CN101946356A - Fuel cell-based system for generating electrical power - Google Patents

Fuel cell-based system for generating electrical power Download PDF

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Publication number
CN101946356A
CN101946356A CN2008801267417A CN200880126741A CN101946356A CN 101946356 A CN101946356 A CN 101946356A CN 2008801267417 A CN2008801267417 A CN 2008801267417A CN 200880126741 A CN200880126741 A CN 200880126741A CN 101946356 A CN101946356 A CN 101946356A
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hydrogen
reforming reactor
fuel cell
reforming
anode
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崔晶瑜
E·E·恩沃尔
M·L·乔希
S·L·韦林顿
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
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    • H01M2008/1293—Fuel cells with solid oxide electrolytes
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The present invention relates to a solid oxide fuel cell system. The system includes a pre-reforming reactor, a reforming reactor, a hydrogen separation apparatus and a solid oxide fuel cell. The anode exhaust outlet of the solid oxide fuel cell is operatively connected to an inlet of the pre-reforming reactor so anode exhaust from the fuel cell may enter the pre-reforming reactor. The pre-reforming reactor also has an inlet for a hydrocarbon feed precursor. The reforming reactor is operatively coupled to the pre-reforming reactor so that a feed produced in the pre-reforming reactor from the feed precursor may be fed to the reforming reactor. The reforming reactor is operatively connected to the hydrogen separation apparatus so that hydrogen produced in the reforming reactor may be separated from the reformed product gases. The anode inlet of the solid oxide fuel cell is operatively connected to the hydrogen separation apparatus so hydrogen may be fed from the hydrogen separation apparatus as fuel to the solid oxide fuel cell.

Description

Be used to produce the system based on fuel cell of electric power
Technical field
The present invention relates to produce the fuel cell system of electric power, and relate to the method that is used to produce electric power.Especially, the present invention relates to produce the solid oxide fuel battery system of electric power and the method that this system of use produces electric power.
Background technology
Solid Oxide Fuel Cell is by the fuel cell of directly forming from the solid-state element of electrochemical reaction generation electric power.This fuel cell be useful because it supplies with high-quality reliable electric power, cleanliness of operation, and be the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of relative compact, thereby make its application very attractive in the urban area.
Solid Oxide Fuel Cell by anode, negative electrode and be clipped in anode and negative electrode between solid electrolyte form.Oxidable fuel gas or the gas that can be restructured as oxidable fuel gas in fuel cell are provided to anode, and oxygen-containing gas (being generally air) is provided to negative electrode so that chemical reactant to be provided.The oxidable fuel gas that is supplied to anode is generally synthesis gas (mixture of hydrogen and carbon monoxide).Fuel cell is operated being generally under 800 ℃ to 1100 ℃ the high temperature, and so that the oxygen in the oxygen-containing gas is changed into oxonium ion, oxonium ion can pass electrolyte and interact with hydrogen and/or carbon monoxide from fuel gas at the anode place.Electric power is by being converted into oxonium ion and producing at the chemical reaction of anode place oxonium ion and hydrogen and/or carbon monoxide at negative electrode place oxygen.Below the chemical reaction that produces electric power in the battery has been described in reaction:
The negative electrode electric charge shifts: O 2+ 4e -→ 2O =
The anode electric charge shifts: H 2+ O =→ H 2O+2e -And
CO+O ＝→CO 2+2e -
Electric loading or storage device can be connected between anode and the negative electrode, so that electric current can flow between anode and negative electrode, thereby offer storage device for the electric loading power supply or with electric power.
Fuel gas is supplied to the anode of fuel cell usually by steam reformer reactors, steam reformer reactors is with low molecular weight hydrocarbon and steam reformation Cheng Qing and oxycarbide.Methane (for example being natural gas) is the preferred low molecular weight hydrocarbon that is used for producing the fuel gas that is used for fuel cell.Alternatively, anode of fuel cell can be designed as in inside and makes the steam and the low molecular weight hydrocarbon (such as methane) that are supplied to anode of fuel cell realize steam reforming reaction.
In some cases, the methane feed of using in steam reformer reactors and/or other low molecular weight hydrocarbon charging can be produced by the liquid fuel such as gasoline, diesel oil or kerosene.Liquid fuel can change into the charging that is used for steam reformer reactors in the pre-reforming reactor.Liquid fuel can be by making fuel and vapor mixing and making fuel and steam reaction under the temperature of 550 ℃ or higher (common 700 ℃ or higher) changes into the charging that is used for steam reformer reactors.
Methane steam reforming provides the fuel gas that contains hydrogen and carbon monoxide according to following reaction:
Figure BPA00001204545000021
Owing to form the reaction of hydrogen and carbon monoxide is the quite reaction of heat absorption, therefore must supply heat to carry out steam reforming reaction.This reaction is usually carried out under 750 ℃ to 1100 ℃ temperature with a large amount of methane or other hydrocarbon and steam-reforming Cheng Qing and carbon monoxide.
Normally, be provided for 1 by burner) cause the heat and (if necessary) 2 of the methane steam reforming reaction in the steam reformer reactors) be used for liquid fuel is changed into the heat of the charging that is used for steam reformer reactors, described burner make oxygen-containing gas and fuel (being generally hydrocarbon fuel) burning such as natural gas to provide calorific requirement.Also utilize flameless combustion to be provided for driving the heat of steam reforming reaction, wherein, also by with hydrocarbon fuel and oxygen-containing gas to avoid causing that the relative populations that flame (flammable) burning is arranged offers Flameless combuster and drives flameless combustion.Obtain and lose because a large amount of heat energy that provided by burning are at large, thus these be used to provide drive steam reforming reaction and/method efficient aspect energy that pre-reforming reaction institute must heat is lower.
System and method are disclosed for U.S. Patent application No.2005/0164051, wherein reforming reactor and pre-reforming reactor can with the fuel cell heat integration.The heat that use is produced by fuel cell provides the heat of the endothermic reaction that drives reforming reactor.By reforming reactor being placed in the hot case identical and/or making reforming reactor and fuel cell heat integration by fuel cell and reformer are placed in the mode of thermo-contact each other with fuel cell.Can be by reformer being placed near fuel cell and fuel cell and reformer being placed to thermo-contact each other, wherein the cathode exhaust gas pipeline of fuel cell can (for example directly contact with reformer, realize by around reformer, twining the cathode exhaust gas pipeline, perhaps comprise that by one or more reformer wall the wall of cathode exhaust gas pipeline realizes) so that provide conduction heat transfer to reformer from the cathode exhaust gas of fuel cell.Additional heat offers reformer from the combustion chamber, and wherein the thermo-contact of fuel cell and reformer has reduced the combustion heat requirement of reformer realization reforming reaction.
Have catalytic and start in the hot case of burner by the pre-reforming reactor is positioned at, and, be provided for the heat of pre-reforming reactor by providing by carrying out the natural gas feed that heat exchange is heated with anode exhaust stream from fuel cell.Yet, owing to use the charging of natural gas as the pre-reforming reactor, so pre-reforming reactor and be not used in the lower molecular weight charging that the liquid feedstock conversion is become to be used for steam reformer reactors.
Although the heat energy that is provided by burning is more effective than catching, but the heat efficiency of this method is still relatively low, this is because 1) because equal or near driving the required temperature (750 ℃ to 1100 ℃) of reforming reaction from the temperature of the heat of the exhaust of fuel cell, so from the shortage of heat of fuel cell to drive reforming reaction fully, and, unless heat exchange completely takes place to be close to, otherwise under situation not, will be not enough to drive reforming reaction from the heat of fuel cell from the additional heat of another thermal source (such as the combustion chamber); With 2) will transmit away from reforming reactor and orientating reaction device convection current ground from the fuel cell heat of exhaust in a large number.The pre-reforming reactor does not change into liquid hydrocarbon feed the lower molecular weight charging that is used for steam reformer reactors yet, and fuel cell can not provide enough heats to carry out this operation probably.
In addition, low with the electrochemical efficiency usually and mode that do not produce high power density of the Solid Oxide Fuel Cell that connects with pre-reforming reactor and reforming reactor is worked.Solid Oxide Fuel Cell is operated with " poor hydrogen " pattern commercial usually, wherein selects for example to produce the condition of fuel gas to be limited in the amount of the hydrogen that leaves fuel cell in the fuel vent by steam reformation.Do like this is for electric energy gesture that makes hydrogen in the fuel gas and the gesture that hydrogen lost (heat+electrochemistry) the energy balance that does not get transformed into electric energy of leaving battery.
Yet, for for producing electric power in the Solid Oxide Fuel Cell, to compare with purer hydrogen fuel gas stream, the efficient of fuel gas that contains non-hydrogen compound (such as carbon monoxide or carbon dioxide) is lower.This is owing to the electrochemical oxidation gesture of hydrogen molecule with respect to other compound.For instance, hydrogen molecule can produce 1.3W/cm under 0.7 volt 2Power density, and carbon monoxide only can produce 0.5W/cm under 0.7 volt 2Power density.Therefore, at produce electric power in Solid Oxide Fuel Cell, the fuel gas stream that contains a large amount of non-hydrogen compounds is effective not as the fuel gas that mainly contains hydrogen.
Taked some measure to catch the energy of the too much hydrogen that leaves fuel cell again, yet, if these measures significantly are being lower than hydrogen carries out electrochemical reaction in fuel cell situation aspect the efficiency.For instance, made and burn and drive turbo-expander (turbine expander) with generation electric power by making fuel gas that anode exhaust that electrochemical reaction produces take place in fuel cell.Yet because heat energy loss takes place and do not change into electric energy by decompressor in a large number, so this significantly is being lower than the electrochemical potential of catching hydrogen in fuel cell aspect efficient.The fuel gas that leaves fuel cell has also burnt to be provided for the heat energy of various heat exchange applications, comprises driving reforming reactor as mentioned above.Yet almost 50% the heat energy that is provided by burning is at large to be obtained and loses.For being used for the ignition combustion device, hydrogen is very expensive gas, therefore, and normally, regulate hydrogen amount used in the Solid Oxide Fuel Cell and produce electric power, and the hydrogen amount of leaving fuel cell in the fuel cell exhaust is reduced as far as possible with most hydrogen that utilization offers fuel cell.
U.S. Patent Application Publication No.2007/0017369 (' 369 open case) provides the method for a kind of operation of fuel cells system, wherein charging is offered the fuel inlet of fuel cell.The hydrogen that provides from the external steam reformer and the mixture of carbon monoxide can be provided in charging, perhaps alternatively, can be included in the hydrocarbon charging that internally is reformatted into hydrogen and carbon monoxide in the fuel cell pack.Make the fuel cell heap operation to produce electric power and to contain hydrogen and the fuel vent of carbon monoxide stream, wherein with the hydrogen in the fuel vent stream and carbon monoxide from the fuel vent flow point from and as the part supply of the charging material inlet that strile-backs.Therefore, the fuel gas that is used for fuel cell is the hydrogen that separates by the hydrogen that hydrocarbon fuel sources reformed obtain and carbon monoxide and from the fuel vent system and the mixture of carbon monoxide.Make from least a portion recirculation in the hydrogen of fuel vent and make it possible to obtain high operating efficiency by fuel cell.This system is further by utilizing about 75% fuel during once and high fuel availability is provided in fuel cell whenever passing pile.
U.S. Patent Application Publication No.2005/0164051 provides the method for a kind of operation of fuel cells system, wherein fuel is provided the fuel inlet to fuel cell.This fuel can be the hydrocarbon fuel such as methane; The natural gas that contains methane and hydrogen and other gas; Propane; Biogas; The hydrocarbon fuel of not reforming that mixes with hydrogen fuel from reformer; Or such as the nonhydrocarbon carbonaceous gas of carbon monoxide, carbon dioxide, such as oxidization of methanol carbonaceous gas or other carbonaceous gas and mixture such as the hydrogen-containing gas of steam or synthesis gas.The operation of fuel cells heap is to produce electricity and the fuel vent stream that contains hydrogen.Utilize hydrogen separator to make of the fuel-side exhaust stream separation of the hydrogen of not utilization from fuel cell.The hydrogen that is separated by the hydrogen separator material battery that can recirculation strile-backs maybe can guide to the subsystem of other purposes that is used to have the hydrogen demand.Can select the strile-back hydrogen amount of material battery of recirculation according to electric demand or hydrogen demand, wherein when electric demand is higher, make more hydrogen recirculation material battery that strile-backs.Fuel cell pack can be operated with 0 to 100% fuel availability according to electric demand.When electric demand was higher, fuel cell was 50% to 80% with high fuel availability operation to increase electricity generation-preferred utilance.
Need in solid oxide fuel cell system, provide further improvement aspect the heat efficiency and the electrical efficiency to increase the method and system of its power density and total energy efficiency.
Summary of the invention
In one aspect, the present invention relates to a kind of system that is used to produce electric power, comprising:
A) Solid Oxide Fuel Cell, it comprises
1) anode, it has
(i) anode inlet; With
(ii) anode exhaust outlet;
2) negative electrode, it has
(i) cathode inlet; With
(ii) cathode exhaust gas outlet; With
3) between described anode and negative electrode, contact anode and negative electrode and the electrolyte of anode and negative electrode separately;
B) pre-reforming reactor, it comprises
1) be suitable for making one or more hydrocarbon cracking in the charging precursor to form the pre-reforming zone of charging, described pre-reforming comprises Cracking catalyst in the zone, and described Cracking catalyst is positioned to contact one or more hydrocarbon of charging precursor and the vaporization mixture of steam;
2) enter the mouth with one or more pre-reforming reactor feed precursor that the gas/fluid mode of communicating connects with described pre-reforming zone, the charging precursor can be introduced the pre-reforming zone by described pre-reforming reactor feed precursor inlet; With
3) one or more pre-reforming reactor anode exhaust inlet that connects with the gas mode of communicating with described pre-reforming zone and connects with the operation of gas mode of communicating with the outlet of described anode exhaust can be by the described pre-reforming reactor anode exhaust introducing pre-reforming zone that enters the mouth from the anode exhaust stream of fuel cell; With
4) be in one or more pre-reforming reactor outlet that gas is communicated with described pre-reforming zone;
C) reforming reactor, it comprises
1) the reformation zone that is suitable for making the vaporization mixture of the charging that comprises one or more gaseous hydrocarbon and steam to reform, described reformation comprises reforming catalyst in the zone, and described reforming catalyst is positioned in the reformation zone and contacts with the vaporization mixture of charging and steam; With
2) one or more reformer section realm entry, it connects with the gas mode of communicating with described reformation zone and connects with the operation of gas mode of communicating with one or more pre-reforming reactor outlet, with the reformation zone that allows to introduce reforming reactor from the charging and the steam of pre-reforming reactor; With
D) hydrogen separation equipment, it has
1) member that can hydrogen be seen through, it is positioned in the reformation zone of reforming reactor and is in gas with the reformation zone of reforming reactor to be communicated with;
2) be in the hydrogen outlet that gas is communicated with described member, described member between the reformation zone of reforming reactor and hydrogen outlet with allow hydrogen from the zone of reforming by this member optionally flowing to hydrogen outlet, wherein, described hydrogen outlet connects to allow hydrogen stream to flow to the anode of fuel cell from the hydrogen separation equipment with the operation of gas mode of communicating with the anode inlet of fuel cell.
In yet another aspect, the present invention relates to a kind of system that is used to produce electric power, comprising:
A) Solid Oxide Fuel Cell, it comprises
1) anode, it has
(i) anode inlet; With
(ii) anode exhaust outlet;
2) negative electrode, it has
(i) cathode inlet; With
(ii) cathode exhaust gas outlet; With
3) between described anode and negative electrode, contact anode and negative electrode and the electrolyte of anode and negative electrode separately;
B) pre-reforming reactor, it comprises
1) be suitable for making one or more hydrocarbon cracking in the charging precursor to form the pre-reforming zone of charging, described pre-reforming comprises Cracking catalyst in the zone, and described Cracking catalyst is positioned to contact one or more hydrocarbon of charging precursor and the vaporization mixture of steam;
2) enter the mouth with one or more pre-reforming reactor feed precursor that the gas/fluid mode of communicating connects with described pre-reforming zone, the charging precursor can be introduced the pre-reforming zone by described pre-reforming reactor feed precursor inlet; With
3) one or more pre-reforming reactor anode exhaust inlet that connects with the gas mode of communicating with described pre-reforming zone and connects with the operation of gas mode of communicating with the outlet of described anode exhaust can be by the described pre-reforming reactor anode exhaust introducing pre-reforming zone that enters the mouth from the anode exhaust stream of fuel cell; With
4) be in one or more pre-reforming reactor outlet that gas is communicated with described pre-reforming zone;
C) reforming reactor, it comprises
1) the reformation zone that is suitable for making the vaporization mixture of the charging that comprises one or more gaseous hydrocarbon and steam to reform, described reformation comprises reforming catalyst in the zone, and described reforming catalyst is positioned in the reformation zone and contacts with the vaporization mixture of charging and steam; With
2) one or more reformer section realm entry, it connects with the gas mode of communicating with described reformation zone and connects with the operation of gas mode of communicating with one or more pre-reforming reactor outlet, with the reformation zone that allows to introduce reforming reactor from the charging and the steam of pre-reforming reactor; With
D) hydrogen separation equipment, it has
1) member that can hydrogen be seen through, the reformation zone of itself and reforming reactor is operatively connected with the gas mode of communicating;
2) be in the hydrogen outlet that gas is communicated with described member, described member between the reformation zone of reforming reactor and hydrogen outlet with allow hydrogen from the zone of reforming by this member optionally flowing to hydrogen outlet, wherein, described hydrogen outlet connects to allow hydrogen stream to flow to the anode of fuel cell from the hydrogen separation equipment with the operation of gas mode of communicating with the anode inlet of fuel cell.
Description of drawings
Fig. 1 is the schematic diagram that is used to carry out a kind of system of the present invention of the inventive method, and described system comprises the pre-reforming reactor, has the reforming reactor and the Solid Oxide Fuel Cell of the hydrogen separation equipment that is positioned at wherein.
Fig. 2 is the schematic diagram that is used to carry out a kind of system of the present invention of the inventive method, and described system comprises pre-reforming reactor, reforming reactor, is operatively connected hydrogen separation equipment and Solid Oxide Fuel Cell to reforming reactor.
Fig. 3 is the schematic diagram of a kind of fundamental system of the present invention, and described fundamental system comprises the pre-reforming reactor, has the reforming reactor and the Solid Oxide Fuel Cell of the hydrogen separation equipment that is positioned at wherein.
Fig. 4 is the schematic diagram of a kind of fundamental system of the present invention, and described fundamental system comprises pre-reforming reactor, reforming reactor, is operatively connected hydrogen separation equipment and Solid Oxide Fuel Cell to reforming reactor.
Embodiment
The invention provides a kind of high efficiency method that is used for producing by liquid hydrocarbon fuels with high power density electric power in the system that utilizes Solid Oxide Fuel Cell.At first, in method of the present invention and the prior art disclosed method to compare heat energy efficiency higher.Heat energy from the fuel cell exhaust is directly delivered in the pre-reforming reactor, and the part of this heat energy is delivered to the reforming reactor from the pre-reforming reactor subsequently.Selectively, heat energy also can be directly delivered to the reforming reactor from fuel cell.The direct transmission of heat energy from the anode exhaust of fuel cell to the pre-reforming reactor is efficiently, thereby this is because to transmit be by making the hot anode exhaust stream from fuel cell be supplied to the charging of reforming reactor to realize subsequently with charging precursor in the pre-reforming reactor and the direct molecular mixing generation of steam.The transmission of heat energy from the pre-reforming reactor to reforming reactor also is efficiently, and this is because heat energy is included in from the pre-reforming reactor and is supplied to the charging of reforming reactor.Heat energy via the optional transmission of fuel battery negative pole exhaust from the fuel cell to the reforming reactor also be heat efficiently, this be since hot transmission can directly in reforming reactor, take place.
To compare the heat efficiency higher for disclosed method in method of the present invention and the prior art, and this is because reforming reactor can realize under the lower temperature that hydrogen produces comparing with typical steam reforming method.In the method for the invention, when reforming reaction takes place in reforming reactor when, can be from reformate gas separation of hydrogen, thereby towards the direction driven equilibrium that produces hydrogen and reduce and realize that hydrogen produces required temperature.In addition, can produce more hydrogen under lower reforming reaction actuator temperature, this is because water gas shift reaction (water gas shift reaction)
Figure BPA00001204545000091
Balance promoted under lower reforming reaction actuator temperature, to produce hydrogen, and under traditional reforming reaction temperature and mustn't go to promotion.Reforming reactor is designed to produce hydrogen under the temperature more much lower than typical reforming reactor, therefore come the heat of the charging of free pre-reforming reactor supply, perhaps, be enough under the situation of no extraneous thermal source, drive the reforming reaction of lower temperature from the heat of charging and from the combination of fuel battery negative pole heat of exhaust.
Method of the present invention can also be compared higher power density by utilizing hydrogen-rich fuel to produce with the disclosed method of prior art in solid oxide fuel battery system.This realizes by making the anode exhaust stream that contains hydrogen and steam carry out recirculation by pre-reforming reactor and reforming reactor.The hydrogen that is not used for producing electric power in the fuel cell is recycled to the pre-reforming reactor continuously, and finally returns fuel cell.This makes and not to get transformed into electric energy and lose the relevant problem of potential energy by eliminating with leave battery owing to hydrogen, can produce high power density with respect to the minimum heat value of fuel.
In an embodiment of the inventive method, the anode of Solid Oxide Fuel Cell is full of hydrogen on the entire path length of anode, the hydrogen concentration that makes the anode electrode place can be used for electrochemical reaction is kept high level on whole anode path, thereby makes the power density maximization of fuel cell.Because comparing with normally used other oxidizable compounds (such as carbon monoxide) in solid oxide fuel battery system, hydrogen has significantly higher electrochemical potential, therefore use main (preferably, almost whole) to make the power density maximization of fuel cell system for the hydrogen-rich fuel of hydrogen in the method.
In one embodiment, method of the present invention also by minimizing but not maximize fuel in the Solid Oxide Fuel Cell pass through fuel availability and the power density of maximize fuel cell system at every turn.Minimize and pass through the concentration of fuel availability at every turn, so that on whole anode path, keep high hydrogen concentration with oxidation product (particularly water) on the whole anode path that reduces fuel cell.Because there is hydrogen excessive for electrochemical reaction in the whole anode path along fuel cell at the anode electrode place, so fuel cell provides high power density.Be intended to obtain high (for example to pass through fuel availability at every turn, fuel availability greater than 50%) in the method, the minimum concentration that equals the hydrogen in the fuel vent of the concentration of oxidation product, and the concentration of oxidation product has reduced the electric power that fuel cell provides in the fuel cell.Because there is hydrogen excessive for electrochemical reaction in the whole anode path along fuel cell at the anode electrode place, so fuel cell provides high power density.Be intended to obtain high (for example to pass through fuel availability at every turn, fuel availability greater than 60%) in the method, fuel advanced by fuel cell in addition half distance before, the concentration of oxidation product can constitute more than 30% of fuel stream, and can be the several times of hydrogen concentration in the fuel cell exhaust, make that the electric power that provides along the anode path can significantly reduce along with the fuel that offers fuel cell advances via anode.
On the other hand, the present invention relates to a kind of system that is used for producing with high power density electric power with efficient way.
When using in this article, term " hydrogen " is meant hydrogen molecule, except as otherwise noted.
When using in this article, " water yield that forms in the fuel cell in the per unit Measuring Time " is calculated as follows: the water yield that forms in the fuel cell in the per unit Measuring Time=[leaving the measured water yield of fuel cell in the anode exhaust of the inherent fuel cell of per unit Measuring Time]-[being present in the water yield in the fuel that is supplied to anode of fuel cell in the per unit Measuring Time].For instance, if measure in the fuel be supplied to anode of fuel cell and in anode exhaust, leave the water yield cost 2 minutes of fuel cell, wherein being supplied to the measured value of water in the fuel of anode is 6 moles, and the measured value that leaves the water of fuel cell in anode exhaust is 24 moles, the water yield that then forms in fuel cell is calculated as follows, (24 moles/2 minutes)-(6 moles/2 minutes)=12 moles/min-3 moles/min=9 moles/min.
When using in this article, when two or more elements were described to " being operatively connected " or " operation connects " and so on, these elements were restricted to and connect directly or indirectly to allow the direct or indirect fluid between the described element to flow.When using in this article, term " fluid flows " is meant flowing of gas or fluid.When two or more elements were described to " optionally being operatively connected " or " optionally operate and connect ", these elements were defined as and connect directly or indirectly or connect to allow selected gas or fluid direct or indirect fluid between these elements to flow.When being used for definition " being operatively connected " or " operation connects ", term " indirectly fluid flow " is meant when fluid or gas and limits between the element when mobile two institutes that two fluid or gas flow that limited between the element can be conducted through one or more additional element one or more aspect with change fluid or gas.Comprise physical features aspect fluid that can in fluid flows indirectly, change or the gas, such as the temperature of gas or fluid or the composition of pressure and/or gas or fluid, for example, by the component of divided gas flow or fluid, for example, change by condensation water outlet from the air-flow that contains steam.Defined in this paper, " fluid flows indirectly " do not comprise by chemical reaction (for example, the oxidation or the reduction of one or more element in fluid or the gas) at two compositions that change gas or fluid between the element that limit.
When using in this article, term " can optionally make hydrogen see through " and so on to be defined as hydrogen molecule or protium can see through and other element or compound impermeable, and 10%, at the most 5% or at the most 1% non-protium or compound can see through hydrogen molecule or the permeable material of protium so that have only at the most.
When using in this article, term " high temperature hydrogen separator " is defined as device or the equipment that the hydrogen of molecule or element state form is effectively separated in (usually under 300 ℃ to 650 ℃ temperature) under at least 250 ℃ the temperature from air-flow.
When using in this article, the term that refers to the utilance of the hydrogen in the fuel in the Solid Oxide Fuel Cell " passes through the hydrogen utilance at every turn " and is defined as in passing once the passing through of Solid Oxide Fuel Cell in order to the hydrogen amount in the fuel that produces electric power with respect to the hydrogen total amount in the fuel that is input to regard to this time passed through in the fuel cell.Can be supplied to hydrogen amount in the fuel of anode of fuel cell by measurement, hydrogen amount in the anode exhaust of measurement fuel cell, deduct hydrogen measured value in the anode exhaust of fuel cell with the hydrogen measured value in the fuel that is supplied to fuel cell determining used hydrogen amount in the fuel cell, and calculate divided by the hydrogen measured value in the fuel that is supplied to fuel cell with the calculated value of used hydrogen in the fuel cell and to pass through the hydrogen utilance at every turn.Passing through the hydrogen utilance can multiply by 100 and be expressed as percentage at every turn by make the hydrogen utilance of passing through that calculates at every turn.
When using in this article, term " reforming reactor " is meant, and hydrocarbon reforming reaction and the reactor that selectively takes place such as other reaction of water gas shift reaction can take place therein.When using in this article, the reaction that takes place in reforming reactor can mainly be hydrocarbon reforming reaction, but to need not mainly be the hydrocarbon reforming reaction.For instance, in some cases, the great majority reaction that takes place in " reforming reactor " in fact can be transformationreation but not hydrocarbon reforming reaction.
When using in this article, term " pre-reforming reactor " is meant and cracking reaction can take place therein and selectively takes place such as other reaction of reforming reaction and the reactor of generating material physical conversion (such as vaporization) selectively.The cracking reaction that can take place in the pre-reforming reactor makes hydrocarbon molecule fragment into more simple molecules.In the pre-reforming reactor, cracking can relate to the minimizing of the molecular weight of the minimizing of strand length of hydrocarbon compound and/or hydrocarbon compound.For instance, the cracking reaction that can take place in the pre-reforming reactor can be reduced to and has the hydrocarbon compound of 3 carbon atoms at the most having at least the strand length of the hydrocarbon compound of four carbon atom.The cracking reaction that can take place in the pre-reforming reactor can be heat cracking reaction or hydrocracking reaction.
Referring now to Fig. 1,, method utilization of the present invention comprises that pre-reforming reactor, hydrogen separate the heat integration system 100 generation electric power of reforming reactor and Solid Oxide Fuel Cell.This method is used the liquid hydrocarbon feed precursor, this liquid hydrocarbon feed precursor can cracking in first reactor 101 (being referred to herein as the pre-reforming reactor) (and part is reformed in one embodiment) become the gaseous hydrocarbon charging, it can be reformed in second reactor 103 (being referred to herein as reforming reactor) subsequently to produce reformate gas, can be by hydrogen separator 107 separation of hydrogen from reformate gas in the reforming reactor 103.Can in Solid Oxide Fuel Cell 105, utilize hydrogen to produce electric power.This method is a heat integration, is wherein provided in order to the heat absorption cracking reaction in the driving pre-reforming reactor 101 and the heat of the heat absorption reforming reaction in the reforming reactor 103 by heat release Solid Oxide Fuel Cell 105.
In the method, the charging precursor that contains liquid hydrocarbon (can obtain hydrogen by it) can be supplied to pre-reforming reactor 101 via pipeline 109.But the charging precursor can contain one or more any vaporised hydrocarbon, and it under atmospheric pressure is liquid (alternatively for oxidation) in the time of 20 ℃, and under atmospheric pressure can vaporize when the temperature up to 400 ℃.This charging precursor can include but not limited to that boiling spread is 50 ℃ to 205 ℃ a light petroleum cut, such as naphtha, diesel oil and kerosene.This charging precursor can also comprise oxygenated hydrocarbon, and it includes but not limited to methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol and butanols.Selectively, the charging precursor can contain at 20 ℃ to descend to be some hydrocarbon of gaseous state that such as methane, ethane, propane, or (atmospheric pressure) is other compound to four carbon atom that contains of gaseous state under 20 ℃.In one embodiment, the charging precursor can contain the hydrocarbon that contains at least five, at least six or at least seven carbon atoms of at least 0.5, at least 0.6, at least 0.7 or at least 0.8 molar fraction.In one embodiment, the charging precursor can be a decane.In a preferred embodiment, the charging precursor can be a diesel fuel.
In one embodiment, the charging precursor can preferably be supplied to pre-reforming reactor 101 under 200 ℃ to 500 ℃ the temperature at least 150 ℃, and wherein as mentioned below, the charging precursor can be heated to temperature required in heat exchanger.At cracked charge precursor not with produce under the situation of coke, the highland selects the charging precursor to be supplied to the temperature of pre-reforming reactor as far as possible, and this temperature may be selected to be 400 ℃ to 500 ℃ temperature usually.Alternatively, but more not preferably, when the sulfur content of charging precursor is low, can for example not add under the situation of hot feed precursor, the charging precursor directly is being supplied to pre-reforming reactor 101 being lower than under 150 ℃ the temperature.
The charging precursor can be supplied to before the pre-reforming reactor 101 in devulcanizer 111 desulfurization to remove sulphur from the charging precursor, so that make the charging precursor not pollute any catalyst in the pre-reforming reactor 101.In one embodiment, the charging precursor is that desulfurization was heated in the past in the devulcanizer 111.The charging precursor can be fed in the system 100 via charging precursor suction line 113, and selectively be fed in the heat exchanger 115 heating by the reformate gas stream of carrying out heat exchange and/or the depleted of hydrogen by leaving reforming reactor 103 with the hydrogen stream that leaves reforming reactor 103, as described in further detail below like that.Selectively, the charging precursor can be supplied to before the pre-reforming reactor 101 in heat exchanger 117 by carrying out heat exchange and further heating with cathode exhaust stream from fuel cell 105.The charging precursor can be in the heat exchanger 117 after the heating (as shown in the figure) or be in the heat exchanger 117 (not shown) before the heating, but is being supplied to desulfurization in devulcanizer 111 before the pre-reforming reactor 101.The charging precursor can carry out desulfurization by the conventional Hydrobon catalyst of contact under conventional desulfurization condition in devulcanizer 111.
The charging precursor is fed in the pre-reforming zone 119 of pre-reforming reactor 101.Pre-reforming zone 119 can and preferably comprise the pre-reforming catalyst really therein.The pre-reforming catalyst can be traditional pre-reforming catalyst, and can be any pre-reforming catalyst known in the prior art.Operable typical pre-reforming catalyst comprises but is not limited to the 8th group 4 transition metal (nickel especially) and is the supporter or the matrix of inertia under the pyroreaction condition.The suitable inert compound that is suitable for use as the supporter of high temperature pre-reforming/hydrocracking catalyst includes but not limited to Alpha-alumina and zirconia.
The anode exhaust stream that separates from the anode 121 of Solid Oxide Fuel Cell 105 also is fed to the pre-reforming zone 119 of pre-reforming reactor 101.Anode exhaust can export 123 from anode exhaust and directly be fed to the pre-reforming reactor 101 via pipeline 125.
Anode exhaust stream comprises product and the unreacted fuel from the fuel oxidation reaction of the anode 121 that is supplied to fuel cell 105, and comprises hydrogen and steam.In one embodiment, anode exhaust stream comprises the hydrogen of at least 0.5, at least 0.6 or at least 0.7 molar fraction.Hydrogen in the anode exhaust stream that is supplied to pre-reforming reactor 101 can help prevent in pre-reforming reactor 101 and form coke.In one embodiment, anode exhaust stream contains at the most 0.4, at the most 0.3 or the water (for vapor form) of at the most 0.2 molar fraction.Be supplied to steam in the anode exhaust stream of pre-reforming reactor 101 also can help prevent in pre-reforming reactor 101 and form coke.
Selectively, steam can be supplied to pre-reforming reactor 101 to mix with charging precursor in the pre-reforming zone 119 of pre-reforming reactor 101 via pipeline 127.Steam can be supplied to pre-reforming reactor 101 suppressing or to prevent to form coke in pre-reforming reactor 101, and selectively, uses in the reforming reaction of carrying out in pre-reforming reactor 101.In one embodiment, steam can be supplied to the pre-reforming zone 119 of pre-reforming reactor 101 with a speed, wherein the molar ratio that is added into the steam of pre-reformer 101 via pipeline 127 is the twice at least that is added into the molal quantity of carbon in the charging precursor of pre-reformer, at least three times or at least four times.Be provided as at least 2: 1, at least 3: 1 or at least 4 in pre-reforming reactor 101: the coke that the molar ratio of carbon can be used for suppressing in the pre-reforming zone 119 of pre-reforming reactor 101 in 1 steam and the charging precursor forms.Can use metering valve 129 control steam to be supplied to the speed of pre-reforming reactor 101 by pipeline 127.
Be supplied to the steam of pre-reforming reactor can be at least 125 ℃, preferably be supplied to the pre-reforming reactor under 150 ℃ to 300 ℃ the temperature, and the pressure that can have 0.1MPa to 0.5MPa preferably has the pressure of the pressure that is equal to or less than the anode exhaust stream that is supplied to pre-reforming reactor 101 as mentioned below.Can be by pressure be 1.0MPa at least, preferably the water under high pressure of 1.5MPa to 2.0MPa is fed in the system 100 via water inlet pipeline 131 and delivers to one or more heat exchanger 133 and generation steam.Water under high pressure heats to form high steam by carry out heat exchange with the charging of leaving the pre-reforming reactor in one or more heat exchanger 133.In case leave heat exchanger 133 or (under situation about utilizing more than a heat exchanger 133) last heat exchanger 133, high steam can be supplied to pipeline 127 via pipeline 135 subsequently.High steam can be supplied to it pre-reforming reactor subsequently by reducing pressure through decompressor expansion high steam to required pressure.Alternatively, can be created in the steam that uses in the pre-reforming reactor in the pre-reforming reactor 101 by low-pressure water is supplied through one or more heat exchanger 133 and gained steam is sent to.
Charging precursor, optional steam and anode exhaust stream can and mix and contact pre-reforming catalyst the cracking of charging precursor under with the temperature that forms charging in the pre-reforming zone 119 at pre-reforming reactor 103 in any charging precursor vaporization that makes non-steam form effectively.In one embodiment, charging precursor, optional steam and anode exhaust stream mix under the temperature of 600 ℃, 750 ℃ to 1050 ℃ or 800 ℃ to 900 ℃ and contact pre-reforming catalyst at least.
Be supplied to the anode exhaust stream of pre-reforming reactor 101 to provide heat from heat release Solid Oxide Fuel Cell 105 to drive the heat absorption cracking reaction the pre-reforming reactor 101.It is very hot being supplied to the anode exhaust stream of pre-reforming reactor 101 from Solid Oxide Fuel Cell 105, has at least 800 ℃ temperature, has the temperature of 850 ℃ to 1100 ℃ or 900 ℃ to 1050 ℃ usually.The transmission of heat energy from Solid Oxide Fuel Cell 105 to pre-reforming reactor 101 is extremely effective, this is owing to the heat energy from Solid Oxide Fuel Cell 105 is included in the anode exhaust stream, and by making anode exhaust stream and charging precursor and steam directly mix the mixture of the charging precursor in the pre-reforming zone 119 that passes to pre-reforming reactor 101, optional steam and anode exhaust stream.
In a preferred embodiment of the inventive method, anode exhaust stream provide by the mixture of charging precursor, optional steam and anode exhaust stream produce charging institute calorific requirement at least 99% or roughly whole.In a special preferred embodiment, except anode exhaust stream, other thermal source need not be offered the pre-reforming reactor so that the charging precursor conversion is become charging.
Can select and control the relative speed that charging precursor, optional steam and anode exhaust stream are supplied to pre-reforming reactor 101, come to make the heat that provides by anode exhaust stream be enough to be provided to produce in the pre-reforming reactor 101 charging institute calorific requirement at least 99% or roughly whole.Can be supplied to the metering valve 137 of the speed of system 100 to control the speed that the charging precursors are supplied to pre-reforming reactor 101 by regulating control charging precursor.Steam the steam in anode exhaust stream is supplied to the speed of pre-reforming reactor 101 can be by accommodometer metered valve 139 (its control water is supplied to the speed of system 100), or by accommodometer metered valve 143 and 141 (its control steam is supplied to the speed of pre-reforming reactor 101 and reforming reactor 103), or by accommodometer metered valve 129 and 145 (its control steam is supplied to the pre-reforming reactor and is supplied to the speed of turbine 147), or control by accommodometer metered valve 161 and 163 (it controls the speed that steam is supplied to reforming reactor 103 and pre-reforming reactor 101).Anode exhaust stream is supplied to the speed of pre-reforming reactor can be by regulating pressure in the reforming reactor 103 increasing or to reduce the hydrogen flux that flows through hydrogen separator 107, or controls by accommodometer metered valve 149 and 151.
Pressure when in one embodiment, the pre-reforming catalyst in the pre-reforming zone 119 of anode exhaust stream, charging precursor and optional steam and pre-reforming reactor 101 contacts can be in the scope of 0.07MPa to 3.0MPa.If high steam is not supplied to the pre-reforming reactor, then anode exhaust stream, charging precursor and optional low-pressure steam can be under the pressure of this scope low side (be generally 0.07MPa to 0.5MPa, or 0.1MPa to 0.3MPa) contacts with pre-reforming catalyst in the pre-reforming zone 119 of pre-reforming reactor 101.If high steam is supplied to the pre-reforming reactor, then anode exhaust stream, charging precursor and steam can be under the pressure of this pressure limit higher-end (be generally 1.0MPa to 3.0MPa, or 1.5MPa to 2.0MPa) contacts with pre-reforming catalyst in the pre-reforming zone 119 of pre-reforming reactor 101.
In pre-reforming reactor 101, under the temperature of at least 600 ℃, 750 ℃ to 1050 ℃ or 800 ℃ to 900 ℃, make charging precursor, steam and anode exhaust stream contact meeting cracked charge precursor and form charging.By reducing in the charging precursor number of carbon atom in the compound and producing the compound of decrease in molecular weight thus and the cracked charge precursor.In one embodiment, the charging precursor can comprise the hydrocarbon that contains at least 5, at least 6 or at least 7 carbon atoms, and what it changed into the charging that can be used as reforming reactor 103 contains at the most 4, at the most 3 or the hydrocarbon of 2 carbon atoms at the most.In one embodiment, the charging precursor can comprise the hydrocarbon that contains at least 5, at least 6 or at least 7 carbon atoms of at least 0.5, at least 0.6 or at least 0.7 molar fraction, and the hydrocarbon of gained charging part can comprise at least 0.5, at least 0.6, at least 0.7 or at least 0.8 molar fraction contain at the most 4 carbon atoms, at the most 3 or the hydrocarbon of 2 carbon atoms at the most.In one embodiment, the charging precursor can react in pre-reforming reactor 101 so that the charging that produces in pre-reforming reactor 101 can comprise 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 molar fraction.In one embodiment, the charging precursor can cracking so that the hydrocarbon of at least 0.7, at least 0.8, at least 0.9 or at least 0.95 molar fraction is a methane in the charging that is produced by the charging precursor.
As indicated above, suppressed in pre-reforming reactor 101, to form coke when forming charging in the cracking of charging precursor from the hydrogen and the steam of anode exhaust stream and the optional steam that is added into pre-reforming reactor 101.In a preferred embodiment, select anode exhaust stream, charging precursor and steam to be supplied to the relative speed of pre-reforming reactor 101, so that hydrogen in the anode exhaust stream and steam and prevent from pre-reforming reactor 101, to form coke via the steam that pipeline 127 is added into pre-reforming reactor 101.
In one embodiment, make charging precursor, steam and anode exhaust in pre-reforming reactor 101, under the temperature of 600 ℃, 750 ℃ to 1050 ℃ or 800 ℃ to 900 ℃, contact reforming to produce hydrogen and oxycarbide (carbon monoxide especially) to small part of hydrocarbon in the charging that can also realize producing in charging precursor and the pre-reforming reactor 101 at least with the pre-reforming catalyst.The reformation amount can be sizable, wherein by the cracking in the pre-reforming reactor and the charging that both obtain of reforming can contain the carbon monoxide of at least 0.05, at least 0.1 or at least 0.15 molar fraction.
Can select temperature and pressure condition in the pre-reforming zone 119 of pre-reforming reactor 101, be gaseous state down in pre-reforming reactor 101, contain the lighter hydrocarbons of 1 to 4 carbon atom usually so that the charging that produces is included in 20 ℃.In a preferred embodiment, the hydrocarbon in the charging comprises the methane of at least 0.6, at least 0.7, at least 0.8 or at least 0.9 molar fraction.Charging also comprises from anode exhaust stream and (if reforming in pre-reforming reaction) hydrogen from the catalytic reforming feedstock precursor compound.Charging also comprises from anode exhaust stream and selectively from the steam of pre-reformer steam feed.If carry out quite a large amount of reformations in pre-reforming reactor 101, then the charging that is supplied to reforming reactor 103 that produces in pre-reforming reactor 101 can also comprise carbon monoxide.
In the method for the invention, charging is supplied to reforming reactor 103 from pre-reforming reactor 101, reforming reactor 103 is operatively connected to pre-reforming reactor 101 via pipeline 153.Selectively, charging can be cooled off in one or more heat exchanger 133 before being supplied to reforming reactor 103.Selectively, charging can also be compressed in compressor 155 before being supplied to reforming reactor 103.
The temperature of leaving the charging of pre-reforming reactor 101 can reduce before being supplied to reforming reactor 103.The charging of leaving the pre-reforming reactor can have 600 ℃ to 1000 ℃ temperature.Charging can be through one or more heat exchanger 133 with the cooling charging.Charging can by be supplied to water in the system 100 to carry out heat exchange to cool off, thereby cooling charging and produce the steam that can be supplied to pre-reforming reactor 101 is as indicated above.If utilize more than a heat exchanger 133, then charging and water/steam can be preferably give in the heat exchanger 133 each with the cooling charging and add hot water/steam so that reflux type is without interruption.Charging can be cooled to the temperature of 150 ℃ to 650 ℃, 150 ℃ to 300 ℃, 400 ℃ to 650 ℃ or 450 ℃ to 550 ℃.Charging through cooling can be supplied to compressor 155 from one or more heat exchanger 133, or in another embodiment, can directly be supplied to reforming reactor 103.Alternatively, but more not preferably, the charging of leaving pre-reforming reactor 101 can be supplied to compressor 155 or reforming reactor 103 under situation about not cooling off.
Except cooling off by one or more heat exchanger 133, if the pressure in the reformation zone 157 of reforming reactor 103 is elevated to the pressure needs of 0.5MPa at least, then charging can be compressed at least 0.5MPa, 1.0MPa, 1.5MPa, 2MPa, 2.5MPa or the pressure of 3MPa at least at least at least at least at least by compressor 155, with keep in the reformation zone 157 of reforming reactor 103 that enough pressure is present in the hydrogen in the charging with driving and the hydrogen that produces by the charging in the reforming reactor 103 by the hydrogen separator 107 in the reforming reactor 103.Compressor 155 is the compressors that can at high temperature operate, and preferably commercially available star-like rotor compressor (StarRotor compressor).
To comprise that (selectively) compression of hydrogen, lighter hydrocarbons, steam and (selectively) carbon monoxide, the charging of (selectively) cooling are supplied to reforming reactor 103.Charging can have the pressure of 0.5MPa at least and 400 ℃ to 800 ℃, preferably 400 ℃ to 650 ℃ temperature.
Selectively, if catalytic reforming feedstock needs, extra steam can be added in the reformation zone 157 of reforming reactor 103 to mix with charging.In a preferred embodiment, can add extra steams and mix with charging when compressor 155 compresses when charging being used for by water under high pressure is injected compressors 155 from water inlet pipeline 131 via pipeline 165.(not shown) in one embodiment can be mixed in heat exchanger 133 one or more of water under high pressure and charging and in the water under high pressure injecting feeding by making.(not shown) in another embodiment, water under high pressure can be in charging being sent to one or more heat exchanger 133 before or later on or in the charging that charging is sent to before the compressor 155 or inject pipeline 153 later on.In one embodiment, water under high pressure can inject pipeline 153, or in the compressor 155, or in one or more heat exchanger 133, wherein said compressor 155 or described one or more heat exchanger 133 are not included in the system 100.
Water under high pressure heats with formation steam by mixing with charging, and charging is cooled off by mixing with water.The needs to one or more heat exchanger 133 can be eliminated or reduce to the cooling that provides to charging by the water that injects wherein, and preferably, the numerical limitations that will be used to cool off the heat exchanger 133 of charging is one at the most.
Alternatively, but more not preferably, the high steam pipeline 153 that can inject the reformation zone 157 of reforming reactor 103 or lead to reforming reactor 103 is to mix with charging.High steam can be by heat the steam that produces via the water under high pressure in water inlet pipeline 131 injected systems 100 owing to carry out heat exchange with the charging of leaving pre-reforming reactor 101 in one or more heat exchanger 133.High steam can be supplied to reforming reactor 101 via pipeline 159.Can use metering valve 161 and 163 control steam flowing to reforming reactor 103.High steam can have and the similar pressure of pressure that is supplied to the charging of reforming reactor 103.Alternatively, high steam can be supplied to pipeline 153 to mix with charging, so that the mixture of steam and charging can be compressed to selected pressure together before charging is supplied to compressor 155.High steam can have 200 ℃ to 500 ℃ temperature.
Can select the speed in water under high pressure or the high steam injecting feeding, thereby provide for reforming reactor 103 can to optimize effectively reforming reaction and water gas shift reaction in reforming reactor 103, to produce the quantity of steam of hydrogen.If in the water under high pressure injecting feeding, then can accommodometer metered valve 139,141 and 143 with control water via the speed in pipeline 165 injecting feedings.If high steam is injected reforming reactor 103 or pipeline 153, then can accommodometer metered valve 139,143,161 and 163 speed with control steam injection reforming reactor 103 or pipeline 153.
Charging and (selectively) extra steam are supplied to the reformation zone 157 of reforming reactor 103.The reformation zone can and preferably comprise the reforming catalyst that is positioned at wherein really.Reforming catalyst can be conventional steam reforming catalyst, and it is known to can be prior art.Spendable typical steam reforming catalyst includes but not limited to the 8th group 4 transition metal (nickel especially).Usually need be at refractory substrates (or supporter) upper support reforming catalyst.Supporter (if you are using) is preferably inert compound.The suitable inert compound that is used as supporter comprises the three races and the tetrels of periodic table, such as oxide or the carbide of Al, Si, Ti, Mg, Ce and Zr.
Charging and (selectively) extra steam mix and the contact reforming catalyst in the zone 157 of reforming under the temperature that can form the reformate gas that contains hydrogen and oxycarbide effectively.Reformate gas can form by the hydrocarbon in the charging is carried out steam reformation.Reformate gas also can be by making the steam in the charging and carbon monoxide generation water gas shift reaction forms and/or produce by steam reforming is carried out in charging.In one embodiment, if carry out quite a large amount of reformations in the pre-reforming reactor, and charging contains quite a large amount of carbon monoxide, and then reforming reactor 103 can play the effect of water-gas shift more.Reformate gas can contain hydrogen and at least a oxycarbide.Oxycarbide in the reformate gas comprises carbon monoxide and carbon dioxide.
One or more high temperature tubulose hydrogen separation membrane 107 can be arranged in the reformation zone 157 of reforming reactor 103, it is positioned to make charging can contact with hydrogen separation membrane 107 with reformate gas, and the membranous wall 167 that hydrogen can pass film 107 is sent to the hydrogen pipeline 169 that is positioned at tubular film 107.The hydrogen pipeline 169 that the membranous wall 167 of each corresponding hydrogen separation membrane 107 makes film 107 not with the reformation zone 157 of reforming reactor 103 in non-hydrogen compound, charging and the steam of reformate gas form gas and be communicated with.Membranous wall 167 can optionally make hydrogen (protium and/or hydrogen molecule) see through, the membranous wall 167 that hydrogen so that reform in the zone 157 can pass film 107 is sent to hydrogen pipeline 169, and other gas that prevents to reform in the zone 157 by membranous wall 167 is sent to hydrogen pipeline 169 simultaneously.
High temperature tubulose hydrogen separation membrane 107 in the reformation zone can comprise the supporter that is coated with the metal or alloy thin layer, and it can optionally make hydrogen see through.Supporter can be formed by pottery that hydrogen is passed or metal material.Porous stainless steel or Woelm Alumina are the preferred materials that is used for the supporter of film 107.The hydrogen selective metal or the alloy that are coated on the supporter can be selected from the 8th family's metal, include but not limited to Pd, Pt, Ni, Ag, Ta, V, Y, Nb, Ce, In, Ho, La, Au and Ru, especially, are alloy form.Palladium and platinum alloy are preferred.The especially preferred film 107 of Shi Yonging has extremely thin palladium alloy membrane in the method, and it has the high surface area that applies the porous stainless steel supporter.Can use U.S. Patent No. 6,152, disclosed method prepares this class film in 987.Platinum or the also suitable hydrogen selective material of doing of platinum alloy film with high surface area.
Pressure in the reformation zone 157 of reforming reactor 103 maintains the level of the pressure in the hydrogen pipeline 169 that is significantly higher than tubular film 107, enters the hydrogen pipeline 169 to force hydrogen to pass membranous wall 167 from the reformation zone 157 of reforming reactor.In one embodiment, hydrogen pipeline 169 is kept under atmospheric pressure or near atmospheric pressure, and the zone 157 of reforming maintains 0.5MPa at least, 1.0MPa, 2MPa or at least under the pressure of 3MPa at least at least.As indicated above, can reform zone 157 and will reform and regional 157 maintain under such high pressure by using compressor 155 compressions the mixture of charging to be injected from the charging of pre-reforming reactor 101 and with high pressure.Alternatively, can high steam be mixed with charging and high-pressure mixture be injected the reformation zone 157 of reforming reactor 103 and the zone 157 of will reforming maintains under such high pressure by as indicated above.Alternatively, can by high steam is mixed with the charging precursor and directly or the high pressure charging that will in pre-reforming reactor 101, produce via one or more heat exchanger 133 inject reforming reactor 103 and will reform and regional 157 maintain under such high pressure.The reformation zone 157 of reforming reactor 103 can maintain 0.5MPa at least, 1.0MPa, 2.0MPa or at least under the pressure of 3.0MPa at least at least.
Temperature when charging and (selectively) extra steam mix contact reforming catalyst also in the reformation zone 157 of reforming reactor 103 is at least 400 ℃, and preferably can be in 400 ℃ to 650 ℃ the scope, most preferably be in 450 ℃ to 550 ℃ the scope.With different at the typical steam reforming reaction that surpasses generation hydrogen under 750 ℃ the temperature, the balance of the reforming reaction of the inventive method is produced hydrogen and is promoted in the reforming reactor operating temperature range at 400 ℃ to 650 ℃, this is owing to removing hydrogen to the hydrogen pipeline 169 of hydrogen separation membrane 107 from the zone 157 of reforming and removing hydrogen from reforming reactor 103 thus.400 ℃ to 650 ℃ operating temperature has also promoted transformationreation, thereby carbon monoxide and steam-reforming are become more hydrogen, subsequently this hydrogen is removed to the hydrogen pipeline 169 of hydrogen separation membrane 107 from zone 103 membranous walls 167 via film 107 of reforming.In reforming reactor 103, realize hydrocarbon and carbon monoxide by reforming and water gas shift reaction almost completely changes into hydrogen and carbon dioxide, this owing to owing to removing hydrogen continuously from reforming reactor 103 from never reaching balance.
Be supplied to the charging of reforming reactor 103 to provide from pre-reforming reactor 101 in order to drive the heat of the reaction the reforming reactor 103.Be supplied to the charging of reforming reactor 103 can contain in order to driving the enough heat energy of the reaction the reforming reactor 103 from pre-reforming reactor 101, and can have 600 ℃ to 1000 ℃ temperature.Heat energy from the charging of pre-reforming reactor 101 can surpass the required heat energy of reaction that drives in the reforming reactor 103, and describe as mentioned, can be charging being supplied to reforming reactor 103 before in one or more heat exchanger 133 and/or by in the water injecting feeding and charging is cooled to 400 ℃ extremely less than 600 ℃ temperature.The cooling charging is preferred before the reforming reactor 103 in that charging is supplied to, so that make 1) temperature that can regulate in the reforming reactor 103 produce to promote the hydrogen in the water gas shift reaction; 2) can prolong life-span of film 107; And 3) improve compressor 155 performances.103 transmission is extremely effective to heat energy from pre-reforming reactor 101 to reforming reactor, and this is owing to be included in the charging from the heat energy of pre-reforming reactor 101, and it is combined closely with the interior reaction of reforming reactor 103.
(though being generally unnecessary) if necessary, additional heat can be supplied to reforming reactor 103 from the hot cathode exhaust stream from Solid Oxide Fuel Cell 105.Temperature is that 800 ℃ to 1100 ℃ hot cathode exhaust stream leaves the negative electrode 171 of fuel cell 105 from cathode exhaust gas outlet 173, and can be supplied to one or more cathode exhaust gas pipeline 177 in the reformation zone 157 that can be positioned at reforming reactor 103 via pipeline 175.When cathode exhaust stream during, can reach between (selectively) extra steam in the charging in the reformation zone 157 of cathode exhaust stream and reforming reactor 103 from the heat of hot cathode exhaust stream and to exchange through cathode exhaust gas pipeline 177.
Always the heat exchange (if present) that flows to heat absorption reforming reactor 101 from the cathode exhaust gas of fuel battery 105 is effective.Cathode exhaust gas pipeline 177 is positioned between the charging that allows in the reformation zone 157 of reforming reactor 103 in hot cathode exhaust streams and the reactor 103 and the extra steam (if present) and carries out heat exchange, thus in the position that reformation and transformationreation take place with heat transferred charging and extra steam (if present).In addition, because pipeline 177 near catalyst bed, is positioned at cathode exhaust gas pipeline 177 reforming catalyst that allows in the zone 157 of reforming in the hot cathode exhaust stream heated reformate zone 157.
Can be supplied to the speed (its operation by metering valve 179 and 181 is controlled) of the cathode exhaust gas pipeline 177 in the reforming reactor 103 to control the heat supply that flows to reforming reactor 103 from cathode exhaust gas by selection and control cathode exhaust stream.The cathode exhaust gas pipeline 177 that is not supplied to of cathode exhaust stream can be via pipeline 178 guiding heat exchangers 117 with the arbitrary portion that heat is provided to reforming reactor 103, and cathode exhaust stream can carry out heat exchange to add the hot feed precursor with the charging precursor therein.Accommodometer metered valve 179 and 181 to be allowing cathode exhaust stream to flow to cathode exhaust gas pipeline 177 in the reforming reactor 103 with selected speed by pipeline 175 in phase, and allow cathode exhaust stream be not used for provide the arbitrary portion of heat to flow to heat exchanger 117 to reforming reactor 103 by pipeline 178.The cathode exhaust stream of cooling that can be by will leaving the cathode exhaust gas pipeline 177 in the reforming reactor 103 is supplied to heat exchanger 117 that more heats are supplied to heat exchanger 117 to add the hot feed precursor via pipeline 180, and wherein Leng Que cathode exhaust stream has in order to the enough heat energy of heat is provided for the charging precursor.
In one embodiment, contain in order to driving enough heats of the reaction in the reforming reactor 103, and cathode exhaust stream is not supplied to reforming reactor 103 but can be supplied to heat exchanger 117 to add the hot feed precursor from the charging of pre-reforming reactor 101.In the present embodiment, in reforming reactor 103, do not need to comprise cathode exhaust gas pipeline 177.
The reformate gas stream of depleted of hydrogen can remove from the zone 157 of reforming via pipeline 183, and wherein the reformate gas stream of depleted of hydrogen can comprise unreacted feed and the non-hydrogen reformate of gaseous state in the reformate gas.Non-hydrogen reformate and unreacted feed can comprise carbon dioxide, water (for steam) and a small amount of carbon monoxide and unreacting hydrocarbon.A small amount of hydrogen also can be included in the reformate gas stream of depleted of hydrogen.
In one embodiment, the reformate gas stream of the depleted of hydrogen of separating from the zone 157 of reforming can be the carbon dioxide gas stream that contains the carbon dioxide of at least 0.8, at least 0.9, at least 0.95 or at least 0.98 molar fraction on the drying regime basis.Carbon dioxide gas stream is to have at least 0.5MPa, 1MPa, the 2MPa or the high pressure draught of the pressure of 2.5MPa at least at least at least.Hereinafter, will call carbon dioxide gas stream to the reformate gas stream of depleted of hydrogen.
The high-pressure carbon dioxide air-flow can leave reforming reactor 103 and in order to add the hot feed precursor and/or be supplied to the oxygen flow of negative electrode 171 of fuel cell 105 in order to heating in heat exchanger 185 in heat exchanger 115.Via charging precursor suction line 113 the charging precursor is supplied in the heat exchanger 115 simultaneously by carbon dioxide gas stream being sent to heat exchanger 115, can utilizes the high-pressure carbon dioxide air-flow to add the hot feed precursor via pipeline 187.In one embodiment, the high-pressure carbon dioxide of resulting cooling stream can be supplied to heat exchanger 185 just being supplied to the oxygen flow of the negative electrode 171 of fuel cell 105 with heating via pipeline 189 subsequently.In another embodiment, the high-pressure carbon dioxide stream of cooling can expand by turbine 147.
Alternatively, the high-pressure carbon dioxide air-flow that leaves the pre-reforming reactor can be used for heating the oxygen flow of the negative electrode 171 that is supplied to fuel cell 105 and does not add the hot feed precursor.The high-pressure carbon dioxide air-flow can be supplied to heat exchanger 185 with heating oxygen flow and cooled carbon dioxide air-flow via pipeline 183 from reforming reactor 103.The carbon dioxide gas stream of cooling can expand by turbine 147 subsequently.
Can by accommodometer metered valve 193 and 195 control high-pressure carbon dioxides streams from reforming reactor 103 to heat exchanger 115 and 185 flow.Can control flowing of carbon-dioxide flow heat exchanger 115 and 185 by accommodometer metered valve 193 and 195 so that charging precursor and/or oxygen flow are heated to selected temperature.Can the charging precursor be heated to certain temperature so that when the charging precursor is supplied to the pre-reforming reactor in conjunction with one or more extra heat exchanger 117, the charging precursor has at least 150 ℃, or 200 ℃ to 500 ℃ temperature.Oxygen-containing gas can be heated to certain temperature so that leave the temperature that the cathode exhaust stream of fuel cell has 750 ℃ to 1100 ℃, wherein oxygen flow can be heated to 150 ℃ to 450 ℃ temperature.Can pass through feedback mechanism accommodometer metered valve 193 and 195 automatically, the feedback mechanism temperature that can measure the temperature of the cathode exhaust stream that leaves fuel cell 105 and/or enter the charging precursor of pre-reforming reactor 101 wherein, and accommodometer metered valve 193 and 195 in setting limited field, maintains desired level with the internal pressures in the reforming reactor 103 with the temperature maintenance of the cathode exhaust stream that will enter pre-reforming reactor 101 and/or charging precursor simultaneously.
The high-pressure carbon dioxide air-flow can contain the water of quite a large amount of vapor form when it leaves reforming reactor 103.In one embodiment, can be by cooling off the high-pressure carbon dioxide air-flow in heat exchanger 115 and/or in the heat exchanger 185 and in (if necessary) one or more extra heat exchanger (not shown) and becoming water and remove steam from the high-pressure carbon dioxide air-flow by vapor condensation.This is useful under the situation of the pure relatively carbon-dioxide flow of needs, for example is used for strengthening from oil reservoir recovering the oil or being used for soda.
After over-heat-exchanger 115 and/or heat exchanger 185, high-pressure carbon dioxide stream can expand to drive turbine 147 and to produce low pressure CO 2 stream by turbine 147.Selectively, can make the high steam that in pre-reforming reactor 101 or reforming reactor 103, does not utilize through pipeline 191, under the situation of no high-pressure carbon dioxide stream, to expand by turbine 147 with high-pressure carbon dioxide stream or (selectively).Turbine 147 can be used for producing the electric power except the electric power that produces by fuel cell 105.Alternatively, turbine 147 can be used to drive one or more compressor, such as compressor 155 and 197.
Can enter into the hydrogen pipeline 169 of hydrogen separation membrane 107 by the membranous wall 167 that can optionally make hydrogen pass hydrogen separation membrane 107 and separate the air-flow (hereinafter being called hydrogen stream) that contains hydrogen from the reformate gas of reforming reactor 103.Hydrogen stream can contain the very hydrogen of high concentration, and can contain the hydrogen of at least 0.9, at least 0.95 or at least 0.98 molar fraction.
Since pass the high hydrogen flux of hydrogen separation membrane 107, can be with relative higher rate separation of hydrogen air-flow from reformate gas.Because hydrogen is present in the reforming reactor 103 with high partial pressures, so hydrogen passes hydrogen separation membrane 107 with the high pass dose rate.The high partial pressures of hydrogen is owing to 1 in the reforming reactor 103) be supplied in the anode exhaust stream of pre-reforming reactor 101 and in charging, send quite a large amount of hydrogen of reforming reactor 103 to; 2) in pre-reforming reactor 101, produce and be supplied to the hydrogen of reforming reactor 103; And 3) hydrogen that in reforming reactor 103, produces by reformation and transformationreation.Because the two-forty from the reformate separation of hydrogen does not need purge gas to assist from the hydrogen pipeline 169 of hydrogen separation membrane 107 and removes hydrogen and hydrogen is removed out reforming reactor 103.
Can be by exhaust line 199 from reforming reactor 103 separation of hydrogen air-flows.Can hydrogen stream be supplied to the anode 121 of Solid Oxide Fuel Cell 105 subsequently by the pipeline 201 that leads to anode inlet 203.Hydrogen stream offers anode 121 to be used for carrying out electrochemical reaction at fuel cell 105 along one or more anode electrode place and the oxidant of anode path with hydrogen.
Hydrogen stream is being supplied to before the anode 121, hydrogen stream or its part can be supplied to heat exchanger 115 to add hot feed precursor and cooled hydrogen stream.Hydrogen stream can have 400 ℃ to 650 ℃ temperature after leaving reforming reactor 103, be generally 450 ℃ to 550 ℃ temperature.Selectively, can be by in heat exchanger 115, carrying out heat exchange with hydrogen stream, and selectively carry out heat exchange with carbon dioxide gas stream and add the hot feed precursor by as indicated above.Can the charging precursor be heated to certain temperature so that when the charging precursor is supplied to the pre-reforming reactor in conjunction with one or more extra heat exchanger 117, the charging precursor has at least 150 ℃, or 200 ℃ to 500 ℃ temperature.
Be supplied to the hydrogen stream of the anode 121 of fuel cell 105 can be cooled to the temperature of 400 ℃ at the most, 300 ℃ at the most, 200 ℃ at the most, 150 ℃ at the most, 20 ℃ to 400 ℃ or 25 ℃ to 250 ℃, thereby with select and control is supplied to the temperature of oxygen flow of the negative electrode 171 of fuel cell 105 to combine, the operating temperature of Solid Oxide Fuel Cell 103 is controlled in 800 ℃ to 1100 ℃ the scope.Usually can be by in heat exchanger 115, carrying out heat exchange and hydrogen stream or its part be cooled to 200 ℃ to 400 ℃ temperature with the charging precursor.Selectively, can be by hydrogen stream or its part be sent to one or more extra heat exchanger (not shown) from heat exchanger 115, further carry out heat exchange with in one or more extra heat exchanger each with the charging precursor or with current, and further cooled hydrogen stream or its part.If use extra heat exchanger in system 100, then hydrogen stream or its part can be cooled to 20 ℃ to 200 ℃, preferably 25 ℃ to 100 ℃ temperature.In one embodiment, the part of hydrogen stream can be at heat exchanger 115 and is selectively cooled off in one or more extra heat exchanger, and whether the part of hydrogen stream can be supplied to the anode 121 of fuel cell 105 under situation about or not cooling off in heat exchanger, and the part of wherein combined hydrogen stream can be supplied to the anode 121 of fuel cell 105 under the temperature of 400 ℃ at the most, 300 ℃ at the most, 200 ℃ at the most, 150 ℃ at the most, 20 ℃ to 400 ℃ or 25 ℃ to 100 ℃.
Can select and control hydrogen stream or its part to heat exchanger 115 with selectively be supplied to the temperature of hydrogen stream of the anode 121 of fuel cell 105 with control to the flow rate of one or more extra heat exchanger.Can select and control hydrogen stream or its a part of flow rate by accommodometer metered valve 205 and 207 to heat exchanger 115 and selectable extra heat exchanger.Can accommodometer metered valve 205 with control hydrogen stream or its part under not cooled hydrogen stream or its a part of situation by pipeline 209 flowing to the anode 121 of Solid Oxide Fuel Cell 105.Can arrive flowing of heat exchanger 115 and any optional extra heat exchanger with control hydrogen stream or its part by pipeline 211 by accommodometer metered valve 207.Accommodometer metered valve 205 and 207 is to provide required cooling degree at the anode 121 that hydrogen stream is supplied to fuel cell 105 with the forward direction hydrogen stream in phase.In one embodiment, can be automatically in response to the feedback of the temperature of the anode exhaust stream that leaves fuel cell 105 and/or cathode exhaust stream is measured accommodometer metered valve 205 and 207 in phase.
The arbitrary portion that is supplied to heat exchanger 115 to reach the hydrogen stream that selectively is supplied to extra heat exchanger can be supplied to make up at the arbitrary portion of pipeline 215 with the hydrogen stream of guiding around heat exchanger 115 via pipeline 209 via pipeline 213 from heat exchanger 115 or via being used for cooling off last extra heat exchanger of first air-flow.In one embodiment, the part of the hydrogen stream of combination can be compressed in compressor 197 increasing the pressure of hydrogen stream, and hydrogen stream can be supplied to the anode 121 of fuel cell 105 via the pipeline 201 that leads to anode inlet 203 subsequently.In one embodiment, hydrogen stream can be compressed to 0.15MPa to 0.5MPa, or the pressure of 0.2MPa to 0.3MPa.Can provide Driven Compressor 197 required all or part of energy by the expansion that high-pressure carbon dioxide stream and/or high steam carry out through turbine 147.
In one embodiment, the purge gas that comprises steam can be injected in the hydrogen pipeline 169 of hydrogen separator 107 with the internal sweep hydrogen stream from membranous wall member 167 via pipeline 217, and increasing the hydrogen flux that passes hydrogen separator 107 thus and increase can be by the speed of hydrogen separator 107 from regional 157 separation of hydrogen of reforming.Hydrogen stream and steam blowing gas can remove from hydrogen separator 107 and reforming reactor 103 by hydrogen exhaust line 199.
In the present embodiment, before hydrogen stream was supplied to anode 107, hydrogen stream and steam blowing gas must cool off with hydrogen stream and the water outlet of steam blowing condensation of gas from combination.Valve 205 can cut out with hydrogen stream that prevents to make up and steam blowing gas and be supplied to anode by pipeline 209, and perhaps, alternatively, if utilize steam blowing gas, then system can not comprise pipeline 209 and valve 205.As indicated above, be supplied to heat exchanger 115 with by carrying out hydrogen stream and the steam blowing gas that combination is cooled off in heat exchange hydrogen stream and steam blowing gas with the charging precursor.Hydrogen stream and steam blowing gas must be cooled to be enough to divide from hydrogen stream dried up, therefore, the hydrogen stream of combination and steam blowing gas can be supplied to hydrogen stream and the steam blowing gas of one or more extra heat exchanger (not shown) with the cooling combination, so that the condensation water outlet from making up.Be used to cool off the hydrogen stream of combination and last heat exchanger of steam blowing gas can be the condenser (not shown), make the steam blowing condensation of gas therein and separate from hydrogen stream.Can be in heat exchanger hydrogen stream be cooled to and be lower than 100 ℃, be lower than 90 ℃, be lower than 70 ℃ or be lower than 60 ℃, with from hydrogen stream condensation and separate vapour purge gas.As indicated above, the dry hydrogen air-flow of separation subsequently can by pipeline 213,215 and 201 and compressor 147 be supplied to the anode 121 of fuel cell 105.
Hydrogen stream (no matter whether separating from reforming reactor 103 with steam blowing gas) can be supplied to the anode 121 of Solid Oxide Fuel Cell 105 via leading to pipeline 201 anode inlet 203 subsequently.Hydrogen stream offers anode 121 to be used for carrying out electrochemical reaction at fuel cell 105 along one or more anode electrode place and the oxidant of anode path with hydrogen.Can be supplied to the speed of reforming reactor 103 to select hydrogen stream to be supplied to the speed of the anode 121 of fuel cell 105 by selecting charging, and be supplied to the speed of pre-reforming reactor 101 to select charging to be supplied to the speed of reforming reactor 103, and control the speed that the charging precursor is supplied to pre-reforming reactor 101 by regulating charging precursor inlet valve 137 by the charging precursor.
Alternatively, can be by selecting hydrogen stream to be supplied to the speed of the anode 121 of fuel cell 105 with coordination mode control metering valve 149 and 151.Can accommodometer metered valve 151 to increase or to reduce hydrogen stream flowing to the anode 121.Can accommodometer metered valve 149 to increase or to reduce hydrogen stream flowing to hydrogen storage tank 223.Can control metering valve 149 and 151 according to coordinated mode, so that the hydrogen stream of selected speed can be supplied to the anode 121 of fuel cell 105 via pipeline 201, surpassing the hydrogen stream part that the selected required hydrogen flowing quantity of speed is provided simultaneously can be supplied to hydrogen jar 223 via pipeline 225.
Oxygen flow is supplied to the negative electrode 171 of fuel cell via pipeline 229 by cathode inlet 227, so that the oxidant that can pass electrolyte and one or more anode electrode place in fuel cell 105 and the hydrogen generation electrochemical reaction in the hydrogen stream to be provided.Oxygen flow can be provided by air compressor or oxygen tank (not shown).In one embodiment, oxygen flow can be air or pure oxygen.In another embodiment, oxygen flow can be the oxygen-enriched air stream that contains at least 21% oxygen, wherein, oxygen-enriched air stream is useful on the more polyoxy that in fuel cell, changes into oxonium ion, so oxygen-enriched air stream is compared the electrical efficiency that provides higher in Solid Oxide Fuel Cell with air owing to containing.
Oxygen flow can heat before the negative electrode 171 that is supplied to fuel cell 105.In one embodiment, oxygen flow can be before the negative electrode 171 that is supplied to fuel cell 105 in heat exchanger 185 by with carry out heat exchange from least a portion of the carbon-dioxide flow of reforming reactor 103 and be heated to 150 ℃ to 350 ℃ temperature.In another embodiment, can be by in heat exchanger 185, carrying out heat exchange with the heating oxygen flow with the carbon-dioxide flow that comes the cooling of automatic heat-exchanger 115.In another embodiment, can be by in heat exchanger 185, carrying out heat exchange with the heating oxygen flow be supplied to the high steam of heat exchanger 185 by pipeline 231.In another embodiment, can be by carrying out heat exchange with the heating oxygen flow in heat exchanger 185 with the cathode exhaust stream that offers the cooling of heat exchanger 185 from heat exchanger 117 via pipeline 233.Alternatively, can perhaps can under situation about not heating, oxygen flow be offered the negative electrode 171 of fuel cell 105 by electric heater (not shown) heating oxygen flow.
The Solid Oxide Fuel Cell 105 of Shi Yonging can be traditional Solid Oxide Fuel Cell (preferably having plane or tubular structure) in the method for the invention, and comprise anode 121, negative electrode 171 and electrolyte 235, wherein electrolyte 235 is between anode 121 and negative electrode 171.Solid Oxide Fuel Cell can comprise a plurality of single fuel cell that is stacked, and described a plurality of single fuel cells are by the cross tie part electrical engagement and be operatively connected so that hydrogen stream can flow through the anode of the fuel cell that piles up and the negative electrode that oxygen-containing gas can flow through the fuel cell that piles up.Solid Oxide Fuel Cell 105 can be single Solid Oxide Fuel Cell or a plurality of Solid Oxide Fuel Cell through being operatively connected or piling up.In one embodiment, anode 121 is by Ni/ZrO 2Cermet forms, and negative electrode 171 is by being impregnated with praseodymium oxide and being coated with the In of doping SnO 2O 3Iron-based alloy or stabilisation ZrO 2Form, and electrolyte 235 is by the ZrO of stabilized with yttrium oxide 2(8mol%Y roughly 2O 3) form.Cross tie part between single fuel cell of each of piling up or the tubular fuel cell can be a doping chromic acid lanthanum.
Solid Oxide Fuel Cell 105 is configured to make hydrogen stream to flow to anode exhaust outlet 123 from the anode 121 of anode inlet 203 by fuel cell 105, thus one or more anode electrode on the anode path of contact outlet 123 from anode inlet 203 to anode exhaust.Fuel cell 105 also is configured to make oxygen-containing gas to flow to cathode exhaust gas outlet 173 by negative electrode 171 from cathode inlet 227, thus one or more cathode electrode on the negative electrode path of contact outlet 173 from cathode inlet 227 to cathode exhaust gas.Electrolyte 235 is positioned in the fuel cell 105 preventing that hydrogen stream from entering negative electrode 171 and preventing that oxygen-containing gas from entering anode 121, and oxonium ion is conducted to anode 121 to be used for carrying out electrochemical reaction at the hydrogen of one or more anode electrode and hydrogen stream from negative electrode 171.
Solid Oxide Fuel Cell 105 arrives under the temperature of anode 121 of fuel cells 105 and operates can making oxonium ion can cross electrolyte 235 from negative electrode 171 effectively.Solid Oxide Fuel Cell 105 can be operated under the temperature of 700 ℃ to 1100 ℃ or 800 ℃ to 1000 ℃.Utilizing oxonium ion is the reaction of a large amount of heat releases at one or more anode electrode place to the oxidation of hydrogen, and the heat of reaction produces the required heat of operation Solid Oxide Fuel Cell 105.The flow rate that temperature that can be by controlling hydrogen stream and oxygen flow independently and these stream flow to fuel cell 105 is controlled the temperature of Solid Oxide Fuel Cell 105 operations.In one embodiment, the temperature that is supplied to the hydrogen stream of fuel cell 105 can be controlled at the temperature of 400 ℃ at the most, 300 ℃ at the most, 200 ℃ at the most, 100 ℃ at the most, 20 ℃ to 400 ℃ or 25 ℃ to 250 ℃, and the temperature of oxygen flow can be controlled at 400 ℃ at the most, 300 ℃ at the most, 200 ℃ at the most, the temperature of 100 ℃ or 150 ℃ to 350 ℃ at the most, maintain with operating temperature in 700 ℃ to 1000 ℃ the scope, preferably in 800 ℃ to 950 ℃ scope Solid Oxide Fuel Cell 105.
In one embodiment, one or more pipeline 263 of one or more pipeline 261 that can be by high steam being sent to the exterior circumferential that is positioned at fuel cell 105 from pipeline 191 or the inside by extending through fuel cell 105 offers fuel cell 105 with cooled fuel cell 105 thereby will replenish cooling.Resulting superheated steam can expand through pipeline 191 and by turbine 147.
For the operation of initial fuel cell 105, fuel cell 105 is heated to its operating temperature.In a preferred embodiment, can be by in catalytic partial oxidation reforming reactor 237, producing hydrogen-containing gas streams, and hydrogen-containing gas streams is supplied to the operation of the anode 121 initial Solid Oxide Fuel Cell 105 of Solid Oxide Fuel Cell via pipeline 239.Can be by in catalytic partial oxidation reforming reactor 237, producing hydrogen-containing gas streams in catalytic partial oxidation reforming reactor 237, burning hydrocarbon charging and source of oxygen under the situation that has conventional partial oxidation reforming catalyst, wherein source of oxygen is to be supplied to catalytic partial oxidation reforming reactor 237 with respect to the hydrocarbon charging for being lower than stoichiometric quantity.The hydrocarbon charging can be supplied to catalytic partial oxidation reforming reactor 237 by suction line 241, and source of oxygen can be supplied to catalytic partial oxidation reforming reactor 237 by pipeline 243.
The hydrocarbon charging that is supplied to catalytic partial oxidation reforming reactor 237 can be the mixture of liquid state or gaseous hydrocarbon or hydrocarbon, and can be the mixture of methane, natural gas or other low molecular weight hydrocarbon or low molecular weight hydrocarbon.In a special preferred embodiment of the inventive method, the hydrocarbon charging that is supplied to catalytic partial oxidation reforming reactor 237 can be and the identical charging of using in pre-reforming reactor 101 of charging precursor-type, the number that carries out the required hydrocarbon charging of this method with minimizing, and can charging be supplied to catalytic partial oxidation reforming reactor 237 via pipeline 245 from feed entrance pipeline 113.
Being supplied to the oxygen charging that contains of catalytic partial oxidation reforming reactor 237 can be pure oxygen, air or oxygen-enriched air.Containing the oxygen charging should be to be supplied to catalytic partial oxidation reforming reactor 237 with respect to the hydrocarbon charging for being lower than stoichiometric quantity, to burn with the hydrocarbon charging in catalytic partial oxidation reforming reactor 237.In one embodiment, be supplied to catalytic partial oxidation reforming reactor 237 contain the oxygen charging and start after to be used for the oxygen flow source of operation of fuel cells 105 identical, and can will contain the oxygen charging from oxygen flow suction line 221 and be supplied to catalytic partial oxidation reforming reactor 237 via pipeline 243.
The hydrogen-containing gas streams that burning by hydrocarbon charging and oxygen-containing gas in catalytic partial oxidation reforming reactor 237 forms contain can be in the anode 121 of fuel cell 105 by in one or more place's catalytic oxidation agent of anode electrode and the compound of oxidation, comprise hydrogen and carbon monoxide, and such as other compound of carbon dioxide.The compound that should not contain one or more anode electrode oxidation in the anode 121 that can make fuel cell 105 from the hydrogen-containing gas streams of catalytic partial oxidation reforming reactor 237.
The hydrogen-containing gas streams that forms in catalytic partial oxidation reforming reactor 237 is hot, and can have the temperature of at least 700 ℃, 700 ℃ to 1100 ℃ or 800 ℃ to 1000 ℃.Use is preferred from the startup of the next initial Solid Oxide Fuel Cell 105 of hot hydrogen stream of catalytic partial oxidation reforming reactor 237 in the method for the invention, and this is because it makes the temperature of fuel cell 105 can rise to the operating temperature of fuel cell 105 almost instantaneously.In one embodiment, when the operation of initial fuel cell 105 during, can in heat exchanger 185, make from the hot hydrogen-containing gas of catalytic partial oxidation reforming reactor 237 and be supplied between the oxygen-containing gas of negative electrode 171 of fuel cell 105 and carry out heat exchange with the heating oxygen-containing gas.
In case reach the operating temperature of fuel cell 105, flowing of hot hydrogen-containing gas streams from catalytic partial oxidation reforming reactor 237 to fuel cell 105 can be cut off by valve 249, will be supplied in the anode 121 from the hydrogen stream of reformation reactor 103 and oxygen flow is supplied in the negative electrode 171 of fuel cell 105 by opening valve 151 simultaneously.If it is identical with the source of charging precursor to flow to the hydrocarbon charging of catalytic partial oxidation reforming reactor, then valve 251 can cut out to prevent that the hydrocarbon feed flow is to catalytic partial oxidation reforming reactor 237 in the operating period of fuel cell 105.Similarly, if flow to catalytic partial oxidation reforming reactor 237 to contain the oxygen charging identical with the oxygen flow source of using in the negative electrode 171 of fuel cell 105, then valve 253 can cut out to prevent containing the oxygen feed flow to catalytic partial oxidation reforming reactor 237 in the operating period of fuel cell 105.The method according to this invention, the continued operation of fuel cell can be carried out subsequently.
In another embodiment, can be before hydrogen stream being introduced in the fuel cell 105, use Jing Guo startup heater 255 from hydrogen storage tank 223 so that fuel cell 105 rises to the operation of the initial fuel cell 105 of hydrogen startup air-flow of its operating temperature.Hydrogen storage tank 223 can be operatively connected to fuel cell 105 and introduce in the anode 121 of Solid Oxide Fuel Cell 105 to allow that hydrogen is started air-flow.Start heater 255 and can indirectly hydrogen be started the temperature that air-flow is heated to 750 ℃ to 1000 ℃.Starting heater 255 can be that electric heater maybe can be a burning heater.In case reach the operating temperature of fuel cell 105, can cut off hydrogen by valve 257 and start gas and flow to flowing in the fuel cell 105, and hydrogen stream and oxygen flow can be introduced in the fuel cell 105 operation with initial fuel cell.
During the operation of fuel cell 105 is initial, oxygen flow can be introduced in the negative electrode 171 of fuel cell 105.Oxygen flow can be air, contain the oxygen-enriched air of at least 21% oxygen, or pure oxygen.Preferably, oxygen flow is the oxygen flow that is supplied to negative electrode 171 after the operation of initial fuel cell in the operating period of fuel cell 105.
In a preferred embodiment, between the starting period of fuel cell 105, be supplied to the oxygen flow of the negative electrode 171 of fuel cell 105 to have at least 500 ℃, preferably at least 650 ℃, more preferably at least 750 ℃ temperature.Oxygen flow can be heated by electric heater (not shown) or burning heater (not shown) before the negative electrode 171 that is supplied to Solid Oxide Fuel Cell 105 indirectly.In a preferred embodiment, be used for the oxygen flow of the operation of initial fuel cell 105 can be before the negative electrode 171 that is supplied to fuel cell 105 at heat exchanger 185 by heating with heat exchange from the hot hydrogen-containing gas streams of catalytic partial oxidation reforming reaction.
In case the operation of fuel cell 105 begins, hydrogen stream can mix with the oxonium ion oxidant to produce electric power at one or more anode electrode place in fuel cell 105.The oxonium ion oxidant is obtained and is guided through the electrolyte 235 of fuel cell by the oxygen in the oxygen flow of the negative electrode 171 that flows through fuel cell 105.By hydrogen stream and oxygen flow are supplied to fuel cell 105 with selected independent rate, while operation of fuel cells under 750 ℃ to 1100 ℃ temperature, and make the hydrogen stream of the anode 121 that is supplied to fuel cell 105 and oxidant be in mixing in the anode 121 at one or more anode electrode of fuel cell 105.
Preferably, hydrogen stream and oxidant mix to press 0.4W/cm at least at one or more anode electrode place of fuel cell 105 2, 0.5W/cm at least preferably 2, 0.75W/cm at least 2, 1W/cm at least 2, 1.25W/cm at least 2Or 1.5W/cm at least 2Power density produce electric power.Can be by selecting and the control hydrogen stream is supplied to the speed of the speed of anode 121 of fuel cell 105 and the negative electrode 171 that oxygen flow is supplied to fuel cell 105 and produces electric power with such power density.Can select and control the flow rate of oxygen flow by regulating oxygen intake valve 259 to the negative electrode 171 of fuel cell 105.
As indicated above, can be by selecting and control charging to be supplied to the speed of reforming reactor 103 to select and control the flow rate that hydrogen flows to the anode 121 of fuel cell 105, and be supplied to the speed of pre-reforming reactor 101 to select and control the speed that charging is supplied to reforming reactor 103, and select and control the speed that the charging precursor is supplied to pre-reforming reactor 101 by regulating charging precursor inlet valve 137 by the charging precursor.Alternatively, as indicated above, can be by selecting and control the speed that hydrogen stream is supplied to the anode 121 of fuel cell 105 with coordination mode control metering valve 149 and 151.In one embodiment, can by feedback mechanism automatically accommodometer metered valve 149 and 151 to keep the selected flow rate that hydrogen flows to anode 121, wherein this feedback mechanism can be based on hydrogen content in the antianode exhaust stream or the water content in the anode exhaust stream, or the water that forms in fuel cell is for the measurement of the ratio of the hydrogen in the anode exhaust stream and operate.
In the method for the invention, by utilizing oxidant to make to be present in a part of oxidation of the hydrogen in the hydrogen stream that is supplied to fuel cell 105, hydrogen stream mixes at one or more anode electrode place with oxidant and produces water (for steam).The water that is produced with oxidant oxidation hydrogen is purged the anode 121 that passes through fuel cell 105 by the non-reacted parts of hydrogen stream, to leave anode 121 as the part of anode exhaust stream.
In an embodiment of the inventive method, can select and control hydrogen stream and be supplied to the flow rate of anode 121 so that the water yield that time per unit forms in fuel cell 105 is at the most 1.0, at the most 0.75, at the most 0.67, at the most 0.43, at the most 0.25 or at the most 0.11 with respect to the ratio of the hydrogen amount in the time per unit anode exhaust.In one embodiment, the water yield that forms in the fuel cell 105 can mole be the unit measurement with the hydrogen amount in the anode exhaust, makes the ratio of the water yield that forms in the time per unit fuel cell of time per unit in mole and the hydrogen amount in the time per unit anode exhaust be at the most 1.0, at the most 0.75, at the most 0.67, at the most 0.43, at the most 0.25 or at the most 0.11.In one embodiment, can select and control the flow rate that hydrogen stream is supplied to anode 121, so that the hydrogen utilance of passing through in the fuel cell 105 is less than 50%, at the most 45%, at the most 40%, at the most 30%, at the most 20% or at the most 10% at every turn.
In another embodiment of the inventive method, can select and control the flow rate that hydrogen stream is supplied to anode 121, so that anode exhaust stream contains the hydrogen of at least 0.6, at least 0.7, at least 0.8 or at least 0.9 molar fraction.In another embodiment, can select and control the flow rate that hydrogen stream is supplied to anode 121 so that anode exhaust stream contain hydrogen in the hydrogen stream that is supplied to anode 121 greater than 50%, at least 60%, at least 70%, at least 80% or at least 90%.
Should select to provide to the flow rate of the oxygen flow of the negative electrode 171 of Solid Oxide Fuel Cell 105 so that enough oxidants to be provided to anode, with box lunch at one or more anode electrode place with from the fuel-bound of hydrogen stream the time with 0.4W/cm at least 2, 0.5W/cm at least 2, 0.75W/cm at least 2, 1W/cm at least 2, 1.25W/cm at least 2Or 1.5W/cm at least 2Power density produce electric power.As indicated above, can select and control the flow rate of oxygen flow by regulating oxygen intake valve 259 to negative electrode 171.In the method for the invention, with regard to the per unit electric power that produces by this method, produce few relatively carbon dioxide.The heat integration (wherein the heat that produces in fuel cell 105 is directly delivered to pre-reforming reactor 101 in and subsequently in the anode exhaust stream from fuel cell 105 and is directly delivered to reforming reactor 103 in the charging from pre-reforming reactor 101) of pre-reforming reactor 101 and reforming reactor 103 and fuel cell 105 reduces and has preferably eliminated the driving additional energy that pre-reforming and reforming reaction need provide that absorbs heat, thereby reduced the needs that this energy for example is provided by burning, having reduced is thus providing energy to drive the amount of the carbon dioxide that produces in the reforming reaction.In addition, make anode exhaust stream by system's 100 recirculation with by separating rich hydrogen first air-flow from the reformed gas product and subsequently first air-flow being supplied to fuel cell 105 and rich hydrogen first air-flow is offered fuel cell 105 having reduced the hydrogen amount that need produce by reforming reactor 301, and improved the electrical efficiency of this method, reduced the generation of the carbon dioxide by-product of following thus.
In the method for the invention, to generate the speed generation carbon dioxide that every kilowatt hour electric power is no more than 400 grams (400g/kWh).In a preferred embodiment, produce carbon dioxide with the speed that is no more than 350g/kWh in the method for the invention, and in a more preferred embodiment, produce carbon dioxide with the speed that is no more than 300g/kWh in the method for the invention.
In another embodiment, method utilization of the present invention comprises the steam reformer of heat integration, the hydrogen separator that is positioned at the steam reformer outside and the system of Solid Oxide Fuel Cell.Referring now to Fig. 2,, the system 200 of method that is used to implement present embodiment is similar with system shown in Figure 1 100, and system unit is numbered substantially in the same manner, difference is reforming reactor 303, hydrogen separator 301 and parts thereof, and hydrogen separator 301 is connected to some pipeline in the system 200.Hydrogen separator 301 is not arranged in reforming reactor 303, but operation is attached to reforming reactor 303, makes in reforming reactor 303 reformate gas that contains hydrogen and oxycarbide that forms and unreacted hydrocarbon and steam be sent to hydrogen separator 301 by pipeline 305.In one embodiment, hydrogen separator 301 is high temperature hydrogen separators, is preferably the permeable film device of tubulose hydrogen as indicated above.In another embodiment, hydrogen separator 301 can be to be lower than 150 ℃ or be lower than the hydrogen separator of operating under 100 ℃ the temperature, such as the pressure adsorbent equipment that swings.
Can will contain the hydrogen stream of hydrogen from reformate gas and unreacted steam and hydrocarbon separation by hydrogen separator 301.In one embodiment, hydrogen separator 301 is that tubulose hydrogen is permeable, hydrogen selective membrane device, wherein, can equal or near the temperature of the operating temperature of reforming reactor 303 under from reformate gas, steam and unreacting hydrocarbon separation of hydrogen air-flow, hydrogen stream subsequently can be directly or is supplied to the anode 121 of fuel cell 105 via heat exchanger 115.Hydrogen stream can directly be supplied to anode 121 from hydrogen separator 301 via pipeline 209 under situation about not cooling off.Alternatively, can hydrogen stream is supplied to before the anode 121 via pipeline 307 hydrogen stream is sent to heat exchanger 115 and in heat exchanger 115 cooled hydrogen stream, wherein valve 309 can be used for controlling hydrogen stream flowing to heat exchanger 115.
In one embodiment, can by in pipeline 311 steam blowing gas injection tube shape hydrogen is permeable, the hydrogen selective membrane equipment 301 to promote the separation of hydrogen stream.In the present embodiment, can be permeable from tubulose hydrogen, hydrogen selective membrane 301 is supplied to heat exchanger 115 with hydrogen stream and steam blowing gas, and be supplied to the condenser (not shown) separating purge gas from hydrogen stream subsequently, and subsequently can the anode 121 that hydrogen stream is supplied to Solid Oxide Fuel Cell 105 as indicated above.
In another embodiment, hydrogen separator 301 can be the pressure adsorbent equipment that swings.In the present embodiment, can be in one or more heat exchanger (not shown) that is operatively connected between reforming reactor 303 and hydrogen separator 301 and connects reformate gas, steam and unreacted feed be cooled to utilize by pipeline 305 pressure swing adsorbent equipment with the temperature of other compound separation in the mixture of hydrogen stream and reformate gas, steam and unreacted feed (be generally be lower than 150 ℃, be lower than 100 ℃ or be lower than 75 ℃ temperature).
Can separate non-hydrogen through reformate and unreacted feed from hydrogen separator 301 via pipeline 313 as the gaseous state of gaseous flow.Non-hydrogenly can comprise carbon dioxide, water (for steam) and carbon monoxide and unreacting hydrocarbon on a small quantity through reformate and unreacted feed.Non-hydrogenly can be supplied to heat exchanger 185 or heat exchanger 115 via pipeline 187, to be used to cool off and to add the hot feed precursor respectively or be supplied to the oxygen-containing gas of the negative electrode 171 of fuel cell 105 through reformate and unreacted feed.Valve 195 and 315 can be used for controlling non-hydrogen through reformate and unreacted feed flowing to heat exchanger 185 and/or heat exchanger 115.
Utilization be positioned at reforming reactor 303 outsides hydrogen separator 301 method remainder can according to above about Solid Oxide Fuel Cell 105 and contain the identical substantially mode of the reforming reactor 103 described methods (as indicated above) of hydrogen separation membrane 107 therein and implement.
On the other hand, the present invention relates to a kind of system that produces electric power.Referring now to Fig. 3,, system 400 comprises pre-reforming reactor 401, reforming reactor 403, Solid Oxide Fuel Cell 405 and hydrogen separation equipment 407.
The Solid Oxide Fuel Cell 405 of system 400 comprises the anode 409 with anode inlet 411 and anode exhaust outlet 413, the negative electrode 415 with cathode inlet 417 and cathode exhaust gas outlet 419, and between anode 409 and negative electrode 415, contact anode 409 and negative electrode 415 and separate the electrolyte 421 of anode 409 and negative electrode 415.The Solid Oxide Fuel Cell, its anode, negative electrode and the electrolyte that are used for system of the present invention above have been described in further detail.
Pre-reforming reactor 401 comprises pre-reforming zone 423, one or more pre-reforming reactor feed precursor inlet 425, one or more pre-reforming reactor anode exhaust inlet 427 and one or more pre-reforming reactor outlet 429.The pre-reforming zone 423 of pre-reforming reactor 401 is suitable for making one or more hydrocarbon cracking of charging precursor to form charging, wherein the crackene in the charging with in the charging precursor, obtain hydrocarbon phase that crackene is derived from carbon content than molecular weight with minimizing and minimizing.Contain Cracking catalyst 431 in the pre-reforming zone 423, it is positioned in the pre-reforming zone 423 and contacts with the vaporization mixture of steam and one or more hydrocarbon.Cracking catalyst 431 can be the pre-reforming catalyst that describes in further detail as mentioned.One or more pre-reforming charging precursor inlet 425 connects with the gas/fluid mode of communicating with the pre-reforming zone 423 of pre-reforming reactor 401, makes liquid state or gaseous feed precursor to enter the mouth in the pre-reforming zone 423 of 425 introducing pre-reforming reactors 401 via pre-reforming reactor feed precursor.One or more pre-reforming reactor anode exhaust inlet 427 connects with the gas mode of communicating with the pre-reforming zone 423 of pre-reforming reactor 401, and connect with the operation of gas mode of communicating with the anode exhaust outlet 413 of fuel cell 405, make that exporting 413 anode exhaust streams that leave fuel cell 405 from anode exhaust can introduce the pre-reforming zone 423 of pre-reforming reactor 401 via one or more pre-reforming reactor anode exhaust inlet 427.In one embodiment, anode exhaust outlet 413 and one or more pre-reforming reactor anode exhaust enter the mouth and 427 directly connect with the gas mode of communicating.One or more pre-reforming reactor outlet 429 is communicated with pre-reforming zone 423 gases of pre-reforming reactor 401.
The reforming reactor 403 of system 400 comprises reform zone 433 and one or more reformer section realm entry 435.The reformation zone 433 of reforming reactor 403 is suitable for making the vaporization mixture of the charging that comprises one or more hydrocarbon and steam to reform containing the reformate gas of hydrogen with formation.Reforming catalyst 437 is contained in reformation zone 433, and it is positioned in the zone 433 of reforming and contacts with the vaporization mixture of charging that comprises one or more hydrocarbon and steam.Reforming catalyst can be the reforming catalyst that describes in further detail as mentioned.One or more reformer section realm entry 435 connects with the gas mode of communicating with the zone 433 of reforming and connects with the operation of gas mode of communicating with one or more pre-reforming reactor outlet 429, to allow in the charging and the reformation zone 433 of steam via reformer section realm entry 435 introducing reforming reactors 403 from pre-reforming reactor 401.
The hydrogen separation equipment 407 of system 400 comprises member 439 and the hydrogen outlet 441 that hydrogen is seen through.The permeable member 439 of the hydrogen of hydrogen separation equipment 407 can be arranged in the reformation zone 433 of reforming reactor 403 with the gas mode of communicating with the reformation zone 433 of reforming reactor 403, but makes bog in the reformation zone 433 of the permeable member 439 contact reforming reactors 403 of hydrogen.Hydrogen outlet 441 connects with the gas mode of communicating with the permeable parts 439 of hydrogen, wherein the permeable member 439 of hydrogen between between the reformation of reforming reactor 403 zone 433 and the hydrogen outlet 441 to allow hydrogen regional 433 optionally to flow to hydrogen outlet 441 via the permeable member 439 of hydrogen from reforming.Hydrogen outlet also connects with the operation of gas mode of communicating with the anode inlet 411 of fuel cell 405, flow to the anode 409 of fuel cell 405 from hydrogen separation equipment 407 to allow hydrogen stream.
In one embodiment, system 400 can comprise first heat exchanger 443.First heat exchanger can connect with the operation of gas mode of communicating with one or more pre-reforming reactor outlet 429 of pre-reforming reactor 401, and connect with the operation of gas mode of communicating with one or more reformer section realm entry 435 of reforming reactor 403, make the heat exchanger of winning to cool off the charging that is sent to reforming reactor 403 from pre-reforming reactor 401.
In one embodiment, system 400 can comprise compressor 445.Compressor 445 can connect with the operation of gas mode of communicating with one or more pre-reforming reactor outlet 429 of pre-reforming reactor 401, and connect with the operation of gas mode of communicating with one or more reformer section realm entry 435 of reforming reactor 403, make compressor 445 can compress the charging that is sent to reforming reactor 403 from pre-reforming reactor 401.In one embodiment, compressor 445 can connect with the gas mode of communicating with the reformer section realm entry 435 of first heat exchanger 443 and reforming reactor 403, make when charging when pre-reforming reactor 401 is sent to reforming reactor 403, compressor 445 can compress the charging of being cooled off by first heat exchanger 443.
In one embodiment, system 400 can comprise second heat exchanger 447.Second heat exchanger 447 can be operationally connected to the hydrogen outlet 441 of hydrogen separation equipment 407, and can be operationally connected to the anode inlet 411 of the anode 409 of fuel cell 405, make second heat exchanger 447 can cool off the hydrogen stream that is sent to the anode 409 of fuel cell 405 from hydrogen separation equipment 447.
In one embodiment, system 400 can comprise condenser 449.Condenser 449 can be operationally connected to the hydrogen outlet 441 of hydrogen separation equipment 407, and can be operationally connected to the anode inlet 411 of the anode 409 of fuel cell 405, make that when utilizing steam blowing gas that hydrogen is purged out hydrogen separation equipment 407 condenser 449 can be from the hydrogen stream condensation water outlet of the anode 409 that is sent to fuel cell 405 by hydrogen separation equipment 407.In one embodiment, second heat exchanger 447 can be operationally connected to the hydrogen outlet 441 of hydrogen separation equipment 407, and can be operationally connected to condenser 449, wherein condenser 449 is operationally connected to the anode inlet 411 of the anode 409 of fuel cell 405, make from hydrogen separation equipment 407 be sent to the hydrogen stream of the anode 409 of fuel cell 405 can be at first second heat exchanger 447 cooling and subsequently in condenser 449 from hydrogen stream condensation water outlet.
In one embodiment, system 400 can comprise catalytic partial oxidation reactor 451.The catalytic partial oxidation reactor can be operationally connected to the anode inlet 411 of the anode 409 of fuel cell 405, and wherein the catalytic partial oxidation reactor can offer the operation of the anode 409 of fuel cell 405 with initial fuel cell 405 with starting hydrogen stream effectively.
In another embodiment, as shown in Figure 4, system 500 can comprise pre-reforming reactor 501, reforming reactor 503, Solid Oxide Fuel Cell 505 and hydrogen separation equipment 507, described about system 400 as mentioned, and difference is that hydrogen separation equipment 507 is positioned at the outside of reforming reactor 503 and is operatively connected with the gas mode of communicating with the reformation zone 533 of reforming reactor 503.Hydrogen is permeable, hydrogen selectivity member 539 connects with the operation of gas mode of communicating with the reformation zone 533 of reforming reactor 503, make the gaseous product of the reformation of generation in the zone 533 of reforming to be sent to member 539 from the zone 533 of reforming, therefore can pass through member 539 separation of hydrogen from reformate gas.
In one embodiment, member 539 can be that high temperature hydrogen is permeable, the hydrogen selective membrane, and is as indicated above.In another embodiment, member 539 can be the pressure absorber that swings.In one embodiment, especially, if member 539 is the pressure absorbers that swing, then between one or more heat exchanger 553 reformation zone 533 that can be connected to reforming reactor 503 with the gas mode of communicating and the member 539, to use member 539 to make hydrogen cool reformate gas before the reformate gas separation.
The hydrogen outlet 541 of hydrogen separation equipment 507 is positioned to be in gas with the member 539 that hydrogen is seen through of hydrogen separation equipment 507 and is communicated with.Can optionally make member 539 that hydrogen sees through between the reformation zone 533 and hydrogen outlet 541 of reforming reactor 503, flow to allow hydrogen to carry out selectivity via the permeable member 539 of hydrogen, and flow out hydrogen separation equipment 507 via hydrogen outlet 541 from the zone 533 of reforming.
Hydrogen outlet 541 connects with the operation of gas mode of communicating with the anode inlet 511 of fuel cell 505, so that produce and can be supplied to by the hydrogen that hydrogen separation equipment 507 separates from reformate gas the anode 509 of fuel cell 505 in reforming reactor 503.It is described to be arranged in the system 400 of reforming reactor 403 about hydrogen separation equipment 407 as mentioned, one or more heat exchanger 547 and condenser 549 can be connected between hydrogen outlet 541 and the anode inlet 511 with gas mode of communicating operation, leave the hydrogen stream of hydrogen outlet 541 and from hydrogen stream condensation water outlet to cool off before the anode 509 that enters fuel cell 505 at hydrogen stream.
In addition, described about system shown in Figure 3 400 as mentioned, the system 500 of Fig. 4 can comprise heat exchanger 543 and the compressor 545 that is operatively connected between pre-reforming reactor 501 and reforming reactor 403, and can comprise the catalytic partial oxidation reactor 551 that is used for initial fuel cell 505 operations of the anode inlet 511 that is operationally connected to fuel cell 505.
In one embodiment, system of the present invention can be as shown in Figure 1 with above to the system described in the description of the inventive method.
In one embodiment, system of the present invention can be as shown in Figure 2 with above to the system described in the description of the inventive method.

Claims (9)

1. system that is used to produce electric power comprises:
A) Solid Oxide Fuel Cell, it comprises
1) anode, it has
(i) anode inlet; With
(ii) anode exhaust outlet;
2) negative electrode, it has
(i) cathode inlet; With
(ii) cathode exhaust gas outlet; With
3) between described anode and negative electrode, contact anode and negative electrode and the electrolyte of anode and negative electrode separately;
B) pre-reforming reactor, it comprises
1) be suitable for making one or more hydrocarbon cracking in the charging precursor to form the pre-reforming zone of charging, described pre-reforming comprises Cracking catalyst in the zone, and described Cracking catalyst is positioned to contact one or more hydrocarbon of charging precursor and the vaporization mixture of steam;
2) enter the mouth with one or more pre-reforming reactor feed precursor that the gas/fluid mode of communicating connects with described pre-reforming zone, physical efficiency is introduced the pre-reforming zone by described pre-reforming reactor feed precursor inlet before the charging; With
3) one or more pre-reforming reactor anode exhaust inlet that connects with the gas mode of communicating with described pre-reforming zone and connects with the operation of gas mode of communicating with the outlet of described anode exhaust can be by the described pre-reforming reactor anode exhaust introducing pre-reforming zone that enters the mouth from the anode exhaust stream of fuel cell; With
4) be in one or more pre-reforming reactor outlet that gas is communicated with described pre-reforming zone;
C) reforming reactor, it comprises
1) the reformation zone that is suitable for making the vaporization mixture of the charging that comprises one or more gaseous hydrocarbon and steam to reform, described reformation comprises reforming catalyst in the zone, and described reforming catalyst is positioned in the reformation zone and contacts with the vaporization mixture of charging and steam; With
2) one or more reformer section realm entry, it connects with the gas mode of communicating with described reformation zone and connects with the operation of gas mode of communicating with one or more pre-reforming reactor outlet, with the reformation zone that allows to introduce reforming reactor from the charging and the steam of pre-reforming reactor; With
D) hydrogen separation equipment, it has
1) member that can hydrogen be seen through, it is positioned in the reformation zone of reforming reactor and is in gas with the reformation zone of reforming reactor to be communicated with;
2) be in the hydrogen outlet that gas is communicated with described member, described member between the reformation zone of reforming reactor and hydrogen outlet with allow hydrogen from the zone of reforming by this member optionally flowing to hydrogen outlet, wherein, described hydrogen outlet connects to allow hydrogen stream to flow to the anode of fuel cell from Hydrogen Separation equipment with the operation of gas mode of communicating with the anode inlet of fuel cell.
2. the system as claimed in claim 1, wherein, described anode exhaust outlet enters the mouth with described one or more pre-reforming reactor anode exhaust and directly connects with the gas mode of communicating.
3. system as claimed in claim 1 or 2, also comprise first heat exchanger, described first heat exchanger connects with the operation of gas mode of communicating with described one or more pre-reforming reactor outlet and connects with the operation of gas mode of communicating with described one or more reformer section realm entry of reforming reactor, so that first heat exchanger can cool off the charging of delivering to reforming reactor from the pre-reforming reactor.
4. system as claimed in claim 3, also comprise compressor, described compressor connects with the gas mode of communicating with the reformer section realm entry of first heat exchanger and reforming reactor, so that the charging of reforming reactor is delivered in the compression of compression function from first heat exchanger.
5. system as claimed in claim 1 or 2, also comprise compressor, described compressor connects with the operation of gas mode of communicating with described one or more reformer section realm entry of described one or more pre-reforming reactor outlet and reforming reactor, so that the charging of reforming reactor is delivered in the compression of compression function from the pre-reforming reactor.
6. as each described system among claim 1 or the claim 2-5, also comprise the condenser that the anode inlet with the hydrogen outlet of hydrogen separation equipment and anode of fuel cell is operatively connected with the gas mode of communicating, described condenser is effectively by the hydrogen stream condensation water outlet of delivering to anode of fuel cell from the hydrogen separation equipment.
7. system as claimed in claim 6, also comprise second heat exchanger, the hydrogen outlet and the condenser of described second heat exchanger and hydrogen separation equipment are operatively connected, and described second heat exchanger makes the hydrogen stream cooling of delivering to condenser from Hydrogen Separation equipment effectively.
8. as each described system among claim 1 or the claim 2-5, also comprise second heat exchanger, the hydrogen outlet of described second heat exchanger and hydrogen separation equipment and the anode inlet of anode of fuel cell are operatively connected, and described second heat exchanger makes the hydrogen stream cooling of delivering to anode of fuel cell from the hydrogen separation equipment effectively.
9. as each described system among claim 1 or the claim 2-8, also comprise the catalytic partial oxidation reactor that the anode inlet with anode of fuel cell is operatively connected, described catalytic partial oxidation reactor provides effectively and starts the operation of hydrogen stream with initial fuel cell.
CN2008801267417A 2007-12-17 2008-12-15 Fuel cell-based system for generating electrical power Pending CN101946356A (en)

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Application publication date: 20110112