heating to its operating temperature---be enough to the temperature of fused electrolyte salt to allow carbanion to flow.As shown in Figure 1, can begin the operation of said molten carbonate fuel cell through the anode 24 that in catalyzing part oxidation reformer 20, produces hydrogen-containing gas streams and said hydrogen-containing gas streams is delivered to molten carbonate fuel cell 12 through pipeline 52 and 34.
Exist under the situation of conventional partial oxidation catalyst; Part through the described hydrocarbon stream that comprises hydrocarbon of burning hereinafter in catalyzing part oxidation reformer 20 or different hydrocarbon streams are (for example; The fuel that is rich in natural gas stream) in catalyzing part oxidation reformer 20, produce hydrogen-containing gas streams with the gas that contains oxidant, wherein be delivered to the substoichiometric of the amount of the oxygen in the gas that contains oxidant of catalyzing part oxidation reformer 20 with respect to the amount of the hydrocarbon in the hydrocarbon stream.Flowing of hydrogen-containing gas streams can be by valve 60 controls.
As shown in Figure 2, through the anode 24 that in oxidation unit 20, produces hydrogen-containing gas streams and said hydrogen-containing gas streams is delivered to molten carbonate fuel cell through pipeline 96,104 and 34 with said fuel cell heating to its operating temperature.Be delivered to the speed of anode 24 via pipeline 96,104 autoxidation unit 20 through triple valve 102 control hydrogen-containing gas streams.Part from the heat of hydrogen-containing gas streams can be passed heat exchanger 98 via pipeline 96, heat provided to first reformer 14 and/or to get into the hydrocarbon stream that comprises hydrocarbon of said first reformer.
See figures.1.and.2, the fuel that is delivered to catalyzing part oxidation reformer 20 can be the mixture of liquid or gaseous hydrocarbon or hydrocarbon, and preferably with provide the hydrocarbon stream that comprises hydrocarbon identical to first reformer 14.Fuel can be delivered to catalyzing part oxidation reformer 20 via pipeline 62.In one embodiment, the fuel that is delivered to catalyzing part oxidation reformer 20 is rich in natural gas and/or from the hydrogen of hydrogen source 64.
The oxidant that is delivered to catalyzing part oxidation reformer 20 can be pure oxygen, air or oxygen-enriched air (hereinafter referred to as " gas that contains oxidant ").Preferably, the said gas that contains oxidant is air.Should said oxidant be provided to catalyzing part oxidation reformer 20, so that the amount of the oxygen in the said oxidant is substoichiometric amount with respect to the hydrocarbon that is delivered to said catalyzing part oxidation reformation.One preferred embodiment in, through pipeline 56 the said gas autoxidator source 42 that contains oxidant is delivered to catalyzing part oxidation reformer 20.The gas (air) that valve 58 may command contain oxidant is delivered to the speed of the negative electrode 26 of catalyzing part oxidation reformer 20 and/or fuel cell 12.In one embodiment, can be through heating the gas that contains oxidant that gets into catalyzing part oxidation reformer 20 with the oxygen depletion cathode exhaust stream exchanged heat of leaving cathode exhaust vent 40.
In catalyzing part oxidation reformer 20, form hydrogen-containing gas streams existing under the situation of conventional partial oxidation catalyst through burning hydrocarbon and oxidant, wherein with respect to hydrocarbon, said oxidant is substoichiometric amount.The hydrogen-containing gas streams that forms through hydrocarbon and oxidant contacting in catalyzing part oxidation reformer 20 contain through with anode electrode in the carbanion of a place or many places contact and compound that can oxidation in anode of fuel cell 24.The compound that does not preferably contain the one or more anode electrodes in the anode 24 of oxidized fuel cell 12 from the hydrogen-containing gas streams of catalyzing part oxidation reformer 20.
Be formed at hydrogen-containing gas streams in the catalyzing part oxidation reformer 20 for heat, and can have the temperature of at least 700 ℃ or 700 ℃ to 1100 ℃ or 800 ℃ to 1000 ℃.In the method for the invention; Use flow from the hot hydrogen of catalyzing part oxidation reformer 20 begin molten carbonate fuel cell 12 startup for preferred, this be because its temperature that makes said fuel cell almost moment is increased to the operating temperature of said fuel cell.In one embodiment, when the operation of the said fuel cell of beginning, heat can be in heat exchanger 22 in from the hot hydrogen-containing gas of catalyzing part oxidation reformer 20 and be delivered between the gas that contains oxidant of negative electrode 26 and exchange.
With reference to Fig. 1, can use valve 60 adjustment from flowing in hot hydrogen-containing gas streams to the fuel cell 12 of catalyzing part oxidation reformer 20, through opening valve 36 hydrogen-containing gas streams is delivered in the anode 24 simultaneously.But from shut off valve 60 after the flowing of the hydrogen-containing gas streams of high temperature hydrogen separator 18, reduce simultaneously or stop the hydrocarbon charging through mobile through pipeline 56 to catalyzing part oxidation reformer 20 of pipeline 62 and oxidant feed in beginning.
With reference to Fig. 2, can use the hot hydrogen-containing gas streams of threeway metering valve 102 adjustment through flowing in pipeline 96 self-catalysis partial oxidation reformer 20 to the fuel cells 12, through opening valve 36 said hydrogen-containing gas streams is delivered in the anode 24 simultaneously.But, reduce simultaneously or stop the hydrocarbon charging and pass through flowing of pipeline 56 to catalyzing part oxidation reformer 20 through pipeline 62 and oxidant feed at shut off valve 102 after high temperature hydrogen separator 18 produces hydrogen-containing gas streams.Then, can carry out the continuation operation of said fuel cell according to the method for the invention.
Threeway metering valve 102 control effluent self-catalysis partial oxidation reformers 20 flowing to anode 24 or negative electrode 26.In start-up course, be rich in hydrogen from the effluent of catalyzing part oxidation reformer 20, therefore after passing heat exchanger 98, said effluent is directed to anode 24 via pipeline 104 via pipeline 96.After beginning to start, and if catalyzing part oxidation reformer 20 be used to produce the carbon dioxide that is used for negative electrode 26, metering valve 102 control effluents flowing then via pipeline 96 self-catalysis partial oxidation reformer 20 to negative electrodes 26.
In another embodiment; As shown in Figure 1; Before hydrogen-containing gas streams being introduced in the fuel cell 12 via pipeline 66, available passing starts the heater (not shown) and the hydrogen from hydrogen source 64 that fuel cell rises to its operating temperature is started air-flow begins the operation of said fuel cell.Hydrogen source 64 can be for receiving the accumulator tank from the hydrogen of high temperature hydrogen separator 18.Can said hydrogen source be may be operably coupled to said fuel cell, hydrogen started in the anode that air-flow is introduced into said molten carbonate fuel cell allowing.Said startup heater can start the air-flow indirect to the temperature from 750 ℃ to 1000 ℃ with hydrogen.Selectively, said startup heater can provide hydrogen through providing from hydrogen source 64 to the imperfect combustion of the hydrogen of said heater.Said startup heater can be electric heater or can be burning heater.After reaching the operating temperature of said fuel cell; Can cut off hydrogen through valve and start flowing in air-flow to the fuel cell, and can hydrogen-containing gas streams be introduced in the said fuel cell to begin the operation of said fuel cell through the valve of opening from the anode of hydrogen generator to fuel cell.
In one embodiment, first reformer 14 comprises the catalyzing part oxidation reformer, and it is used for when starting, hydrogen being provided to molten carbonate fuel cell.First reformer 14 can comprise one or more catalyst beds, and it allows said first reformer when in a single day said molten carbonate fuel cell has reached operating temperature, to be used for self-heating recapitalization and to be used for steam reformation subsequently.
In case fuel cell 12 has begun operation, negative electrode 26 promptly sends exhaust with anode 24.Exhaust from negative electrode 26 and anode 24 is hot; And can be integrated producing hot integrated form system from the heat of said exhaust with other unit heat, said hot integrated form system produces necessary all fuel of operation (hydrogen) and the oxidant (carbanion) of said fuel cell.
As depicted in figs. 1 and 2; Method described herein is utilized system, and said system comprises hot integrated form hydrogen and separates separator 18, molten carbonate fuel cell 12, first reformer 14 and second reformer 16 and catalyzing part oxidation reformer 20 (in some embodiments).High temperature hydrogen separator 18 comprises one or more high temperature hydrogen separating films 68, and operationally is coupled to molten carbonate fuel cell 12.The hydrogen-containing gas streams that high temperature hydrogen separator 18 will mainly contain molecular hydrogen provides the anode 24 to fuel cell 12, and provides to first reformer 14 from the exhaust of the anode of molten carbonate fuel cell 12.Two unit that first reformer 14 and second reformer 16 can be a unit or operationally be coupled.First reformer 14 and second reformer 16 can comprise one or more reformer section.In one embodiment, first reformer 14 and second reformer 16 are for comprising a unit of first reformer section and second reformer section.
To comprise that via pipeline 62 hydrocarbon stream of hydrocarbon provides to first reformer 14, and anode exhaust will be mixed with hydrocarbon.Said method is hot integrated form, wherein directly in said first reformer by the anode exhaust of the molten carbonate fuel cell 12 of heat release and/or with providing the hydrocarbon to the hydrocarbon stream of said first reformer that the heat that drives the heat absorption reforming reaction in first reformer 14 is provided.In one embodiment, mix with hydrocarbon in heat exchanger from the part of the heat of said anode exhaust, said heat exchanger is arranged in said first reformer or operationally is coupled to said first reformer.As shown in Figure 2, to the extra heat of first reformer 14 from the beginning the hot-fluid of self-catalysis partial oxidation reformer 20 go out logistics and provide.In first reformer 14, from least a portion of the hydrocarbon of hydrocarbon stream through cracking and/or reform and provide to the incoming flow of second reformer 16 via pipeline 70 to produce.
Second reformer 16 operationally is coupled to high temperature hydrogen separator 18, and the high temperature hydrogen separator produces at least a portion, major part, at least 75 volume % or at least 90 volume % or all get into the hydrogen-containing gas of the anode 24 of molten carbonate fuel cell 12 basically.The high temperature hydrogen separator can be positioned on after second reformer 16 with molten carbonate fuel cell 12 before.One preferred embodiment in, high temperature hydrogen separator 18 is the film separative element, it is the part of second reformer 16.The product of high temperature hydrogen separator 18 separation of hydrogen and reformation.The hydrogen that separates is provided to the anode 24 of molten carbonate fuel cell 12.
In an execution mode of said method, hydrocarbon stream contains one or more in any transpirable hydrocarbon, and said transpirable hydrocarbon is liquid down in atmospheric pressure (optional through oxygenation), 20 ℃, at atmospheric pressure, be up under 400 ℃ the temperature and can evaporate.These hydrocarbon can comprise but be not limited to have the petroleum distillate of 50 ℃ to 360 ℃ boiling spread, for example naphtha, diesel oil, jet fuel, gas-oil and kerosene.In one embodiment, said hydrocarbon stream is a decane.One preferred embodiment in, said hydrocarbon stream is a diesel fuel.In one embodiment, said hydrocarbon stream contains the hydrocarbon of the carbon number with scope of 5 to 25.One preferred embodiment in, said hydrocarbon stream contains the hydrocarbon that at least five or at least six or at least seven carbon atoms of at least 0.5 or at least 0.6 or at least 0.7 or at least 0.8 molfraction.
Said hydrocarbon stream can be chosen wantonly to contain at 25 ℃ and be down some hydrocarbon of gaseous state, for example 25 ℃ be down gaseous state contain a methane, ethane, propane or other compound to four carbon atom.Said hydrocarbon stream can be before being delivered to first reformer 14 treated and/or in heat exchanger 72 through heating, can be to remove to being used for arbitrary catalyst that hydrocarbon with higher molecular weight is converted into lower molecular weight hydrocarbon is caused any material of adverse effect in said first reformer.For example, said hydrocarbon stream can experience a series of processing to remove metal, sulphur and/or nitrogen compound.
In an execution mode of said method, said hydrocarbon stream mixes with the natural gas of the carbon dioxide that contains 20 volume % or 50 volume % or 80 volume % at least at least at least.If necessary, then said natural gas is treated to remove hydrogen sulfide.In one embodiment, the hydrocarbon stream of carbon dioxide of carbon dioxide or at least 70 volume % that has carbon dioxide, at least 50 volume % of at least 20 volume % can be used as fuels sources.
In one embodiment, said hydrocarbon stream can provide to first reformer 14 under at least 150 ℃, preferred 200 ℃ to 400 ℃ temperature, and wherein said hydrocarbon stream can be heated to temperature required in the described heat exchanger like hereinafter.The temperature that said hydrocarbon stream is delivered to first reformer 14 may be selected to be and highly as far as possible not produce coke to evaporate said hydrocarbon.The temperature of said hydrocarbon stream can be 150 ℃ to 400 ℃ scope.Selectively (but more not preferred) if the sulfur content of said hydrocarbon stream is low, then can directly be delivered to said hydrocarbon stream first reformer 14 and not heat said hydrocarbon stream for example being lower than under 150 ℃ the temperature.
As shown in Figure 1, can make said hydrocarbon stream pass one or more heat exchangers 72 to heat said charging.Said hydrocarbon stream can be through separating with negative electrode 26 from molten carbonate fuel cell 12 and heating via the cathode exhaust stream exchanged heat that pipeline 74 is delivered to heat exchanger 72.Can come the control cathode exhaust stream to be delivered to the speed of heat exchanger 72 and 22 through adjustment metering valve 76 and 78.
One preferred embodiment in, via pipeline 80 independent anode exhaust stream is delivered in one or more reformer section of first reformer 14.Can control the speed that anode exhaust stream is delivered to first reformer 14 through adjustment metering valve 82.The temperature of anode exhaust can be about 500 ℃ to about 700 ℃ scope, and be preferably about 650 ℃.
Anode exhaust stream comprises hydrogen, steam and from the product and the unreacted fuel of the fuel oxidation of the anode that is delivered to fuel cell 12 24.In one embodiment, anode exhaust stream contains the hydrogen of at least 0.5 or at least 0.6 or at least 0.7 molfraction.Be delivered in the anode exhaust stream of reformer section of first reformer 14 or said first reformer hydrogen can help stop the formation of coke in said first reformer.In one embodiment, said anode exhaust stream contains 0.0001 to about 0.3 or 0.001 to about 0.25 or 0.01 to about 0.2 molfraction water (as steam).Outside the dehydrogenation, the steam that is present in the anode exhaust stream of the reformer section that is delivered to first reformer 14 or said first reformer also can help to stop the formation of coke in said first reformer.Said anode exhaust stream can contain sufficient hydrogen and be restructured as methane, hydrogen and carbon monoxide to suppress coking and to contain sufficient steam with the major part with the hydrocarbon in the hydrocarbon stream.Therefore, can need less steam to come reforming hydrocarbon in said first reformer and/or said second reformer.
The reformer section that randomly, can steam be delivered to first reformer 14 or said first reformer via pipeline 84 with the reformer section of said first reformer or said first reformer in hydrocarbon stream mix.The reformer section that can steam be delivered to first reformer 14 or said first reformer is to suppress or to stop coke in said first reformer, to form and randomly be used in the reforming reaction that said first reformer realized.In one embodiment; With given pace steam is delivered to the reformer section of first reformer 14 or said first reformer, the molar ratio that wherein is added into total steam of said first reformer is twice at least or at least three times that are added into the mole of the carbon in the hydrocarbon stream of said first reformer.The total steam that is added into said first reformer can comprise steam from anode exhaust, from steam (for example, through pipeline 84) or its mixture of external source.In the reformer section of first reformer 14 or said first reformer, provide at least 2: 1 or at least 2.5: 1 or at least 3: 1 or at least 3.5: 1 the steam and the mol ratio of carbon can be used for suppressing the formation of coke in said first reformer.Metering valve 86 can be used for controlling steam is delivered to the reformer section of first reformer 14 or said first reformer through pipeline 84 speed.Because said anode exhaust comprises a large amount of hydrogen, therefore less coking often takes place in reforming process.Therefore, the amount that is delivered to the optional steam of first reformer 14 can significantly be less than the amount of the steam that is used for conventional reformer unit.
Steam can be delivered to first reformer 14 under at least 125 ℃, preferred 150 ℃ to 300 ℃ temperature; And the pressure that can have 0.1MPa to 0.5MPa preferably has and is equal to or less than the pressure that is delivered to like the pressure of the anode exhaust stream of first reformer described herein.Can having at least through heating, the water under high pressure of the pressure of 1.0MPa, preferred 1.5MPa to 2.0MPa (passing heat exchanger 90 through transmitting said water under high pressure via pipeline 88) produces steam.Through heating said water under high pressure to form high steam with the cathode exhaust gas exchanged heat of after the cathode exhaust gas charging is passed heat exchanger 72 by pipeline 74, carrying.Selectively, can said cathode exhaust gas directly be delivered to heat exchanger 90 (not shown)s or one or more heat exchanger.If utilized more than a heat exchanger, then after leaving heat exchanger 90 or final heat exchanger, said high steam can be delivered to pipeline 84 via pipeline 92 subsequently.Can said high steam be expanded said high steam is decompressed to required pressure, then it is delivered to said first reformer through passing decompressor.Selectively, can supply the steam that uses in said first reformer through passing that one or more heat exchangers 90 are carried low-pressure water and gained steam being passed to produce in first reformer 14.
Randomly, the high steam that does not utilize in first reformer 14 or second reformer 16 can pass through other power set (for example, turbine (not shown)) and expand with arbitrary high-pressure carbon dioxide stream that does not utilize or optional stream with high-pressure carbon dioxide.Power supply can be used for producing electricity and/or except that the electricity that is produced by fuel cell 12, also produces.The power that is produced by power supply and/or fuel cell can be used for to employed any other compressor power supply in compressor 94 and/or the method for the present invention.
Hydrocarbon stream, optional steam and anode exhaust stream mix with reforming catalyst in the reformer section of first reformer 14 or said first reformer under the charging efficient temperature and contact to form not being any hydrocarbon and the said hydrocarbon of cracking that are the steam form to evaporation.
Said reforming catalyst can be conventional reforming catalyst, and can be any catalyst well known in the prior art.Spendable typical reforming catalyst comprises but is not limited to the VIII group 4 transition metal, is in particular nickel and under the pyroreaction condition, is the carrier of inertia or matrix.Comprise as the suitable inert compound of the carrier of high temperature reformations/hydrocracking catalyst but be not limited to Alpha-alumina and zirconia.
One preferred embodiment in, hydrocarbon stream, anode exhaust and optional steam about 500 ℃ to about 650 ℃ or about 550 ℃ to the 600 ℃ temperature with catalyst mix and contact, wherein necessary all heat of reforming reaction are by the anode exhaust supply.In one embodiment, hydrocarbon stream, optional steam and anode exhaust stream at least 400 ℃ or 450 ℃ to 650 ℃ or 500 ℃ to 600 ℃ temperature under with catalyst mix and contact.
Heat by the anode exhaust stream supply of the reformer section that is delivered to first reformer 14 or said first reformer from heat-release melting carbonate fuel battery 12 drives endothermic pyrolysis and reforming reaction said first reformer.The anode exhaust stream of reformer section that is delivered to first reformer 14 and/or said first reformer from molten carbonate fuel cell 12 is very warm, has at least 500 ℃ temperature, has the temperature of 550 ℃ to 700 ℃ or 600 ℃ to 650 ℃ usually.Heat energy is quite effective from the transmission of the reformer section of molten carbonate fuel cell 12 to first reformers 14 or said first reformer; This is because be included in the anode exhaust stream from the heat energy of said fuel cell, and through directly said anode exhaust stream and hydrocarbon stream and vapor mixing being passed to hydrocarbon stream in the reformer section of first reformer 14 or said first reformer, optional steam and the mixture of anode exhaust stream.
One of method described herein preferred embodiment in, anode exhaust stream provides at least 99% or all heat basically from the required heat of the generation charging of the mixture of hydrocarbon stream, optional steam and anode exhaust.In certain preferred execution mode, except that anode exhaust stream, do not have other thermal source provide to first reformer 14 so that hydrocarbon stream is converted into charging.
Pressure when in one embodiment, said anode exhaust stream, hydrocarbon stream and optional steam contact with reforming catalyst in first reformer 14 can be the scope of 0.07MPa to 3.0MPa.If high steam is not transported to first reformer 14, then said anode exhaust stream, hydrocarbon stream and optional low-pressure steam can contact with reforming catalyst in said first reformer under the pressure (0.07MPa to 0.5MPa or 0.1MPa to 0.3MPa usually) of the lower end of said scope.If high steam is transported to first reformer 14, then said anode exhaust stream, hydrocarbon stream and steam can be located to contact with said reforming catalyst in the higher-end (1.0MPa to 3.0MPa or 1.5MPa to 2.0MPa usually) of pressure limit.
With reference to Fig. 2, first reformer 14 can be through being heated above the temperature of 630 ℃ or 650 ℃ to 900 ℃ or 700 ℃ to 800 ℃ via pipeline 96 and effluent exchanged heat from catalyzing part oxidation reformer 20.Pipeline 96 operationally is coupled to heat exchanger 98.Heat exchanger 98 can be the part of pipeline 96.Heat exchanger 98 can be arranged in first reformer 14 or be connected to first reformer so that can with the hydrocarbon stream exchanged heat that gets into said first reformer.Can control the speed that effluent self-catalysis partial oxidation reformer 20 is delivered to first reformer 14 with threeway metering valve 102 through adjustment metering valve 100.
Under the temperature of at least 500 ℃ or 550 ℃ to 950 ℃ or 600 ℃ to 800 ℃ or 650 ℃ to 750 ℃, in first reformer 14, contact at least a portion of hydrocarbon stream, steam, catalyst and anode exhaust stream cleavable and/or the said hydrocarbon of reforming and form charging.Hydrocarbon in cracking and/or the reformation hydrocarbon stream reduces the number of the carbon atom in the hydrocarbon compound in the hydrocarbon stream, therefore produces the hydrocarbon compound of the molecular weight with minimizing.In one embodiment, hydrocarbon stream can comprise the hydrocarbon that contains at least 5 or at least 6 or at least 7 carbon atoms, and it is converted into 4 or 3 or the hydrocarbon of 2 carbon atoms at the most at the most of containing at the most that can be used as to the charging of second reformer 16.In one embodiment; Hydrocarbon in the said hydrocarbon stream can react in the reformer section of first reformer 14 or said first reformer so that the charging that produces from said first reformer can by no more than 0.1 no more than 0.05 or the hydrocarbon with four carbon atom or more carbon atoms of no more than 0.01 molfraction form.In one embodiment, the hydrocarbon in the hydrocarbon stream can be by cracking and/or reformation, so that the gained hydrocarbon of at least 0.7 or at least 0.8 or at least 0.9 or at least 0.95 molfraction in the charging that the hydrocarbon in hydrocarbon stream produces is a methane.In one embodiment, the hydrocarbon in the generation of the hydrocarbon in cracking and/or the reformation hydrocarbon stream charging has 1.3, at the most 1.2 or at the most 1.1 average carbon number purpose charging at the most.
As stated, suppress the formation of coke in first reformer from the hydrogen of anode exhaust stream and steam and the optional steam that is added into first reformer 14 when forming charging at the cracking hydrocarbon.One preferred embodiment in; Select anode exhaust stream, hydrocarbon stream and steam to be delivered to the relative speed of first reformer 14, so the hydrogen in the anode exhaust stream is added into the formation of steam prevention coke in said first reformer of said first reformer with steam and via pipeline 84.
In one embodiment; Some reformation at least of the charging that is produced in the hydrocarbon that under the temperature of at least 500 ℃ or 550 ℃ to 700 ℃ or 600 ℃ to 650 ℃, hydrocarbon stream, steam and anode exhaust is contacted also can to realize in the hydrocarbon stream with reforming catalyst and first reformer 14 and produce hydrogen and oxycarbide (specifically, carbon monoxide).The amount of reforming can be in a large number, and the charging that wherein in the reformer section of first reformer 14 or said first reformer, is produced by cracking and reformation can contain the carbon monoxide of at least 0.05 or at least 0.1 or at least 0.15 molfraction.
Can select the temperature and pressure condition in the reformer section of first reformer 14 or said first reformer, the charging that is therefore produced in said first reformer is included in 20 ℃ down for gaseous state, contain the lighter hydrocarbons of 1 to 4 carbon atom usually.One preferred embodiment in, the hydrocarbon in the charging (hereinafter referred to as " steam reformation charging ") that is produced by said first reformer is made up of the methane of 0.6 or 0.7 or 0.8 or 0.9 molfraction at least at least at least at least.The steam reformation charging also comprises the hydrogen from anode exhaust stream, and if in first reformer, realize further reforming, then comprise hydrogen from the hydrocarbon of reforming.The steam reformation charging also comprises from anode exhaust stream and optional steam from the reformer steam feed.If realize a large amount of the reformation in the reformer section of first reformer 14 or said first reformer, then provide to the charging that produces from said first reformer of second reformer 16 to comprise that carbon dioxide also comprises carbon monoxide.
In the method for the invention, the steam reformation charging provides to second reformer 16 that may be operably coupled to said first reformer through pipeline 70 from first reformer 14.The steam reformation charging of leaving first reformer 14 can have the temperature of 500 ℃ to 650 ℃ or 550 ℃ to 600 ℃.Before the steam reformation charging that will leave first reformer 14 is delivered to second reformer 16, can through before being delivered to second reformer 16 in one or more heat exchangers 90 exchanged heat reduce the temperature of the said steam reformation charging of leaving first reformer.Randomly, before getting into said second reformer, do not cool off said steam reformation charging.At first reformer 14 (for example through other source; As shown in Figure 2; Steam and/or heat from catalyzing part oxidation reformer 20) in the execution mode of heating, the charging of leaving first reformer can have the temperature of 650 ℃ to 950 ℃ or 700 ℃ to 900 ℃ or 750 ℃ to 800 ℃.
Can be through cooling off said steam reformation charging with being delivered to water exchanged heat in the said system, cooling charging and producing the steam that can be delivered to like described first reformer 14 of preceding text.If utilize more than a heat exchanger 90, then said steam reformation charging and water/steam can be delivered to each in the heat exchanger successively, preferably with convection type to cool off said charging and to heat said water/steam.Can said steam reformation charging be cooled to the temperature of 150 ℃ to 650 ℃ or 150 ℃ to 300 ℃ or 400 ℃ to 650 ℃ or 450 ℃ to 550 ℃.
But the steam reformation charging automatic heat-exchanger 90 through cooling is delivered to compressor 94, or can directly be delivered to second reformer 16 in another embodiment.Selectively (but more not preferred), the steam reformation charging of leaving the reformer section of first reformer 14 or said first reformer can promptly be delivered to the compressor 94 or second reformer 16 without cooling.The compressor of compressor 94 for can at high temperature operating, and be preferably the StarRotor compressor that can buy from market.The steam reformation charging can have pressure and 400 ℃ to 800 ℃ of 0.5MPa at least, preferred 400 ℃ to 650 ℃ temperature.Said steam reformation charging can be compressed to 0.5MPa or 1.0MPa or 1.5MPa or 2MPa or 2.5MPa or the pressure of 3MPa at least at least at least at least at least at least by compressor 94, with the sufficient pressurising force in the reformer section 108 of keeping second reformer 16.In one embodiment, incoming flow is being provided to second reformer, said steam reformation charging is being compressed to the pressure of 0.5MPa to 6.0MPa.
To comprise that the optional compression of hydrogen, lighter hydrocarbons, steam and optional carbon monoxide, the steam reformation charging of optional cooling are delivered to second reformer 16.Said steam reformation charging can have pressure and 400 ℃ to 800 ℃ of 0.5MPa at least, preferred 400 ℃ to 650 ℃ temperature.In one embodiment; If necessary, then can, the steam reformation charging that is produced by first reformer 14 pass the temperature that heat exchanger 90 and/or 72 increases the steam reformation charging that is produced by said first reformer after leaving compressor 94 through the part circulation that makes said charging.
Randomly, if for the said charging of reforming for necessary, then can extra steam be added in the reformer section 108 of second reformer 16, mix with said steam reformation charging being used for by said first reformer generation.One preferred embodiment in, can water under high pressure is injected in the compressor 94 from water inlet pipeline 88 add extra steam through passing pipeline 110, mix with said charging when the said charging of said compressor compression being used for.In an execution mode (not shown), can said water under high pressure be injected in the said charging through in heat exchanger 90, water under high pressure being mixed with charging.In another execution mode (not shown), can before or after said charging is passed to heat exchanger 90 or before or after said charging is passed to compressor 94, in pipeline 110, water under high pressure be injected in the charging.In one embodiment, can water under high pressure be injected in the pipeline 70, or be injected in the compressor 94, or be injected in the heat exchanger 90, wherein said compressor or said heat exchanger are not contained in the said system.
Said water under high pressure heats with formation steam through mixing with the steam reformation charging, and said steam reformation charging is cooled off through mixing with said water.Provide to cooling wherein and can eliminate or reduce the demand to heat exchanger 90 through being injected in water in the steam reformation charging, the numerical limitations of heat exchanger that preferably will be used for the cooling steam catalytic reforming feedstock is to one at the most.
Selectively (but more not preferred) can be injected to high steam in the reformer section 108 of second reformer 16 or be injected to the pipeline 70 of said second reformer, to mix with the steam reformation charging.High steam can be through heating in heat exchanger 90 (through with the charging exchanged heat of leaving first reformer 14) pass water inlet pipeline 88 and be injected to the steam that the water under high pressure in the said system produces.High steam can be delivered to second reformer 16 through pipeline 112.Metering valve 114 can be used for controlling steam flowing to said second reformer.Said high steam can have the pressure of the pressure that is similar to the charging that just is transported to said second reformer.Selectively, said high steam can be transported to pipeline 70, to be transported to compressor 94 in said charging before, mix with said charging, so steam can be compressed to selected pressure with the mixture of charging.Said high steam can have 200 ℃ to 500 ℃ temperature.
Can select and control water under high pressure or high steam and be delivered to speed in the said system will the reaction of optimizing in the reformer being provided to first reformer 14 and/or second reformer 16 to produce the effective quantity of steam of hydrogen-containing gas streams.Can provide to the speed of first reformer 14 through adjustment metering valve 116 and 118 (its control water is delivered to the speed of said system) or through adjusting the steam that metering valve 86,120 and 114 (it controls the speed that steam is delivered to first reformer 14, second reformer 16) controls will the steam in anode exhaust stream.Can steam be supplied to the additional assemblies (for example, turbine) in the said system.
If water under high pressure is injected in second reformer 16, then adjustable gauge metered valve 114 and 120 is injected to the speed in second reformer with control water through pipeline 112.If high steam is injected in second reformer 16 or is injected in the pipeline 70, then adjustable gauge metered valve 114,116 and 118 is with in control vapor injection to the second reformer 16 or be injected to the speed in the pipeline 70.Can adjust flowing of steam and be at least 2: 1 or at least 2.5: 1 or at least 3: 1 or at least 3.5: 1 with the molar ratio that steam and carbon are provided.
To be delivered in the reformer section 108 of second reformer 16 with (choosing wantonly) extra steam through the steam reformation charging that first reformer produces.Said reformer section can and preferably contain reforming catalyst really therein.Said reforming catalyst can be conventional steam reforming catalyst, and can be known in the prior art.Spendable typical steam reforming catalyst comprises but is not limited to VIII group 4 transition metal, specifically nickel.Usually can expect said reforming catalyst is carried on the fire-resistant matrix (or carrier).Said carrier (if use) is preferably inert compound.The III and IV family element, the for example oxide of Al, Si, Ti, Mg, Ce and Zr or the carbide that contain the periodic table of elements as the suitable inert compound of carrier.
The extra steam of said steam reformation charging and (choosing wantonly) mixes with reforming catalyst in reformer section 108 under the product gas efficient temperature to the reformation that forms hydrogeneous and carbon dioxide and contacts.The product gas of said reformation can form through the hydrocarbon in the steam reformation charging.The product gas of said reformation also can form and/or produce through the said charging of steam reformation through making the carbon monoxide generation water gas shift reaction in steam and the charging.In one embodiment, contain a large amount of carbon monoxide if realized a large amount of reformations and said steam reformation charging in the reformer section of first reformer 14 or said first reformer, then second reformer 16 can more serve as water-gas shift reactor.The product gas of said reformation comprises hydrogen and at least a oxycarbide.In one embodiment, the product gas of said reformation comprises gaseous hydrocarbon, hydrogen and at least a oxycarbide.The oxycarbide that can be in the product gas of said reformation comprises carbon monoxide and carbon dioxide.
In one embodiment, from the heat of the effluent of catalyzing part oxidation reformer 20 can with just provide to and/or the steam reformation incoming flow that is in the reformer section 108 carry out heat exchange.Can be the scope of 750 ℃ to 1050 ℃ or 800 ℃ to 1000 ℃ or 850 ℃ to 900 ℃ from the temperature of the effluent of catalyzing part oxidation reformer 20.From the heat of said effluent can the reformer section 108 of second reformer 16 be heated to about 500 ℃ to about 850 ℃ or about 550 ℃ to 700 ℃ temperature.Temperature in the reformer section 108 of second reformer 16 can be enough to reform from all or all charging basically of first reformer 14, comprises the product gas of the reformation of hydrogen and at least a oxycarbide with generation.
The product gas of said reformation can get into the high temperature hydrogen separator 18 that operationally is coupled to second reformer 16.As depicted in figs. 1 and 2, high temperature hydrogen separator 18 is the part of second reformer 16.As shown in Figure 3, high temperature hydrogen separator 18 separates with second reformer 16 and operationally is coupled to second reformer via pipeline 122.
High temperature hydrogen separator 18 can comprise one or more high temperature tubulose hydrogen separating films 68.Film 68 can be arranged in the reformer section 108 of second reformer 16, but and through locating so that the product gas contact membrane 68 of said charging and reformation.Hydrogen can pass the membrane wall (not shown) of film 68 to the hydrogen conduit 124 that is positioned at film 68.The membrane wall of each film with hydrogen conduit 124 from the reformer section 108 of second reformer 16 in product gas, charging and the steam of reformation in the gas of non-hydrogen compound be communicated with and separate.Membrane wall is optionally permeable to hydrogen (element and/or molecule), makes the hydrogen in the reformer section 108 can pass membrane wall to the hydrogen conduit 124 of film 68, and other gas in the reformer section then is prevented from being passed to the hydrogen conduit through said membrane wall.Can increase or reduce the hydrogen flux of crossing over high temperature hydrogen separator 18 through the pressure of adjusting in second reformer 16.Pressure in second reformer 16 can be delivered to the rate controlled of first reformer 14 by anode exhaust stream.
With reference to Fig. 3, be delivered to high temperature hydrogen separator 18 via pipeline 122 from the charging of second reformer 16.High temperature hydrogen separator 18 can comprise the optionally permeable member of hydrogen (being molecule or element form).One preferred embodiment in, said high temperature hydrogen separator comprises the optionally permeable film of hydrogen.In one embodiment, the high temperature hydrogen separator comprises tubular film, and it is coated with optionally permeable palladium of hydrogen or palldium alloy.
The air-flow that gets into high temperature hydrogen separator 18 via pipeline 122 can comprise hydrogen, oxycarbide and hydrocarbon.Said air-flow can contact tubulose hydrogen separating film 68, and hydrogen can pass membrane wall to the hydrogen conduit 124 that is positioned at film 68.Said membrane wall separates hydrogen conduit 124 from being communicated with the gas of non-hydrogen compound; And it is optionally permeable to hydrogen (element and/or molecule); Make the hydrogen that is got in the gas can pass said membrane wall to hydrogen conduit 124, other gas then is prevented from being passed to said hydrogen conduit through said membrane wall.
High temperature tubulose hydrogen separating film 68 among Fig. 1 and Fig. 2 can comprise carrier, and it is coated with the hydrogen thin layer of permeable metal or alloy optionally.Said carrier can be formed by the pottery or the metal material of permeation hydrogen.Porous stainless steel or Woelm Alumina are the preferred material that is used for the carrier of film 68.Be coated on the said carrier hydrogen optionally metal or alloy can be selected from following VIII family metal, comprise but be not limited to Pd, Pt, Ni, Ag, Ta, V, Y, Nb, Ce, In, Ho, La, Au and Ru (specifically being alloy form).Palladium and palldium alloy are preferred.Employed preferred especially film 68 has palladium alloy membrane as thin as a wafer in this method, and said film has the high surface that applies the porous stainless steel carrier.Use disclosed method in No. the 6th, 152,987, the United States Patent (USP) can prepare the film of this type.Having the platinum of high surface or the film of platinum alloy will also be suitable for as the hydrogen selective material.
Pressure in the reformer section 108 of second reformer 16 is maintained the level of the pressure in the hydrogen conduit 124 that is significantly higher than tubular film 68, so that force hydrogen to pass in membrane wall to the hydrogen conduit 124 from the reformer section 108 of second reformer 16.In one embodiment, hydrogen conduit 124 is kept under atmospheric pressure or near atmospheric pressure, and reformer section 108 is maintained 0.5MPa at least or 1.0MPa or 2MPa or at least under the pressure of 3MPa at least at least.As stated, can reformer section 108 be maintained under the pressure of raising through being injected in the reformer section 108 from the charging of first reformer 14 and the incoming mixture that will be in high pressure with compressor 94 compression.Selectively, can be through making high steam and described charging mixes and high-pressure mixture is injected in the reformer section 108 of second reformer 16 reformer section 108 is kept under high pressure like preceding text.Selectively, can reformer section 108 be kept under high pressure through in the reformer section of first reformer 14 or said first reformer, high steam being mixed with hydrocarbon stream and the high pressure charging that is produced in said first reformer being injected in second reformer 16 directly or through one or more heat exchangers 90.Can the reformer section 108 of second reformer 16 be maintained 0.5MPa at least or 1.0MPa or 2.0MPa or at least under the pressure of 3.0MPa at least at least.
Steam reformation charging and optional extra steam in the reformer section 108 of second reformer 16, mix with reforming catalyst and when contacting residing temperature be at least 400 ℃, and preferably can be 400 ℃ to 650 ℃ scope, most preferably 450 ℃ to 550 ℃ scope.Typical steam reformer under 750 ℃ or higher temperature operation to obtain sufficiently high equilibrium conversion.In the method, through hydrogen is removed to the hydrogen conduit 124 of film 68 (and therefore removing from second reformer 16) continuously from reformer section 108, in 400 ℃ to 650 ℃ reformer operation temperature range, to drive the generation of reforming reaction towards hydrogen.In this way, this method can obtain the conversion completely that is close to of reactant to hydrogen under the situation of no equilibrium-limited.400 ℃ to 650 ℃ operating temperature also helps transfer reaction, thereby is more hydrogen with carbon monoxide and steam-reforming, passes the membrane wall of film then said hydrogen is removed to hydrogen conduit 124 from reformer section 108.Can realize in second reformer 16 that this is because owing to remove dehydrogenation continuously and will never reach balance from said second reformer through reforming and the hydrocarbon of water gas shift reaction and the intimate conversion fully of carbon monoxide to hydrogen and carbon dioxide.
In one embodiment, provide steam reformation feed heat to second reformer 16 to drive the reaction in said second reformer from the reformer section of first reformer 14 and/or said first reformer.Can contain sufficient heat energy driving the reaction in said second reformer to the steam reformation charging that produces from the reformer section of first reformer 14 and/or said first reformer of second reformer 16, and can have 400 ℃ to 950 ℃ temperature.Heat energy from the steam reformation charging that the reformer section of first reformer 14 and/or said first reformer produces can exceed the required heat energy of reaction that drives in second reformer 16; And such as preceding text description, can be in heat exchanger 90 before said charging being delivered to second reformer 16 and/or through with in water injection to the said charging said charging being cooled to 400 ℃ to the temperature less than 600 ℃.Have be in or near the charging of the required temperature of second reformer 16 for preferred, make 1) can adjust temperature in second reformer 16 to help the generation of hydrogen in water gas shift reaction; 2) can prolong life-span of film 68; And the 3) usefulness of improved compressor 94.Heat energy is quite effective from the transmission of first reformer, 14 to second reformers 16, and this is to be contained in the said charging because of the heat energy from first reformer, and the reaction in said second reformer is participated in said charging nearly.
In high temperature hydrogen separator 18, form hydrogeneous stream through optionally making hydrogen pass the product gas of reforming with the product gas and the hydrogen-containing gas streams cause of separation reformation in membrane wall to the hydrogen conduit 124 of hydrogen separating film 68.Hydrogen-containing gas streams can contain high hydrogen concentration, and can contain the hydrogen of at least 0.9 or at least 0.95 or at least 0.98 molfraction.
Because hydrogen passes the high flux of hydrogen separating film 68, therefore can separate hydrogen-containing gas streams from the product gas of reforming with relative two-forty.In one embodiment, residing temperature is at least 300 ℃ or about 350 ℃ to about 600 ℃ or 400 ℃ to 500 ℃ during the product gas through hydrogen separating film 68 separation of hydrogen and reformation.Because hydrogen is present in second reformer 16 with high partial pressures, so hydrogen passes hydrogen separating film 68 with high flux speed.The high partial pressures of the hydrogen in second reformer 16 be because: 1) be delivered to first reformer 14 and in charging, be passed to a large amount of hydrogen in the anode exhaust stream of second reformer; 2) in first reformer, produce and be delivered to the hydrogen of second reformer; With 3) hydrogen through reforming with the transfer reaction generation in second reformer.Because therefore the two-forty that hydrogen separates from the product of reforming does not need residual gas to assist hydrogen to remove and shift out high temperature hydrogen separator 18 from hydrogen conduit 124.
To shown in Figure 2, hydrogen-containing gas streams leaves high temperature hydrogen separator 18 and enters the mouth to anode through pipeline 126 and 34 via hydrogen conduit 124 and gets into the anode 24 of molten carbonate fuel cell 12 in 30 like Fig. 1.Selectively, said hydrogen-containing gas directly is delivered to anode inlet 30 via pipeline 126.Said hydrogen stream provides hydrogen to anode 24, to be implemented in along the one or more anode electrodes place of the anode path in the fuel cell 12 and the electrochemical reaction of oxidant.The dividing potential drop that gets into the molecular hydrogen of second reformer 16 is higher than the dividing potential drop of the molecular hydrogen in the hydrogen-containing gas streams that leaves high temperature hydrogen separator 18.Second reformer 16 and leave partial pressure difference between the dividing potential drop of the molecular hydrogen in the hydrogen-containing gas streams of high temperature hydrogen separator 18 and drive reforming reaction and/or water gas shift reaction to process more hydrogen.In some embodiments, can residual gas (for example, steam) be injected in the hydrogen conduit so that hydrogen is removed to the hydrogen conduit from the interior section of membrane wall member, therefore increasing can be through the speed of hydrogen separating film from said reformer section separation of hydrogen.
Before hydrogen-containing gas streams is delivered to anode 24, can said hydrogen-containing gas streams or its part be delivered to heat exchanger 72 with heating hydrocarbon stream and cooled hydrogen stream via pipeline 128.After leaving high temperature hydrogen separator 18, said hydrogen-containing gas streams can have 400 ℃ to 650 ℃ temperature (being generally 450 ℃ to 550 ℃ temperature).The pressure that leaves the hydrogen-containing gas of high temperature hydrogen separator 18 can have the pressure of about 0.1MPa or 0.01MPa to 0.5MPa or 0.02MPa to 0.4MPa or 0.3 to 0.1MPa.One preferred embodiment in, the hydrogen-containing gas streams that leaves high temperature hydrogen separator 18 has about 450 ℃ temperature and the pressure of about 0.1MPa.The pressure and temperature that leaves the hydrogen-containing gas streams of high temperature hydrogen separator 18 can be suitable for directly said hydrogen-containing gas streams directly being delivered to the anode inlet 30 of molten carbonate fuel cell 12.
Can choose wantonly through in heat exchanger 72 with hydrogen stream exchanged heat and optional through as hereinafter is described and carbon dioxide gas stream exchanged heat heats hydrocarbon stream.With select and control is delivered to the temperature combinations that contains oxidizer flow of the negative electrode 26 of molten carbonate fuel cell 12, can the hydrogen stream of the anode that is delivered to molten carbonate fuel cell 12 24 be cooled at the most 400 ℃ or at the most 300 ℃ at the most 200 ℃ or at the most 150 ℃ the temperature of temperature or 20 ℃ to 400 ℃ or 25 ℃ to 250 ℃ be controlled at 600 ℃ to 700 ℃ scope with operating temperature with molten carbonate fuel cell.Usually can be through in heat exchanger 72, hydrogen-containing gas streams or its part being cooled to 200 ℃ to 400 ℃ temperature with hydrocarbon stream exchanged heat.Randomly; Can be through hydrogen stream or its a part of automatic heat-exchanger 72 be passed to one or more extra heat exchanger (not shown)s, further come the further said hydrogen stream of cooling or its part with in said one or more extra heat exchangers each with hydrocarbon stream or with water flow exchange heat.If adopt extra heat exchanger in the said system, then said hydrogen stream or its part can be cooled to 20 ℃ to 200 ℃, preferred 25 ℃ to 100 ℃ temperature.In one embodiment; The part of hydrogen stream can be cooled off with choosing wantonly in one or more extra heat exchangers at heat exchanger 72; And the part of said hydrogen stream can be not in heat exchanger cooling promptly be delivered to the anode 24 of molten carbonate fuel cell 12, the built-up section of wherein said hydrogen stream can be at 400 ℃ or 300 ℃ or 200 ℃ or be delivered to the anode of said fuel cell at the most under 150 ℃ the temperature of temperature or 20 ℃ to 400 ℃ or 25 ℃ to 100 ℃ at the most at the most at the most.
Can select and control said hydrogen stream or its part to heat exchanger 72,22 and optional flow velocity, be delivered to the temperature of hydrogen stream of the anode 24 of molten carbonate fuel cell 12 with control to one or more extra heat exchangers.Can select and control the flow velocity of hydrogen stream or its part to heat exchanger 22 and optional extra heat exchanger through adjustment metering valve 36,130 and 132.Adjustable gauge metered valve 36 and 130 is with the flowing of the anode 24 of control hydrogen stream or its part through pipeline 126 to molten carbonate fuel cell 12, and do not cool off said hydrogen stream or its part.Metering valve 130 is flowing of may command hydrogen stream or its part to heat exchanger 22 also.Adjustable gauge metered valve 132 is with control hydrogen stream or its part flowing through pipeline 128 to heat exchanger 72 and the extra heat exchanger of choosing wantonly.Tunable ground adjustment metering valve 130 and 132 is to provide required cooling degree to said hydrogen stream before the anode that hydrogen stream is delivered to molten carbonate fuel cell 12 24.The feedback of temperature that in one embodiment, can be adapted to leave anode exhaust stream and/or the cathode exhaust stream of fuel cell 12 is measured and metering valve 130 and 132 is adjusted on automatic synchronization ground.Said hydrogen stream with hydrogen provide to anode 24 to be implemented in along the one or more anode electrodes place of the anode path in the fuel cell 12 and the electrochemical reaction of oxidant.Can select hydrogen stream to be delivered to the speed of the anode 24 of molten carbonate fuel cell 12 through the speed of selecting charging to be delivered to second reformer 16; And the speed that charging is delivered to second reformer 16 can be selected through the speed that hydrocarbon stream is delivered to first reformer 14, and hydrocarbon stream is delivered to the speed of first reformer 14 and can controls through adjustment hydrocarbon stream inlet valve 106.
The arbitrary part that is delivered to the heat exchanger 72 and the hydrogen-containing gas streams of optional extra heat exchanger can be carried from said heat exchanger or through last the extra heat exchanger that is used to cool off said hydrogen-containing gas streams, and arbitrary part of wherein said hydrogen stream is sent to the anode of molten carbonate fuel cell around said heat exchanger.In one embodiment, can in the compressor (not shown), compress the built-up section of said hydrogen-containing gas streams or leave the pressure of the hydrogen-containing gas streams of high temperature hydrogen separator 18, and can said hydrogen stream be delivered to said anode subsequently with the increase hydrogen stream.In one embodiment, can said hydrogen stream be compressed to 0.15MPa to 0.5MPa or 0.2MPa to 0.3MPa or be up to 0.7MPa or be up to the pressure of 1MPa.Can through such as hereinafter expansion and/or the high steam that passes one or more turbines of the high-pressure carbon dioxide stream that forms of description provide and drive all the required energy of said compressor or the part of said energy.
Selectively, can be through selecting hydrogen stream to be delivered to the speed of the anode 24 of molten carbonate fuel cell 12 with coordination mode control metering valve 36 and 134.Adjustable gauge metered valve 36 is to increase or to reduce flowing in hydrogen stream to the anode 24.Adjustable gauge metered valve 134 is to increase or to reduce flowing of hydrogen stream to hydrogen source 64.Can control metering valve 36 and 134 with coordination mode; So that the hydrogen stream of selected speed can be delivered to the anode 24 of molten carbonate fuel cell 12 through pipeline 34, and a part that exceeds the hydrogen stream of the amount that the required hydrogen stream of said selected speed is provided can be delivered to hydrogen source 64 through pipeline 136.
Can remove the product gas flow of the reformation that dehydrogenation exhausts from high temperature hydrogen separator 18 via pipeline 48, the product gas flow of the reformation that wherein said hydrogen exhausts can comprise the product of the non-hydroforming of gaseous state in the product gas of unreacted feed and said reformation.The product of said non-hydroforming and unreacted feed can comprise carbon dioxide, water (as steam) and a small amount of carbon monoxide and unreacted hydrocarbon.Also can contain little hydrogen in the product gas flow of the reformation that hydrogen exhausts.
In one embodiment, the product gas flow of leaving the reformation that the hydrogen of high temperature hydrogen separator 18 exhausts can be the carbon dioxide gas stream of the carbon dioxide that on dry-basis, contains at least 0.8 or at least 0.9 or at least 0.95 or at least 0.98 molfraction.Said carbon dioxide gas stream is to have 0.5MPa or 1MPa or the 2MPa or the high pressure draught of the pressure of 2.5MPa at least at least at least at least.Hereinafter, the product gas of the reformation that exhausts of hydrogen will be called as the high-pressure carbon dioxide air-flow.The temperature of high-pressure carbon dioxide air-flow of leaving hydrogen separator 18 is at least 400 ℃ or be generally 425 ℃ to 600 ℃ or 450 ℃ to 550 ℃.
The high-pressure carbon dioxide air-flow can leave high temperature hydrogen separator 18, and is delivered to the negative electrode 26 of fuel cell 12 via pipeline 48 and 44.As shown in the figure, the high-pressure carbon dioxide air-flow passes heat exchanger 22, and can be used for the heated oxidant air-flow.In one embodiment, the part of said carbon-dioxide flow is directly mixed with the oxidizer flow that gets into negative electrode 26 via pipeline 44.
One preferred embodiment in, via pipeline 48 with high-pressure carbon dioxide gas delivery to catalyzing part oxidation reformer 20.In catalyzing part oxidation reformer 20; Residual hydrocarbons in the carbon-dioxide flow (for example; Methane, ethane and propane) under the situation that exists via the oxygen of pipeline 56 autoxidator sources, 42 inputs or air, burn, pass heat exchanger 22 and be delivered to the hot effluent combustion flow of negative electrode 26 via pipeline 44 to form via pipeline 138.In one embodiment, combustion flow directly is delivered to negative electrode 26 via pipeline 138 and 44.The amount that is delivered to the molecular oxygen in the stream that contains oxidant of catalyzing part oxidation reformer 20 is at least 0.9 times of the required stoichiometry of the hydrocarbon completing combustion in the carbon-dioxide flow but no more than 1.1 times.
Hot combustion flow can comprise great amount of carbon dioxide, but also can comprise the nitrogen G&W.The hot combustion flow of leaving catalyzing part oxidation reformer 20 can have the temperature of the scope of at least 750 ℃ to 1050 ℃ or 800 ℃ to 1000 ℃ or 850 ℃ to 900 ℃.Heat from hot combustion gas can exchange with the air-flow that contains oxidant with the hydrogen-containing gas streams exchange and/or in said heat exchanger in heat exchanger 22.As shown in Figure 2, from leave catalyzing part oxidation reform 20 combustion flow heat at least a portion can via pipeline 96 in heat exchanger 98 with 14 exchanges of first reformer.
In one embodiment, hot combustion gas can directly be delivered to cathode exhaust gas inlet 38.Can adjust the temperature of the gas that contains oxidant so that leave the temperature of the cathode exhaust stream of said fuel cell is 550 ℃ to 700 ℃.Can and/or heat the gas temperature that will contain oxidant through cooling in heat exchanger 22 and be adjusted to 150 ℃ to 450 ℃ temperature.Can control air-flow the flowing that contains oxidant through adjustment metering valve 46,58 and 140 from high temperature hydrogen separator 18 to heat exchanger 22 and/or catalyzing part oxidation reformer 20.
Leave catalyzing part oxidation at hot burning gas stream and reformed 20 o'clock, it can contain a large amount of water as steam.In one embodiment, can come to remove devaporation through heat of cooling combustion-gas flow in heat exchanger 22 and/or in heat exchanger 72 and (if desired) one or more extra heat exchanger (not shown)s and by steam condensate (SC) from said hot burning gas stream.
Through hydrocarbon stream pipeline 62 hydrocarbon stream is delivered to the high-pressure carbon dioxide air-flow that is used in the heat exchanger 72 from high temperature hydrogen separator 18 simultaneously and heats said hydrocarbon stream through making carbonated air-flow pass pipeline 142 to heat exchanger 72.Can control hot, high pressure carbonoxide stream flowing through adjustment metering valve 144 by high temperature hydrogen separator 18 to heat exchanger 72.Adjustable gauge metered valve 144 flow to flowing of heat exchanger 72 with the control carbon dioxide, so that said hydrocarbon stream is heated to selected temperature.Can said hydrocarbon stream be heated to uniform temperature, so that said hydrocarbon stream has the temperature of at least 150 ℃ or 200 ℃ to 500 ℃ when said hydrocarbon stream is transported to first reformer 14.
Can adjust metering valve 46,58 and 140 automatically through feedback mechanism; The temperature that wherein said feedback mechanism can be measured the temperature of the cathode exhaust stream that leaves fuel cell 12 and/or get into the hydrocarbon stream of first reformer 14; And adjustment metering valve 46,58 and 140 with said cathode exhaust stream and/or the temperature maintenance of hydrocarbon stream that gets into first reformer 14 in setting restriction, simultaneously the internal pressures in second reformer 16 and/or the high temperature hydrogen separator 18 are maintained desired level.
Hydrogen stream and the oxidant (carbanion) that produces through the reaction of oxygen and carbon dioxide at the negative electrode place preferably mix at one or more anode electrodes place of fuel cell 12 (such as preceding text description) with 0.1W/cm at least 2, more preferably 0.15W/cm at least 2, or 0.2W/cm at least 2Or 0.3W/cm at least 2Electrical power density produce.Can produce with such electrical power density through speed and the speed of the negative electrode 26 of gas delivery to the fuel cell 12 that contains oxidant selected and the control hydrogen stream is delivered to the anode 24 of fuel cell 12.Can select and be controlled to the flow velocity of the air-flow that contains oxidant of the negative electrode 26 of fuel cell 12 through adjustment oxidant gas inlet valve 46.
Such as preceding text description; Can select and control the flow velocity of the anode 24 of hydrogen stream to fuel cell 12 through the speed of selecting and control is delivered to second reformer 16 with charging; And the speed that charging is delivered to second reformer 16 can be selected and control through the speed that hydrocarbon stream is delivered to first reformer 14, and the speed that hydrocarbon stream is delivered to first reformer 14 can be selected and controls through adjustment hydrocarbon stream inlet valve 106.Selectively, such as preceding text description, can be through selecting and control the speed that hydrogen stream is delivered to the anode 24 of fuel cell 12 with coordination mode control metering valve 36,130,132 and 134.In one embodiment; Can come adjustment metering valve 36,130,132 and 134 automatically through feedback mechanism; Keeping the selected flow velocity of hydrogen stream to anode 24, wherein said feedback mechanism can be based on formed water in the hydrogen content in the antianode exhaust stream or water content in the anode exhaust stream or the said fuel cell for the measurement of the ratio of the hydrogen in the said anode exhaust stream and operate.
In the method for the invention, the part and the oxidation of said oxidant that hydrogen stream and oxidant are mixed through being present in the hydrogen in the said hydrogen stream that is delivered to fuel cell 12 at one or more anode electrodes place produce water (as steam).Water by the oxidation of hydrogen and oxidant produces is removed the anode 24 that passes fuel cell 12 through the non-reacted parts of hydrogen stream, to leave anode 24 as the part of anode exhaust stream.
In an execution mode of method of the present invention; Can select and control the flow velocity that hydrogen stream is delivered to anode 24, so the ratio of the amount of amount and the hydrogen in the time per unit anode exhaust of formed water is at the most 1.0 or at the most 0.75 or at the most 0.67 or at the most 0.43 or at the most 0.25 or at the most 0.11 in the time per unit fuel cell 12.In one embodiment; Can measure the amount of formed water in the fuel cell 12 and the amount of the hydrogen in the anode exhaust with mole, so that the ratio of the amount of the hydrogen in the amount of formed water and the said anode exhaust of time per unit is a time per unit in mole at the most 1.0 or at the most 0.75 or at the most 0.67 or at the most 0.43 or at the most 0.25 or at the most 0.11 in the said fuel cell of time per unit.In one embodiment, can select and control the flow velocity that hydrogen stream is delivered to anode 24, so the whenever logical Cheng Qing utilance in the fuel cell 12 is less than 50% or at the most 45% or at the most 40% or at the most 30% or at the most 20% or at the most 10%.
In another execution mode of method of the present invention, can select and control the flow velocity that hydrogen stream is delivered to anode 24, so anode exhaust stream contains the hydrogen of at least 0.6 or at least 0.7 or at least 0.8 or at least 0.9 molfraction.In another embodiment; Can select and control the flow velocity of the hydrogen stream that is delivered to anode 24, therefore said anode exhaust stream contain hydrogen in the hydrogen stream that is delivered to anode 24 greater than 50% or at least 60% or at least 70% or at least 80% or at least 90%.
In some embodiments, can select and control carbon-dioxide flow and be delivered to the flow velocity of negative electrode 26 so that the dividing potential drop of the carbon dioxide in the major part of the cathode portion of said molten carbonate fuel cell is higher than the dividing potential drop of the carbon dioxide in the major part of anode part of said molten carbonate fuel cell.In one embodiment, can select and control carbon-dioxide flow and be delivered to the flow velocity of negative electrode 26 so that leave the dividing potential drop of the dividing potential drop of the carbon dioxide in the cathode exhaust stream of said fuel cell greater than the carbon dioxide in the anode exhaust stream that leaves said fuel cell.Select and the flow velocity of control carbon dioxide so that molten carbonate fuel cell at least 75% at least 95% or basically the dividing potential drop of the carbon dioxide in all cathode portion be higher than at least 75%, 95% or the dividing potential drop of the carbon dioxide of all anode parts basically of said molten carbonate fuel cell.
Operate said molten carbonate fuel cell with under arbitrary air concentration and/or arbitrary hydrogen utilance with Δ P CO2Be controlled under the pressure that is higher than 0 place, it is not enough and strengthen the cell potential of said molten carbonate fuel cell to suppress the carbon dioxide of molten carbonate fuel cell.Can select and control carbon-dioxide flow be delivered to molten carbonate fuel cell 12 negative electrode 26 flow velocity so that the hydrogen utilance at the most 60%, at the most 50% or at the most 40%, at the most 30%, at the most 20% or at the most 10% o'clock as by equation (Δ P CO2)=(P CO2 c)-(P CO2 a) Delta (delta) of the partial pressure of carbon dioxide confirmed is for about 0 crust or be higher than 0 crust, 0.01 to 0.2 crust or 0.05 to 0.15 crust, and/or control is empty flows so that the molar ratio of carbon dioxide and molecular oxygen is about 2.
Embodiment
Set forth non-restrictive example below.
With detailed process simulation to UniSim
Figure BPA00001481538800391
simulation program (Honeywell) the structure molten carbonate fuel cell system of the present invention of the calculation combination of cell potential.The UniSim program is used to obtain material balance and energy balance data.Repeatedly separate said detailed process simulation to different hydrogen utilance values and other relevant system parameters.Said detailed process simulation output comprises the detailed composition data of all process streams that get into and leave molten carbonate fuel cell.
For high-temperature fuel cell, activation loss is little, and can in the actual current density range, obtain cell potential through only considering the loss of ohm and electrode.Therefore, the cell potential of molten carbonate fuel cell (V) is poor between (iR) of open circuit voltage (E) and loss, shown in equation (1).
V＝E-iR (1)
Wherein V and E have the unit of volt or millivolt, and i is current density (mA/cm 2) and R (Ω cm 2) be ohm (R that electrolyte, negative electrode and anode groups are lumped together Ohm), negative electrode (η c) and anode (η a) combination of resistance, shown in equation (2).
R＝R ohm+η c+η a (2)
E is obtained by nernst equation:
E＝E o+(RT/2F)ln(P H2P O2 0.5/P H2O)+(RT/2F)ln(P CO2 c/P CO2 a)
(3)
Embodiment 1 uses the described detailed process of preceding text to simulate to molten carbonate fuel cell system simulated battery voltage described herein current density and power density is formed, and wherein heats first reformer through anode exhaust, does not have other heating.For example, the system that Fig. 1 described.Heat the heat that is used for second reformer through exchanging with hot effluent from the catalyzing part oxidation reformer.Through using cathode exhaust gas to increase output temperature from the effluent of said catalyzing part oxidation reformer with preheating catalytic oxidation reformer air feed.
Embodiment 2 uses the described simulation of preceding text to come to molten carbonate fuel cell system simulated battery voltage described herein current density and power density formation, wherein heats first reformer through anode exhaust with from the heat of catalyzing part oxidation reformer.For example, system depicted in figure 2.
For embodiment 1 and 2, under the temperature of pressure and 650 ℃ of 1 crust (about 0.1MPa or about 1atm), operate said molten carbonate fuel cell.To flowing and mobile convection current of the charging of the negative electrode of said molten carbonate fuel cell to the charging of anode.Use air as oxygen source.Using the value of air to come under various hydrogen utilances, to produce carbon dioxide is 2 mol ratio to molecular oxygen.Operating condition, the steam of in table 1, having listed the percentage hydrogen utilance of the said molten carbonate fuel cell of embodiment 1 and 2 simulations, said first and second reformers transform the ratio of carbon and the percentage of benzene to hydrogen.From J.Power Sources 2002,112, the 509-518 page or leaf obtains the R in the equation 2, and is assumed to and equals 0.75 Ω cm 2
Will from be used for embodiment 1 and 2 the simulation data with by people such as Larmine at " Fuel Cell Systems Explained " (2003; Wiley & Sons, the 199th page) in the literature value of cell voltage, current density and power density of molten carbonate fuel cell of the prior art level described compare.
Table 1
Figure BPA00001481538800411
Fig. 4 describes cell voltage (mV) to current density (mA/cm to the molten carbonate fuel cell system of being simulated among the embodiment 1 and 2 2) and have the literature value as the molten carbonate fuel cell of the reformate of charging.Hydrogen utilance with 20% and 30% is operated said molten carbonate fuel cell.Data wire 160 is depicted in cell voltage (mV) under 20% the hydrogen utilance to current density (mA/cm to the molten carbonate fuel cell system of embodiment 1 and 2 2).Data wire 162 is depicted in cell voltage (mV) under 30% the hydrogen utilance to current density (mA/cm to embodiment 1 and 2 2).Data wire 164 to as by people such as Larmine at " Fuel Cell Systems Explained " (2003; Wiley & Sons, the 199th page) described in the molten carbonate fuel cell system of prior art level describe cell voltage (mV) to current density (mA/cm 2).As shown in Figure 4, for given current density, the cell voltage of molten carbonate fuel cell system described herein is higher than the cell voltage that has as the molten carbonate fuel cell of the prior art level of the reformate gas of charging.
Fig. 5 describes power density (W/cm to the molten carbonate fuel cell system of being simulated among the embodiment 1 and 2 that under 20% and 30% hydrogen utilance, operates 2) to current density (mA/cm 2) and have the literature value as the molten carbonate fuel cell of the reformate gas of charging.Data wire 166 is depicted in the power density (W/cm under 20% the hydrogen utilance to embodiment 1 and 2 2) to current density (mA/cm 2).Data wire 168 is depicted in power density (W/cm2) under 30% the hydrogen utilance to current density (mA/cm to embodiment 1 and 2 2).Data wire 170 to as describe power density (W/cm by the molten carbonate fuel cell system of the prior art level of people such as Larmine described in " Fuel Cell Systems Explained " (2003, Wiley & Sons, the 199th page) 2) to current density (mA/cm 2).As shown in Figure 5, for given current density, the power density of molten carbonate fuel cell system described herein is higher than the power density that has as the molten carbonate fuel cell of the reformate gas of charging.
Fig. 6 describes excess carbon dioxide (Δ P to embodiment 1 CO2(crust)) and total fuel cell current potential (mV) to the hydrogen utilance.Data wire 172 expression excess carbon dioxide values are (at given hydrogen utilance and 200mA/cm 2Current density under).Data 174 are illustrated in the average excess carbon dioxide value under the given hydrogen utilance.The total cell potential (mV) under given hydrogen utilance as confirming of the said fuel cell of data wire 176 expressions by nernst equation.As shown in Figure 6, along with the hydrogen utilance increases, Δ P CO2Reduce and cell potential increases, therefore the said fused carbonate fuel system of operation causes the cell potential of the enhancing of said molten carbonate fuel cell under less than 50% hydrogen utilance and under the carbon dioxide situation of flooding.
The carbon dioxide part of the fuel cell current potential (mV) of Fig. 7 depiction 6.Carbon dioxide part (for example, (RT/2F) ln (P of nernst equation of the cell potential (mV) of data wire 178 expression fuel cells CO2 c/ P CO2 a) part).As shown in Figure 7, when flooding the cathode portion of said fuel cell with carbon dioxide, the cell voltage of said fuel cell raises.For example, under 20% hydrogen utilance and with about 0.105 the said fuel cell of excess carbon dioxide Value Operations, total fuel cell current potential of 30mV is caused by said excess carbon dioxide.
Like Fig. 6 and shown in Figure 7, when providing to excessive (the Δ P of amount of the carbon dioxide of fuel cell CO2＞0) and during percentage hydrogen utilance low (for example) less than 35%, less than 30% or less than 20%, the cell potential maximization.Therefore; Under less than 50% hydrogen utilance, operate said fused carbonate fuel system and the cathode portion to said molten carbonate fuel cell is provided excess carbon dioxide; Make the dividing potential drop of the carbon dioxide in the major part of cathode portion of said molten carbonate fuel cell be higher than the dividing potential drop of the carbon dioxide in the major part of anode part of said molten carbonate fuel cell, and therefore strengthen the cell voltage of said molten carbonate fuel cell.
Embodiment 3 to the fusion carbonic acid fuel cell system that comprises first reformer that heats through anode exhaust (for example; System depicted in figure 1), use the described simulation of preceding text to confirm current density, cell voltage and the power density of the molten carbonate fuel cell of operation under 7 crust (about 0.7MPa or about 7atm).Under the temperature of pressure and 650 ℃ of 7 crust, operate said molten carbonate fuel cell with 20% or 30% hydrogen utilance.Said first reformer has 2.5 the steam ratio to carbon.Allow the variations in temperature of said first reformer.Has 500 ℃ the temperature and the pressure of 15 crust with second reformer of high temperature hydrogen separator combination.Use air as oxygen source.Use the value of air,, therefore minimize the cathode side concentration polarization so that the carbon dioxide in the negative electrode charging is stoichiometric to the ratio of molecular oxygen.In all scenario, use benzene as the carbon conversion values of the combination of the system of charging between 93% and 95%.The reaction heat that is used for second reformer by the integrated supply of said intrasystem heat.Independent item through calculating individually in the above equation 2 in the method described in the J.Electrochem.Soc. (Vol.138, No.12, in December, 1991) with C.Y.Yuh and J.R.Selman calculates R.For embodiment 3, calculating R is 0.57 Ω .cm 2
Fig. 8 is to describing cell voltage (mV) to current density (mA/cm like molten carbonate fuel cell depicted in figure 1 2).Data wire 180 is depicted in cell voltage (mV) under 20% the hydrogen utilance to current density (mA/cm 2).Data wire 182 is depicted in cell voltage (mV) under 30% the hydrogen utilance to current density (mA/cm 2).Fig. 4 and Fig. 8 are compared, under given current density, compare with the cell voltage of the molten carbonate fuel cell system of operation under 1 crust, the molten carbonate fuel cell system of operation is observed higher cell voltage under the pressure of about 7 crust.
Fig. 9 is to describing power density (W/cm like molten carbonate fuel cell system depicted in figure 1 2) to the state of current density and said molten carbonate fuel cell.Data wire 184 is depicted in the power density (W/cm under 20% the hydrogen utilance 2) to current density (mA/cm 2).Data wire 186 is depicted in the power density (W/cm under 30% the hydrogen utilance 2) to current density (mA/cm 2).Data point 188 to as describe power density (W/cm by the molten carbonate fuel cell system of the prior art level of J.R.Selman described in the Journal of Power Sources (2006, the 852 to 857 pages) 2) to current density (mA/cm2).As shown in Figure 9, at about 300mA/cm 2Current density under, the power density of molten carbonate fuel cell system described herein is higher than the power density of the molten carbonate fuel cell of said prior art level.
Embodiment 4 uses simulation mentioned above to compare as the methane of the fuels sources that is used for molten carbonate fuel cell system and the use of benzene, and wherein first reformer is heated by anode exhaust, does not have other heating.For example, system depicted in figure 1.Hot integrated through within the said system, supply is used for the reaction heat of second reformer.For these simulations, under the temperature of pressure and 650 ℃ of 1 crust (about 0.1MPa or about 1atm), operate said molten carbonate fuel cell.Use air as oxygen source.Using the value of air to come under various hydrogen utilances, to produce carbon dioxide is 2 molar ratio to molecular oxygen.The amount that is delivered to the fuel-feed of first reformer is 100kgmol/hr for benzene, and is 600kgmol/hr for methane.In table 2 to benzene and operating condition and the steam of percentage hydrogen utilance, first and second reformers of in table 3, listing said molten carbonate fuel cell to methane to the ratio of carbon.
As obtaining, suppose that the R in the equation 2 equals 0.75 Ω .cm from the 2002,112, the 509th to 518 pages of J.Power Sources 2
Table 2
Figure BPA00001481538800441
Table 3
Figure BPA00001481538800451
Figure 10 is to using the act as a fuel molten carbonate fuel cell system in source of benzene or methane to describe cell voltage (mV) to current density (mA/cm 2).Data wire 190 describe to use benzene as the cell voltage (mV) of feed source under 20% hydrogen utilance to current density (mA/cm 2).Data wire 192 describe to use methane as the cell voltage (mV) of feed source under 20% hydrogen utilance to current density (mA/cm 2).Shown in figure 10, when benzene was used as the fuels sources of first reformer, said molten carbonate fuel cell system was observed higher cell voltage.
Figure 11 is directed against at 200mA/cm 2Current density under use act as a fuel average excess carbon dioxide (the Δ P of molten carbonate fuel cell system in source of benzene or methane CO2 (avg)) to percentage hydrogen utilance.Data wire 194 expressions are to the average excess carbon dioxide value of benzene under given hydrogen utilance.Data wire 196 expressions are to the average excess carbon dioxide value of methane.Shown in figure 11, under less than 50% hydrogen utilance, benzene provides than methane and more manys excess carbon dioxide under given hydrogen utilance.Therefore, when using benzene to act as a fuel the source, every moles of hydrogen produces more moles carbon dioxide.
Shown in embodiment 1 to 4, molten carbonate fuel cell system as herein described and method provide current density, current/voltage, the power density of enhancing through following steps and suppress the carbon dioxide deficiency of said fuel cell: the hydrogeneous stream that will comprise molecular hydrogen provides the anode part to molten carbonate fuel cell; Control the said hydrogeneous flow velocity that flow to said anode so that the molecular hydrogen utilance in the said anode less than 50%; To comprise from the anode exhaust of the molecular hydrogen of molten carbonate fuel cell and mixing that the said anode exhaust of wherein mixing with said hydrocarbon stream has 500 ℃ to 700 ℃ temperature with the hydrocarbon stream that comprises hydrocarbon; Make anode exhaust contact the steam reformation charging that comprises one or more gaseous hydrocarbons, molecular hydrogen and at least a oxycarbide with generation with catalyst with at least a portion of the said mixture of said hydrocarbon stream; At least a portion of separating said molecular hydrogen from said steam reformation charging; Provide to said fused carbonate fuel battery anode as the said at least a portion of the hydrogeneous stream of molecular hydrogen that comprises with at least a portion the molecular hydrogen that is separated.

Claims (10)

1. the method for an operating molten carbonate fuel cells, it comprises:
The hydrogeneous stream that will comprise molecular hydrogen provides the anode part to molten carbonate fuel cell;
Control the said hydrogeneous flow velocity that flow to said anode so that the molecular hydrogen utilance in the said anode less than 50%;
To comprise from the anode exhaust of the molecular hydrogen of said molten carbonate fuel cell and mixing that the said anode exhaust of wherein mixing with said hydrocarbon stream has 500 ℃ to 700 ℃ temperature with the hydrocarbon stream that comprises hydrocarbon;
At least a portion of the mixture of said anode exhaust and said hydrocarbon stream is contacted with catalyst, comprise the steam reformation charging of one or more gaseous hydrocarbons, molecular hydrogen and at least a oxycarbide with generation;
At least a portion of separating said molecular hydrogen from said steam reformation charging; With
At least a portion of the molecular hydrogen of said separation is provided to said fused carbonate fuel battery anode as the said at least a portion of the hydrogeneous stream of molecular hydrogen that comprises.
2. method as claimed in claim 1, wherein said hydrogeneous stream comprise at least 0.6 or at least about the molecular hydrogen of 0.95 molfraction.
3. method as claimed in claim 1, some hydrocarbon at least of wherein said hydrocarbon stream comprise that one or more have the transpirable hydrocarbon that is at least 4 carbon number.
4. method as claimed in claim 1; Further comprise with certain amount carbon dioxide is delivered to the cathode portion of said molten carbonate fuel cell, so that the partial pressure of carbon dioxide in the major part of the cathode portion of said molten carbonate fuel cell is higher than the partial pressure of carbon dioxide in the major part of anode part of said molten carbonate fuel cell.
5. method as claimed in claim 4, the difference between the partial pressure of carbon dioxide at the air exit place of the partial pressure of carbon dioxide at the inlet of the cathode portion of wherein said molten carbonate fuel cell or air exit place and the anode part of said molten carbonate fuel cell is at least 0.05 crust or at least 0.1 crust or at least 0.15 crust.
6. method as claimed in claim 4 wherein provides at least a portion of the carbon dioxide of the cathode portion that is provided to said molten carbonate fuel cell through the high temperature hydrogen separator.
7. method as claimed in claim 1; Further may further comprise the steps: separate from said steam reformation charging and comprise that at least a hydrogen at least a and gaseous hydrocarbon in the oxycarbide exhausts at least a portion of air-flow; At least a portion of the hydrogen spent stream of being separated is contacted with oxidant to produce through the stream of heating and will provide to said anode exhaust from least a portion of the heat of said stream through heating and/or the hydrocarbon stream that comprises hydrocarbon to said is provided.
8. method as claimed in claim 1 comprises further with air and carbon dioxide the negative electrode to said molten carbonate fuel cell being provided that wherein said air comprises molecular oxygen; With the flow velocity of control said air and/or carbon dioxide so that the molar ratio of carbon dioxide and molecular oxygen is at least 2.
9. method as claimed in claim 1; Further comprise making to provide and mix with oxidant to one or more anode electrodes place of at least a portion in the anode of said molten carbonate fuel cell of the said molecular hydrogen of said fused carbonate anode and with 0.1W/cm at least 2Electrical power density produce from said molten carbonate fuel cell.
10. fused carbonate system, it comprises:
Molten carbonate fuel cell, it is set to receive the hydrogeneous stream that comprises molecular hydrogen with certain flow rate, so that the hydrogen utilance in the anode of said molten carbonate fuel cell is less than 50%;
One or more reformers; It operationally is coupled to said molten carbonate fuel cell; At least one reformer is configured to receive hydrocarbon and from the anode exhaust of said molten carbonate fuel cell; And be configured to allow said anode exhaust and said hydrocarbon to mix fully with some hydrocarbon in the said hydrocarbon of reforming at least in part and flow to produce the product of reforming, the product stream of wherein said reformation comprises molecular hydrogen and at least a oxycarbide; With
The high temperature hydrogen separator; Its in the said reformer at least one part or be coupled at least one in the said reformer; And operationally be coupled to said molten carbonate fuel cell, wherein said high temperature hydrogen separator comprises one or more high temperature hydrogen separating films and is configured to receive the product stream of reformation and will comprises that the stream of at least a portion of molecular hydrogen provides to said molten carbonate fuel cell.
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