CN105580179B - Use the integrated power generation of solid oxide fuel cell and chemical production - Google Patents

Use the integrated power generation of solid oxide fuel cell and chemical production Download PDF

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Publication number
CN105580179B
CN105580179B CN201480053460.9A CN201480053460A CN105580179B CN 105580179 B CN105580179 B CN 105580179B CN 201480053460 A CN201480053460 A CN 201480053460A CN 105580179 B CN105580179 B CN 105580179B
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China
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fuel cell
anode
fuel
solid oxide
method
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CN201480053460.9A
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Chinese (zh)
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CN105580179A (en
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P·J·贝洛维茨
T·A·巴尔克霍尔兹
A·S·李
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埃克森美孚研究工程公司
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Priority to US201361884565P priority
Priority to US201361884545P priority
Priority to US61/884,565 priority
Priority to US61/884,605 priority
Priority to US61/884,586 priority
Priority to US61/884,635 priority
Priority to US61/889,757 priority
Priority to US201361889757P priority
Priority to US14/197,613 priority
Priority to US14/197,613 priority patent/US9774053B2/en
Priority to US14/197,391 priority
Priority to US14/197,391 priority patent/US20140272613A1/en
Priority to US14/197,551 priority
Priority to US14/197,551 priority patent/US20140272615A1/en
Priority to US14/197,430 priority patent/US20140272614A1/en
Priority to US14/197,430 priority
Priority to US14/207,712 priority patent/US9343763B2/en
Priority to US14/207,714 priority patent/US9343764B2/en
Priority to US14/207,708 priority
Priority to US14/207,706 priority patent/US9455463B2/en
Priority to US14/207,710 priority
Priority to US14/207,711 priority patent/US9735440B2/en
Priority to US14/207,712 priority
Priority to US14/207,710 priority patent/US9362580B2/en
Priority to US14/207,728 priority patent/US20140261090A1/en
Priority to US14/207,706 priority
Priority to US14/207,690 priority patent/US9553321B2/en
Priority to US14/207,691 priority
Priority to US14/207,697 priority patent/US9923219B2/en
Priority to US14/207,687 priority
Priority to US14/207,726 priority
Priority to US14/207,690 priority
Priority to US14/207,728 priority
Priority to US14/207,687 priority patent/US9941534B2/en
Priority to US14/207,691 priority patent/US9257711B2/en
Priority to US14/207,726 priority patent/US9263755B2/en
Priority to US14/207,721 priority patent/US9520607B2/en
Priority to US14/207,708 priority patent/US9647284B2/en
Priority to US14/207,714 priority
Priority to US14/207,699 priority
Priority to US14/207,698 priority
Priority to US14/207,686 priority patent/US20140272633A1/en
Priority to US14/207,698 priority patent/US9419295B2/en
Priority to US14/207,693 priority patent/US9786939B2/en
Priority to US14/207,699 priority patent/US20140272635A1/en
Priority to US14/207,721 priority
Priority to US14/207,686 priority
Priority to US14/207,711 priority
Priority to US14/207,693 priority
Priority to US14/207,697 priority
Priority to US14/315,439 priority
Priority to US14/315,507 priority patent/US9077007B2/en
Priority to US14/315,419 priority patent/US9178234B2/en
Priority to US14/315,419 priority
Priority to US14/315,479 priority
Priority to US14/315,479 priority patent/US9077006B2/en
Priority to US14/315,527 priority
Priority to US14/315,507 priority
Priority to US14/315,527 priority patent/US9077008B2/en
Priority to US14/315,439 priority patent/US9077005B2/en
Priority to US14/486,159 priority patent/US9755258B2/en
Priority to US14/486,159 priority
Application filed by 埃克森美孚研究工程公司 filed Critical 埃克森美孚研究工程公司
Priority to PCT/US2014/058015 priority patent/WO2015048626A1/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637Direct internal reforming at the anode of the fuel cell
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0475Composition of the impurity the impurity being carbon dioxide
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0495Composition of the impurity the impurity being water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
    • C01B2203/067Integration with other chemical processes with fuel cells the reforming process taking place in the fuel cell
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84Energy production
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells
    • Y02E60/56Fuel cells integrally combined with other energy production systems
    • Y02E60/566Production of chemical products inside the fuel cell; incomplete combustion

Abstract

In in all fields, the system and method that solid oxide fuel cell is run under conditions of can improve or optimize the synthesis electrical efficiency and chemical efficiency of fuel cell are provided.Instead of the maximized conventional conditions of electrical efficiency for selecting to make fuel cell, operating condition may be allowed the output of excess syngas and/or hydrogen in the anode exhaust of fuel cell.Then synthesis gas and/or hydrogen can be used for various applications, including chemical synthesis process and collection hydrogen are used as fuel.

Description

Use the integrated power generation of solid oxide fuel cell and chemical production

Invention field

In in all respects, the present invention relates to use solid oxide fuel cell production electric power integration chemical production And/or electrification technique.

Background of invention

Solid oxide fuel cell utilizes hydrogen and/or other fuel power generation functions.It can be by fuel cell upstream or combustion Reforming methane or other reformable fuel provide hydrogen in steam reformer in material battery.Reformable fuel may include can be with The hydrocarbonaceous material for generating the gaseous products of hydrogen is reacted with steam and/or oxygen at elevated temperatures and/or pressures.Or or In addition, fuel can be reformed in the anode pool of solid oxide fuel cell, it is suitable to create that the fuel cell can be run The condition of fuel reforming in the anode.Alternatively or in addition, can outwardly and inwardly being reformed in fuel cell.

Traditionally, solid oxide fuel cell is run so that the generated energy of per unit fuel input maximizes, this can be with Electrical efficiency referred to as fuel cell.This maximization can be based on fuel cell alone or in the heat and power application of combination In.In order to realize generated energy and the management fever of raising, the fuel availability in fuel cell generally remains in 70% to 85%.

U.S. Patent Application Publication No.2005/0123810 describes a kind of system and side for hydrogen and electric energy coproduction Method.The co-generation system includes fuel cell and is configured to receive anode exhaust stream and separates the separative unit of hydrogen.A part Anode exhaust is also recycled to anode inlet.The range of operation provided during ' 810 are open seems based on fused carbonate fuel electricity Pond.Solid oxide fuel cell is described as substitute.

Summary of the invention

On the one hand, it provides and produces electricity and hydrogen or synthesis using the solid oxide fuel cell with anode and cathode The method of gas.This method will introduce the anode and solid of solid oxide fuel cell comprising the fuel streams of reformable fuel The relevant inside reforming element of the anode of oxide fuel cell, or combinations thereof in;It will include O2Cathode inlet stream introduce In the cathode of solid oxide fuel cell;It generates electricity in solid oxide fuel cell;Take out from anode exhaust includes H2 Air-flow, include H2With the air-flow or their combination of CO, wherein the electrical efficiency of solid oxide fuel cell is about 10% To about 50%, total fuel cell manufacture rate of solid oxide fuel cell is at least about 150mW/cm2

Brief description

Fig. 1 schematically shows an example of the configuration of solid oxide fuel cell and related reforming sections and segregation section.

Fig. 2 schematically shows another example of the configuration of solid oxide fuel cell and related reforming sections and segregation section.

Fig. 3 schematically shows an example of the operation of solid oxide fuel cell.

Embodiment is described in detail

Summary

In in all respects, provide by solid oxide fuel cell (SOFC) with high total fuel cell efficiency in addition to production The system and method for a large amount of hydrogen or synthesis gas are also produced except electricity.Flat plate cell or tubulose electricity can be used in various aspects of the present invention Pond.Total fuel cell efficiency is commonly referred to as the synthesis electrical efficiency and chemical efficiency of fuel cell.Total fuel cell is then provided The more complete definition of efficiency.

Can using any other parameter as cost under design and run typical fuel cell system for optimizing electric effect Rate.It can use original position and/or since burning waste gas and the heat of anodic product generation extremely maintain fuel cell to transport with limit Degree required for row.As most of electricity-generating method, conventional fuel cell system mainly payes attention to electric product.Traditional fuel electricity It is in the application for produce efficient electrical power, in distributed power generation or spare power generation that cell system, which can be used in main purpose,.

Various aspects of the present invention can establish fuel cell operation parameter to cause total fuel cell efficiency to be more than traditional fuel electricity Pond efficiency.Additionally or alternatively, the present invention provides improve total fuel cell manufacture rate to maintain very high overall system efficiency simultaneously Method.On the one hand, productivity are as follows: for the fuel cell capacity of design flow, the useful products generated per unit time are (as closed At air and heat, electricity) total amount, such as measured by the cross-sectional area of fuel cell.Fuel-cell electrical efficiency is maximized instead of selection Conventional conditions, service condition can produce the total fuel cell efficiency and/or productivity of much higher whole system, if allowed Electrical efficiency is down to the best electrical efficiency sought in above-mentioned typical fuel cells system or less.As described in more detail below, always Fuel cell efficiency be by fuel cell generate energy amount relative to the energy for being delivered to fuel cell amount measurement, and Productivity is size (such as anode of the amount of the energy (total chemistry, electrically and thermally can) generated by fuel cell relative to fuel cell Area) measurement.The condition that high total fuel cell efficiency and/or productivity can be achieved may be allowed the anode exhaust of fuel cell Middle excess syngas and/or hydrogen export and can be by separating outputting and inputting for anode and cathode completely or partially (decoupling) it is realized with allowing some products excessively to produce.The excess can for example pass through the electrical efficiency (example of reduction battery As by running at the lower voltage) and/or be used to effectively produce (such as synthesis gas form) change using the heat generated in situ Be able to achieve.Therefore, compared with known in the art, fuel cell can be processed it is much bigger to the total fuel input of anode, together When maintain similar or higher total delivery efficiency (the sum of chemistry, electricity and useful thermal energy).Higher productivity allows fuel cell More effectively it is used in integrated system.

It includes at least H that the electrochemical method occurred in anode, which can lead to anode output synthesis air-flow,2, CO and CO2Combination. Then water gas shift reaction can be used to generate the composition of required synthesis gas and/or make H2Yield is relative to other synthesis gas components Increase or maximizes.Then synthesis gas and/or hydrogen, including but not limited to chemical synthesis process can be used in various applications And/or it collects hydrogen and is used as " cleaning " fuel.

As used herein, the electrochemical kinetics that term " electrical efficiency " (" EE ") is defined as being generated by fuel cell are divided by fuel The rate of the low heat value (" LHV ") of battery fuel input.The fuel input of fuel cell include be sent to the fuel of anode with And any fuel for keeping the temperature of fuel cell, such as it is sent to the fuel of burner relevant to fuel cell.In this theory In bright book, the power generated by the fuel can be described with LHV (el) fuel rate (fuel rate).

As used herein, term " electrochemical kinetics " or LHV (el) are by connecting cathode and anode in fuel cell The transfer of circuit and oxonium ion through fuel-cell electrolyte and the power generated.Electrochemical kinetics do not include fuel cell upstream or The equipment in downstream generates or the power of consumption.For example, not being considered as electrification by the thermogenetic electricity in fuel cell exhaust stream Learn a part of power.It similarly, is not to generate by the power that the gas turbine of fuel cell upstream or other equipment generate A part of electrochemical kinetics." electrochemical kinetics " do not consider the electric power consumed in fuel cell operation or are turned by direct current It is melted into any loss caused by alternating current.In other words, it does not subtract from the direct current power that fuel cell generates for supplying fuel The electric power of battery operation or in other ways fuel cell operation.Power density used herein is current density multiplied by voltage. Current density used herein is the electric current of per unit area.Total fuel battery power used herein is power density multiplied by combustion Expect cell area.

The term as used herein " anode fuel input " is referred to as LHV (anode_in), is the combustion in anode inlet stream Doses.Term " fuel input " is referred to as LHV (in), is intended in the total amount of fuel of fuel cell, including anode inlet stream Fuel quantity and fuel quantity for keeping the temperature of fuel cell.Based on the definition of reformable fuel provided herein, the combustion Material may include reformable and non-reformable fuel.Fuel input is different from fuel availability.

The term as used herein " total fuel cell efficiency " (" TFCE ") is defined as: the electrochemistry generated by fuel cell Power adds the rate (rate of LHV) of the LHV of the synthesis gas generated by fuel cell, inputs divided by the fuel of anode The rate of LHV.In other words, TFCE=(LHV (el)+LHV (sg net))/LHV (anode_in), wherein LHV (anode_in) Refer to fuel element (such as H for being sent to anode2、CH4And/or CO) LHV rate, and LHV (sg net) refers to and produces in the anode GCMS computer gas (H2, CO) rate, be the difference that the synthesis gas input of anode is exported with the synthesis gas of anode.LHV (el) description The electrochemical kinetics of fuel cell generate.Total fuel cell efficiency does not include being generated by the fuel cell for the fuel cell The outer beneficial heat utilized.In operation, the heat generated by fuel cell may be by upstream device beneficial to utilization.For example, the heat It can be used for generating additional electric power or for heating water.When using the term in this application, implement outside fuel cell These purposes are not a part of total fuel cell efficiency.Total fuel cell efficiency is wrapped only for fuel cell operation, and not The power for including fuel cell upstream or downstream is generated or is consumed.

The term as used herein " chemical efficiency " is defined as the H in the anode exhaust of fuel cell2It is sent out with the low level of CO Calorific value or LHV (sg out) are divided by fuel input or LHV (in).

The term as used herein " total fuel cell manufacture rate " (" TFCP ") is defined as the conversion due to inputting fuel, often The total energy value for the product that unit fuel cells cross-sectional area generates per unit time.Fuel can be anti-in oxidation reaction, reformation Answer, and/or water gas shift reaction in convert.The gross energy of product can be with any convenient unit such as mW/cm2It indicates.Combustion The product for expecting that battery generates may include electrochemical kinetics, synthesis gas and/or hydrogen and heat.The heat of generation can be by measuring anode The temperature difference between entrance and anode export measures.For example, the productivity of fuel cell can be with mW/cm2Anode of fuel cell Cross-sectional area indicate.It can select fuel cell operating conditions arbitrarily to generate high total fuel cell manufacture rate and high total combustion Expect battery efficiency.

The term as used herein " total reformable fuel production rate " (" TRFP ") is based on per unit2Fuel cell cross-section Long-pending anode reformable fuel input LHV and exported by anode received reformable fuel LHV difference.Anode inlet and The amount that the difference of reformable fuel in outlet can be approximately equal to be converted to the reformable fuel of synthesis gas and/or hydrogen subtracts finally Generate the amount of the newly generated synthesis gas and/or hydrogen that consume in the oxidation reaction of electricity.Newly generated synthesis gas and/or hydrogen exist In anode or it is to generate in related reforming sections that fuel cell is thermally integrated.Feed the synthesis gas and/or hydrogen of anode inlet It is not newly generated.It can select fuel cell operating conditions arbitrarily to generate high total reformable fuel production rate and high total combustion Expect battery efficiency.

In certain aspects, the operation of fuel cell can be characterized based on electrical efficiency.When fuel cell operation is with low electricity When efficiency (EE), solid oxide fuel cell can be run to have about 50% or lower, such as about 45%EE or more Low, about 40%EE or lower, about 35%EE or lower, about 30%EE or lower, about 25%EE or lower, about 20%EE or lower, about 15%EE or lower or about 10%EE or lower electrical efficiency.Additionally or alternatively, EE can be with It is at least about 5%, perhaps at least about 10% or at least about 15%, at least about 20%, at least about 25%, or Person at least about 30%.Still further or alternatively, it can be based on total fuel cell efficiency (TFCE), such as the synthesis electrical efficiency of fuel cell With the operation of chemical efficiency characterization fuel cell.If fuel cell operation is with high total fuel cell efficiency, Ke Yiyun Row solid oxide fuel cell to have about 55% or higher, such as about 60% or higher, or about 65% or higher, Or about 70% or higher, or about 75% or higher, or about 80% or higher, or about 85% or higher TFCE (and/ Or integrate electrical efficiency and chemical efficiency).It is to be noted, that for total fuel cell efficiency and/or comprehensive electrical efficiency and chemical efficiency, It may not include any additional power being thermally generated using the excess that fuel cell generates in efficiency calculation.

It, can be based on needed for about 50% or lower required electrical efficiency and 55% or higher in various aspects of the present invention The operation of total fuel cell efficiency characterization fuel cell.When fuel cell operation is with required electrical efficiency and required total fuel electricity When the efficiency of pond, solid oxide fuel cell can be run to have 50% or lower electrical efficiency and about 55% or higher TFCE, such as about 40% or lower EE and about 60% or higher TFCE, about 35% or lower EE and about 65% or higher TFCE, about 30% or lower EE and about 70% or higher TFCE, or about 20% or lower EE and about 75% or higher TFCE, perhaps about 15% or lower EE and about 80% or higher TFCE or About 10% or lower EE and about 85% or higher TFCE.

In various aspects of the present invention, about 150mW/cm can be based on2Or higher required total fuel cell manufacture rate The operation of total fuel cell efficiency characterization fuel cell needed for (" TFCP ") and 55% or higher.When fuel cell is big to have About 150mW/cm2When above required TFCP and required total fuel cell efficiency are run, solid oxide fuel electricity can be run Pond is to have an about 55% or higher TFCE, such as about 60% or higher, about 65% or higher, about 70% or more Height, perhaps about 75% or higher perhaps about 80% or higher or about 85% or higher.When fuel cell is to have Needed for 55% or higher when total fuel cell efficiency operation, solid oxide fuel cell can be run to have at least about 150mW/cm2TFCP, or at least about 200mW/cm2, or at least about 250mW/cm2, or at least about 300mW/ cm2, or at least about 350mW/cm2.In in all respects, TFCP can be about 800mW/cm2Or it is lower, or about 700mW/cm2Or it is lower, or about 600mW/cm2Or it is lower, or about 500mW/cm2Or it is lower, or about 400mW/ cm2Or it is lower.

In various aspects of the present invention, about 75mW/cm can be based on2Or it is higher needed for total reformable fuel production rate and The operation of total fuel cell efficiency characterization fuel cell needed for 55% or higher.When fuel cell operation is to have about 75mW/cm2When above required reformable fuel production rate and required total fuel cell efficiency, soild oxide combustion can be run Expect battery to have an about 55% or higher TFCE, such as about 60% or higher, about 65% or higher, about 70% or It is higher, perhaps about 75% or higher perhaps about 80% or higher perhaps about 85% or higher or about 90% or It is higher.When fuel cell operation is to have 55% or higher required total fuel cell efficiency, soild oxide can be run Fuel cell is to have at least about 75mW/cm2Reformable fuel production rate, or at least about 100mW/cm2, Huo Zhezhi Few about 125mW/cm2, or at least about 150mW/cm2, or at least about 175mW/cm2, or at least about 200mW/ cm2, or at least about 300mW/cm2.In these areas, reformable fuel production rate can be about 600mW/cm2It is lower, Or about 500mW/cm2It is lower, or about 400mW/cm2It is lower, or about 300mW/cm2It is lower, or about 200mW/cm2It is lower.

Solid oxide fuel cell is run with can with required electrical efficiency, chemical efficiency and/or total fuel cell efficiency It realizes in various ways.In some respects, the chemical efficiency of solid oxide fuel cell can be by improving in fuel cell The hydrogen aoxidized in the amount and anode of the reformation that (and/or in related reforming sections in fuel cell module) carry out to generate electricity The relative value of amount and improve.Traditionally, solid oxide fuel cell has been run so that power generation efficiency is relative to fuel The amount of consumption maximizes while maintaining suitable thermal balance to keep total system temperature.It is big in anode under this kind of service condition The fuel availability of about 70% to about 85% is preferably, to make electrical efficiency most under the voltage to electricity output ideal (i.e. high) Bigization simultaneously maintains thermal balance in fuel cell.Under high fuel availability value, only the hydrogen (or synthesis gas) of appropriate amount retains Synthesis gas is used to form in anode exhaust.For example, under about 75% fuel availability, into the big of the fuel in anode About 25% can be used as synthesis gas and/or the combination of unreacted fuel is left.The hydrogen or synthesis gas of appropriate amount can usually be enough Maintain enough hydrogen concentrations of anode to promote anodic oxidation reactions and provide enough fuel to heat reactant and/or entrance material Stream is until suitable temperature of fuel cell operation.

It is from tradition operation different, solid oxide fuel can be run with low fuel utilization rate and higher fuel flow rate Battery, and it is less or without fuel from anode off-gas recirculation to anode inlet.It is same by being run under low fuel utilization rate When make to be recycled to the fuel of anode inlet and reduce or minimize, available a greater amount of H in anode exhaust2And/or CO. Excess H2It can be used as syngas product with CO and/or hydrogen gas product taken out.Fuel benefit in all respects, in fuel cell It can be at least about 5%, such as at least about 10%, perhaps at least about 15% or at least about 20% with rate.In addition or Alternatively, fuel availability can be about 60% or lower, or about 50% or lower in terms of low fuel utilization rate, or Person about 40% or lower.

An option for improving the chemical efficiency of fuel cell is the reformable hydrogen for improving the fuel for being delivered to fuel cell Content.For example, the reformable hydrogen for the reformable fuel being delivered in the input stream of anode and/or reforming sections relevant to anode Content can be higher by least about 50% than the net amount of the hydrogen reacted at anode, such as height at least about 75%, or high at least big About 100%.Additionally or alternatively, that is sent to anode and/or the fuel being sent in the input stream of reforming sections relevant to anode can Reforming hydrogen content can be higher by least about 50% than the net amount of the hydrogen reacted at anode, and such as high at least about 75% or high at least About 100%.In in all respects, the reformable hydrogen content of reformable fuel is relative to the hydrogen reacted in anode in fuel streams The ratio between amount can be at least about 1.5:1, perhaps at least about 2.0:1 perhaps at least about 2.5:1 or at least about 3.0:1.Additionally or alternatively, in fuel streams reformable fuel reformable hydrogen content relative to the hydrogen reacted in anode amount it Than can be about 20:1 or smaller, such as about 15:1 or smaller, or about 10:1 or smaller.On the one hand, it is contemplated that anode enters Reformable hydrogen content in mouthful stream can be converted to hydrogen less than 100%.For example, the reformable hydrogen in anode inlet stream contains At least about the 80% of amount can be converted to hydrogen in the anode and/or in related reforming sections, and such as at least about 85%, or extremely Few about 90%.

Hydrogen or synthesis gas can be used as chemical energy output and take out from anode exhaust.Hydrogen can be used as in burning Shi Busheng At the clean fuel of greenhouse gases.In addition, hydrogen can be for the valuable of various refinery processes and/or other synthesis technologies The charging of value.Synthesis gas is also possible to for polytechnic valuable charging.In addition to fuel value, synthesis gas may be used also As the raw material for producing other higher value products, such as by using synthesis gas as F- T synthesis and/or methanol conjunction At the charging of technique.

In in all respects, anode exhaust may have about the H of 1.5:1 to about 10:12/ CO ratio, such as at least about 3.0: 1, perhaps at least about 4.0:1 or at least about 5.0:1, and/or about 8.0:1 or smaller, or about 6.0:1 or smaller. Synthesis gas stream can be taken out from anode exhaust.In in all respects, the synthesis gas stream taken out from anode exhaust can have At least about 0.9:1, such as at least about 1.0:1, perhaps at least about 1.2:1 perhaps at least about 1.5:1 or at least big About 1.7:1, the perhaps H of at least about 1.8:1 or at least about 1.9:12/ CO molar ratio.Additionally or alternatively, it is arranged from anode The H in synthesis gas taken out in gas2/ CO molar ratio can be about 3.0:1 or smaller, such as about 2.7:1 or smaller, Huo Zhe great About 2.5:1 or smaller, perhaps about 2.3:1 or smaller perhaps about 2.2:1 or smaller or about 2.1:1 or smaller.So And the synthesis gas application of many types benefits from have at least about 1.5:1 to about 2.5:1 or smaller H2/ CO molar ratio Synthesis gas, so formed H2The molar ratio of/CO content be such as about 1.7:1 to about 2.3:1 synthesis gas stream for Some applications may be ideal.

Synthesis gas can be taken out from anode exhaust by any convenient method.It in certain aspects, can be by right Anode exhaust is separated to remove the H in anode exhaust2At least part with CO is different from component and from anode exhaust Take out synthesis gas.For example, can make anode exhaust by optional water gas shift stage to adjust H first2With the relative quantity of CO. Then one or more segregation sections can be used and remove H from anode exhaust2O and/or CO2.Therefore the remainder of anode exhaust It can be equivalent to synthesis gas stream, then can be taken out in any convenient manner for using.Additionally or alternatively, can make to take out Synthesis gas stream pass through one or more water gas shift stages and/or pass through one or more segregation sections.

It is to be noted, that changing the H in the synthesis gas taken out2The mode additionally or alternatively of/CO molar ratio can be from sun H is isolated in pole exhaust and/or synthesis gas2Stream, such as by implementing UF membrane progress.Form individual H2Export stream This separation can what convenient position in office carry out, such as before making anode exhaust pass through water gas shift reaction section and/or Later, and anode exhaust is made to be different from H by one or more segregation sections to remove in anode exhaust2Divide it with the group of CO It is preceding and/or later.It is optionally possible to separating H from anode exhaust2Water gas shift stage is all used before and after stream. In an embodiment additionally or alternatively, H optionally can be separated from the synthesis gas stream of taking-up2.In certain aspects, Isolated H2Stream can be equivalent to high-purity H2Stream such as contains at least about H of 90 volume %2, such as at least about 95 volume % H2Or the H of at least about 99 volume %2H2Stream.

As increase, supplement and/or the substitution of fuel cell operation strategy described herein, solid oxide fuel cell (such as fuel cell module) can be relative to the excessive reformable operating fuel of amount of the hydrogen reacted in anode of fuel cell.Instead of It selects the service condition of fuel cell to improve or maximize the electrical efficiency of fuel cell, excessive reformable fuel can be sent Enter the anode of fuel cell to improve the output of the chemical energy of fuel cell.Optionally but preferably, this can lead to based on fuel electricity The synthesis electrical efficiency in pond and the fuel cell gross efficiency of chemical efficiency improve.

In certain aspects, it is sent to anode and/or is sent to reformable in the input stream of reforming sections relevant to anode The reformable hydrogen content of fuel can be higher than the hydrogen amount aoxidized in the anode by least about 50%, such as height at least about 75% or high At least about 100%.In in all respects, the reformable hydrogen content of reformable fuel in anode relative to reacting in fuel streams The ratio between amount of hydrogen can be at least about 1.5:1, perhaps at least about 2.0:1 perhaps at least about 2.5:1 or at least big About 3.0:1.Additionally or alternatively, amount of the reformable hydrogen content of reformable fuel relative to the hydrogen reacted in anode in fuel streams The ratio between can be about 20:1 or lower, such as about 15:1 or lower or about 10:1 or lower.On the one hand, it is contemplated that anode enters Reformable hydrogen content in mouthful stream can be converted to hydrogen less than 100%.For example, the reformable hydrogen in anode inlet stream contains At least about the 80% of amount can be converted to hydrogen in the anode and/or in related reforming sections, and such as at least about 85%, or extremely Few about 90%.

Additionally or alternatively, the amount for being sent to the reformable fuel of anode can the low heat value (LHV) based on reformable fuel It is characterized with the relative value of the LHV of the hydrogen aoxidized in the anode.This can be referred to reformable fuel excess rate.In the alternative In, reformable fuel excess rate can be at least about 2.0, such as at least about 2.5, perhaps at least about 3.0 or at least big About 4.0.Additionally or alternatively, reformable fuel excess rate can be about 25.0 or lower, and such as about 20.0 or lower, or about 15.0 or lower, or about 10.0 or lower.

In various aspects of the present invention, at least about 150mW/cm can be based on2Required total fuel cell manufacture rate The operation of (" TFCP ") and required reformable fuel excess rate characterization fuel cell.For example, solid oxide fuel can be run Battery is to have at least about 150mW/cm2TFCP and at least about 2.0 reformable fuel excess rate, such as at least about 2.5, perhaps at least about 3.0 or at least about 4.0.Additionally or alternatively, TFCP can be about 150mW/cm2More than, it can Fuel reforming excess rate can be about 25.0 or smaller, such as about 20.0 or smaller, or about 15.0 or smaller, Huo Zhe great About 10.0 or smaller.When fuel cell operation is with at least about 2.0 reformable fuel excess rate, solid can be run Oxide fuel cell is to have at least about 150mW/cm2TFCP, or at least about 200mW/cm2, or at least about 250mW/cm2, or at least about 300mW/cm2, or at least about 350mW/cm2.In this aspect, TFCP can be about 800mW/cm2Or it is smaller, or about 700mW/cm2Or it is smaller, or about 600mW/cm2Or it is smaller, or about 500mW/ cm2Or it is smaller, or about 400mW/cm2Or it is smaller.

In various aspects of the present invention, about 75mW/cm can be based on2Or it is higher needed for total reformable fuel production rate and The operation of required reformable fuel excess rate characterization fuel cell.It in certain aspects, can be big to have with fuel cell operation About 75mW/cm2Above required reformable fuel production rate and at least about 2.0, such as at least about 2.5, or at least about 3.0, or at least about 4.0 reformable fuel excess rate.Additionally or alternatively, total reformable fuel production rate can be about 75mW/cm2More than, reformable fuel excess rate can be about 25.0 or smaller, and such as about 20.0 or smaller, or about 15.0 or smaller, or about 10.0 or smaller.When fuel cell operation is with the reformable fuel excess at least about 2.0 When rate, solid oxide fuel cell can be run to have at least about 75mW/cm2Reformable fuel production rate, or At least about 100mW/cm2, or at least about 125mW/cm2, or at least about 150mW/cm2, or at least about 175mW/cm2, or at least about 200mW/cm2, or at least about 300mW/cm2.In these aspects, reformable fuel Productivity can be about 600mW/cm2Or it is lower, or about 500mW/cm2Or it is lower, or about 400mW/cm2Or more It is low, or about 300mW/cm2Or it is lower, or about 200mW/cm2Or it is lower.

As increase, supplement and/or the substitution to fuel cell operation strategy described herein, solid oxidation can be run Object fuel cell selects reformation amount in order to relative to amount of oxidation to realize the required thermal ratio of fuel cell.It is used herein " thermal ratio " is defined as the heat generated by the exothermic reaction in fuel cell module divided by occurring in fuel cell module The heat absorption demand of reforming reaction.It is expressed with mathematical way, thermal ratio (TH)=QEX/QEN, wherein QEXIt is to be generated by exothermic reaction Heat summation and QENIt is the heat summation of the endothermic reaction consumption occurred in fuel cell.It is to be noted, that being generated by exothermic reaction Heat be equivalent to be attributed to the battery in reforming reaction, any heat of water gas shift reaction and electrochemical reaction.It can be based on Desired electrochemical gesture across the fuel cell reaction of electrolyte subtracts the actual output voltage calculating of fuel cell by electrochemistry React the heat generated.For example, based on the net reaction occurred in the battery, it is believed that the desired electrochemical gesture of the reaction in SOFC is big About 1.04V.In the operational process of SOFC, due to various losses, which is typically below the output voltage of 1.1V.Example Such as, common output/operating voltage can be about 0.65V, perhaps about 0.7V perhaps about 0.75V or about 0.8V. The electrochemical potential (for example,~1.04V) that the heat of generation is equal to the battery subtracts operating voltage.For example, when output voltage be~ It is~0.34V by the heat that the electrochemical reaction in battery generates when 0.7V.Therefore, in this case, electrochemical reaction generates The electricity of~0.7V and the thermal energy of~0.34V.In such instances ,~0.7V electric energy is not as QEXA part.In other words, hot It can not be electric energy.

In in all respects, the operating parameter of settable SOFC is to realize at least 0.7V operating voltage below, for example, at least 0.65V hereinafter, such as at least 0.6V hereinafter, such as at least 0.5V hereinafter, such as at least 0.4V hereinafter, For example, at least 0.3V or less.

It, can be to any convenient fuel cell structure, as only in fuel cell pack, fuel cell pack in all respects Vertical fuel cell, the fuel cell pack with integrated reforming sections, the fuel cell pack with integrated endothermic reaction section or its Combination measurement thermal ratio.It can also be to the different units in fuel cell pack, such as fuel cell or the component meter of fuel cell pack Calculate thermal ratio.For example, can to the single anode in single fuel cell, the anode segment in fuel cell pack or with integrated weight Whole section and/or integrated endothermic reaction segment element (from being thermally integrated in terms of angle enough in close proximity to the anode segment to be integrated) are together Anode segment in fuel cell pack calculates thermal ratio." anode segment " used herein includes the share common in fuel cell pack Multiple anodes of entrance or outlet manifold.

In aspects of the present invention, the operation of fuel cell can be characterized based on thermal ratio.If fuel cell operation Solid oxide fuel cell with required thermal ratio, then can be run to have about 1.5 or lower, such as about 1.3 Or it is lower, or about 1.15 or lower, or about 1.0 or lower, or about 0.95 or lower, or about 0.90 or lower, or About 0.85 or lower, or about 0.80 or lower, or about 0.75 or lower thermal ratio.Additionally or alternatively, thermal ratio can Think at least about 0.25, or at least about 0.35, or at least about 0.45, or at least about 0.50.

In various aspects of the present invention, about 75mW/cm can be based on2Or it is higher needed for total reformable fuel production rate and The operation of required thermal ratio characterization fuel cell.It in certain aspects, can be with fuel cell operation to have about 75mW/cm2 Above required reformable fuel production rate and about 1.5 or smaller, such as about 1.3 or smaller, or about 1.15 or more It is small, perhaps about 1.0 or smaller perhaps about 0.95 or smaller perhaps about 0.90 or smaller or about 0.85 or more It is small, perhaps about 0.80 or smaller or about 0.75 or smaller thermal ratio.Additionally or alternatively, total reformable fuel production Rate can be about 75mW/cm2More than, thermal ratio can be at least about 0.25, perhaps at least about 0.35 or at least big About 0.45, or at least about 0.50.It, can be with when fuel cell operation is with thermal ratio with about 0.25 to about 1.3 Solid oxide fuel cell is run to have at least about 75mW/cm2, or at least about 100mW/cm2, or it is at least big About 125mW/cm2, or at least about 150mW/cm2, or at least about 175mW/cm2, or at least about 200mW/cm2, Or at least about 300mW/cm2Reformable fuel production rate.In these aspects, reformable fuel production rate can be big About 600mW/cm2Or it is lower, or about 500mW/cm2Or it is lower, or about 400mW/cm2Or it is lower, or about 300mW/cm2Or it is lower, or about 200mW/cm2Or it is lower.

In various aspects of the present invention, about 150mW/cm can be based on2Or it is higher needed for total fuel cell manufacture rate and The operation of required thermal ratio characterization fuel cell.It in one aspect, can be with fuel cell operation to have about 150mW/cm2With On required total fuel cell manufacture rate, and about 1.5 or smaller, such as about 1.3 or smaller, or about 1.15 or more It is small, perhaps about 1.0 or smaller perhaps about 0.95 or smaller perhaps about 0.90 or smaller or about 0.85 or more It is small, perhaps about 0.80 or smaller or about 0.75 or smaller thermal ratio.Additionally or alternatively, total fuel cell manufacture rate It can be about 150mW/cm2More than, thermal ratio can be at least about 0.25, perhaps at least about 0.35 or at least big About 0.45, or at least about 0.50.It, can be with when fuel cell operation is with thermal ratio with about 0.25 to about 1.3 Solid oxide fuel cell is run to have at least about 150mW/cm2, or at least about 200mW/cm2, or it is at least big About 250mW/cm2, or at least about 300mW/cm2, or at least about 350mW/cm2TFCP.In these aspects, TFCP can be about 800mW/cm2Or it is lower, or about 700mW/cm2Or it is lower, or about 600mW/cm2Or it is lower, Or about 500mW/cm2Or it is lower, or about 400mW/cm2Or it is lower.

It additionally or alternatively, in certain aspects, can be with fuel cell operation to have about 40 DEG C or smaller, such as about 20 DEG C or it is smaller, about 10 DEG C or it is smaller anode input anode output between heating.Still further or alternatively, it can transport Row fuel cell is to have about 10 DEG C of supreme about 10 DEG C of anode export temperature lower than anode inlet temperature.Still further or or Person, can be such as at least about 5 DEG C high or high with fuel cell operation to have the anode inlet temperature higher than anode export temperature At least about 10 DEG C, or it is at least about 20 DEG C high or at least about 25 DEG C high.It still further or alternatively, can be with fuel cell operation It is such as about 80 DEG C or lower high to have than about 100 DEG C or lower of anode export warmer, or about 60 DEG C or lower, or About 50 DEG C or lower, or about 40 DEG C or lower, or about 30 DEG C or lower, or about 20 DEG C or lower, or about 10 DEG C Or lower anode inlet temperature.Solid oxygen can be assisted in keeping by minimizing the difference between anode inlet temperature and outlet temperature The mechanical integrity of ceramic component in compound fuel cell.

As increase, supplement and/or the substitution to fuel cell operation strategy described herein, can be improved can provide Power density under conditions of run solid oxide fuel cell (such as fuel cell module).The power density phase of fuel cell When in real work voltage VAMultiplied by current density I.For in voltage VAThe solid oxide fuel cell of lower operation, the fuel Battery also tends to generate waste heat, and waste heat is defined as (V0–VA) * I, it is based on VAWith the fuel cell of offer current density I Desired voltage V0Difference.Reformation of the reformable fuel in the anode of fuel cell can consume a part of this waste heat.Remainder This waste heat divided can be absorbed by the fuel cell structure of surrounding and air-flow, lead to the temperature difference across fuel cell.In tradition Under service condition, the power density of fuel cell can be held based on fuel cell in the case where not damaging fuel cell integrality Perhaps waste heat is restricted.

In in all respects, by carrying out a effective amount of endothermic reaction in fuel cell, fuel cell, which can be improved, to be held Perhaps waste heat.One example of the endothermic reaction includes reformable fuel in anode of fuel cell and/or in related reforming sections, Such as the steam reformation in the integrated reforming sections in fuel cell pack.Pass through anode to fuel cell (or Xiang Jicheng/correlation weight Whole section) additional reformable fuel is provided, additional reformation can be carried out in order to consume additional waste heat.This can be reduced across combustion Expect the amount of the temperature difference of battery, thus fuel cell is allowed to run under the service condition with the waste heat improved.Electrical efficiency Loss can by generate can be used for various uses (including additional power generation) additional product stream offset, the additional product Stream is, for example, synthesis gas and/or H2, with the power bracket of the further expansion system.

In in all respects, the waste heat that fuel cell generates, (V as defined above0–VA) * I can be at least about 30mW/ cm2, such as at least about 40mW/cm2, or at least about 50mW/cm2, or at least about 60mW/cm2, or at least about 70mW/ cm2, or at least about 80mW/cm2, or at least about 100mW/cm2, or at least about 120mW/cm2, or at least about 140mW/cm2, or at least about 160mW/cm2, or at least about 180mW/cm2, or at least about 200mW/cm2, or it is at least big About 220mW/cm2, or at least about 250mW/cm2, or at least about 300mW/cm2.Additionally or alternatively, fuel cell generates Waste heat can be less than about 400mW/cm2, such as less than about 300mW/cm2, or it is less than about 200mW/cm2, or be less than about 175mW/cm2, or it is less than about 150mW/cm2

Although the waste heat generated may be relatively high, such waste heat is not necessarily represented fuel cell and is transported with poor efficiency Row.On the contrary, waste heat can be generated due to the fuel cell operation under the power density of raising.The power for improving fuel cell is close The part of degree may include the fuel cell operation under sufficiently high current density.In in all respects, the electric current of fuel cell generation Density can be at least about 150mA/cm2, such as at least about 160mA/cm2, or at least about 170mA/cm2, or at least about 180mA/cm2, or at least about 190mA/cm2, or at least about 200mA/cm2, or at least about 300mA/cm2, or it is at least big About 400mA/cm2, or at least about 800mA/cm2.Additionally or alternatively, the current density that fuel cell generates can be about 800mA/cm2Or it is lower, such as 450mA/cm2Or lower or 300mA/cm2Or lower or 250mA/cm2Or lower or 200mA/ cm2Or it is lower.

In in all respects, in order to the fuel cell operation under the generation of the waste heat of the power generation of raising and raising, it can carry out A effective amount of endothermic reaction (such as reforming reaction).Alternatively, can be connected by being arranged in fuel cell array with anode or cathode heat Logical but " plate " or section that are not in fluid communication and utilize waste heat using unrelated other endothermic reactions are run with anode.It is a effective amount of The endothermic reaction can be in related reforming sections, integrated reforming sections, the integrated Nuclear fuel for carrying out the endothermic reaction or combinations thereof Middle progress.A effective amount of endothermic reaction, which can be equivalent to, to be enough for the heating from fuel cell inlet to fuel exit to be decreased to About 100 DEG C or lower, such as about 90 DEG C or lower, or about 80 DEG C or lower, or about 70 DEG C or lower, or about 60 DEG C Or it is lower, or about 50 DEG C or lower, or about 40 DEG C or lower, or about 30 DEG C or lower amount.Additionally or alternatively, effectively The endothermic reaction of amount, which can be equivalent to, is enough to make about 100 DEG C of cooling from fuel cell inlet to fuel exit or more It is low, such as about 90 DEG C or lower, or about 80 DEG C or lower, or about 70 DEG C or lower, or about 60 DEG C or lower, or about 50 DEG C or lower, or about 40 DEG C or lower, or about 30 DEG C or lower, or about 20 DEG C or lower, or about 10 DEG C or more Low amount.When a effective amount of endothermic reaction is more than the waste heat generated, can occur from fuel cell inlet to fuel exit Cooling.Additionally or alternatively, this can be equivalent to the endothermic reaction (as reformed the combination with another endothermic reaction) consumption fuel cell At least about the 40% of the waste heat of generation, such as waste heat of consumption at least about 50%, or at least about 60% waste heat, or at least About 75% waste heat.Still further or alternatively, the endothermic reaction can consume about 95% or less waste heat, such as about 90% or more Few waste heat, or about 85% or less waste heat.

Additional definitions

Synthesis gas: in the present specification, synthesis gas is defined as H2With the mixture of any ratio of CO.Optionally, H2O And/or CO2It may be present in synthesis gas.Optionally, inert compound (such as nitrogen) and the reformable fuel compound of residual may be present In synthesis gas.If H2It is present in synthesis gas with the component other than CO, H in synthesis gas2It can be with the total volume percent of CO For at least 25 volume % of synthesis gas total volume, such as at least 40 volume %, or at least 50 volume %, or at least 60 volume %.Separately Outer or alternatively, H in synthesis gas2Can be 100 volume % or lower with the total volume percent of CO, such as 95 volume % or lower or 90 volume % or lower.

Reformable fuel: reformable fuel is defined as containing reformable generation H2Carbon-hydrogen link fuel.Hydrocarbon is can to weigh The example of whole fuel, other hydrocarbonaceous compounds, such as alcohol and.Although CO and H2O may participate in water gas shift reaction to form hydrogen Gas, CO are not considered as the reformable fuel under this definition.

Reformable hydrogen content: the reformable hydrogen content of fuel is defined as then being driven by fuel by reforming the fuel Water gas shift reaction is completely so that H2Generate the H for maximizing and being formed2Molecular number.It is to be noted, that H2It is weighed by definition with 1 Whole hydrogen content, although H2Itself it is not defined as reformable fuel herein.Similarly, CO has 1 reformable hydrogen content. Although CO be not strictly it is reformable, drive water gas shift reaction completely and will lead to CO being exchanged into H2.As can weigh The example of the reformable hydrogen content of whole fuel, the reformable hydrogen content of methane are 4 H2Molecule, and the reformable hydrogen content of ethane For 7 H2Molecule.More briefly, if the group of fuel becomes CxHyOz, the fuel is under 100% reformation and Water gas shift/WGS Reformable hydrogen content be n (H2Maximum is reformed)=2x+y/2-z.Based on this definition, the fuel availability in battery can be therewith It is expressed as n (H2ox)/n(H2Maximum is reformed).Certainly, can determine component mixture based on the reformable hydrogen content of each component can Reform hydrogen content.It can also calculate in a similar manner containing other hetero atoms, as the reformable hydrogen of oxygen, sulphur or nitrogen compound contains Amount.

Oxidation reaction: in this discussion, the oxidation reaction in the anode of fuel cell is defined as being comparable to pass through With O2-Reaction and by H2Oxidation forms H2The reaction of O.It is to be noted, that not including sun in this definition of oxidation reaction in the anode Reforming reaction in extremely, the compound in reforming reaction containing carbon-hydrogen link are converted to H2With CO or CO2.Water gas shift reaction Similarly except this definition of oxidation reaction.It is further noted that referring to that being defined is to H to combustion reaction2Or contain The compound of carbon-hydrogen link in non-electrochemical burner, as burning energy supply generator combustion zone in O2Reaction forms H2O and carbon The reaction of oxide refers to.

Anode fuel parameter is adjusted to realize the required range of operation of fuel cell in aspect of the invention.Anode fuel ginseng Number directly and/or with other fuel cell process can be characterized relatively in the form of one or more ratios.For example, can One or more ratios, including fuel availability, fuel cell utilization rate of heat value, fuel are realized to control anode fuel parameter Excess rate, reformable fuel excess rate, reformable hydrogen content fuel ratio and combinations thereof.

Fuel availability: fuel availability is an option for characterizing anode operation, based on relative to input material The fuel quantity of the oxidation of the reformable hydrogen content of stream can be used for determining the fuel availability of fuel cell.In this discussion, " combustion Material utilization rate " is defined as the hydrogen amount (as described above) aoxidized in the anode for power generation and anode and inputs (including any phase Close reforming sections) reformable hydrogen content ratio.Reformable hydrogen content is defined above to reform the combustion for that can be passed through by fuel Expect and then drives water gas shift reaction completely so that H2Generate the H for maximizing and being formed2Molecular number.For example, introducing anode and sudden and violent Each methane being exposed under steam reforming conditions causes to generate 4H under maximum production2Molecular equivalency.(depend on reformation and/or sun Limited condition, reformate can be equivalent to non-Water gas shift/WGS product, wherein one or more H2Molecule is instead with CO points The form presence of son).Therefore, methane is defined as 4 H2The reformable hydrogen content of molecule.As another example, at this One, which defines lower ethane, has 7 H2The reformable hydrogen content of molecule.

Fuel availability in anode can also by based on due to anode of fuel cell reaction and aoxidize in the anode The ratio of the low heat value of hydrogen and the low heat value for all fuel for being sent to anode and/or reforming sections relevant with anode Utilization rate of heat value is defined to characterize.The flow velocity for entering and leaving the fuel element of anode of fuel cell and low level fever can be used It is worth (LHV) and calculates " fuel cell utilization rate of heat value " used herein.Therefore, fuel cell utilization rate of heat value can be used as (LHV (anode_in)-LHV (anode_out))/LHV (anode_in) calculates, wherein LHV (anode_in) and LHV (anode_ Out fuel element (such as H in anode inlet and outlet stream or stream) is referred respectively to2、CH4And/or CO) LHV.In this definition In, the numerical value summation that can be used as each fuel element in input and/or output stream calculates the LHV of stream or stream.Each fuel element It is (such as burnt multiplied by the LHV of fuel element that share in the summation can be equivalent to the flow velocity (such as mol/hr) of fuel element Ear/mole).

Low heat value: low heat value is defined as fuel element and burns into gas phase complete oxidation product (for example, gas phase CO2And H2O product) enthalpy.For example, any CO present in anode input stream2The fuel content for not constituting anode input, because For CO2Complete oxidation.For this definition, since the amount of oxidation that anode fuel cell reacts and occurs in the anode is defined For the H in the anode of a part as the electrochemical reaction in anode as defined above2Oxidation.

It is to be noted, that being H for the sole fuel in anode inlet flow2Special circumstances, it is generable in the anode to be related to Unique reaction of fuel element is H2It is converted to H2O.In this special circumstances, fuel availability is simplified to (H2Rate-enters- H2Rate-goes out)/H2Rate-enters.In this case, H2It is unique fuel element, therefore H2LHV can disappear from the equation It goes.In the case where more common, anode feed may contain the CH of for example various amounts4、H2And CO.Since these species usually may be used It is present in anode export with not same amount, it may be necessary to which summation is as described above to measure fuel availability.

As to the substituted or supplemented of fuel availability, the utilization rate of other reactants in fuel cell can be characterized. For example, additionally or alternatively, the operation of fuel cell can be characterized with regard to " oxidant " utilization rate.Oxygen can be provided in a similar manner The value of agent utilization rate.

Fuel excess rate: the another way of the reaction in characterization solid oxide fuel cell is by being based on being sent to anode And/or the low heat value of all fuel of reforming sections relevant to anode reacted with due to anode of fuel cell and in the anode The ratio of the low heat value of the hydrogen of oxidation defines utilization rate.This amount is referred to as fuel excess rate.Therefore, fuel excess Rate can be used as (LHV (anode_in)/(LHV (anode_in)-LHV (anode_out)) calculate, wherein LHV (anode_in) and LHV (anode_out) refers respectively to fuel element (such as H in anode inlet and outlet stream or stream2、CH4And/or CO) LHV. In aspects of the present invention, can run solid oxide fuel cell with have at least about 1.0, such as at least about 1.5, Or at least about 2.0, or at least about 2.5, or at least about 3.0, or at least about 4.0 fuel excess rate.In addition or or Person, fuel excess rate can be about 25.0 or lower.

It is to be noted, that not all reformable fuel in anode input stream can be all reformed.Preferably, into anode At least about 90% reformable fuel can weigh before leaving anode in the input stream of (and/or entering related reforming sections) It is whole, such as at least about 95% or at least about 98%.In in terms of other, the reformation amount of reformable fuel can be about 75% to about 90%, such as at least about 80%.

The above-mentioned definition of fuel excess rate is provided relative to the consumed fuel quantity that generates electricity in anode of fuel cell It is characterized in a kind of method of the amount of the reformation occurred in anode and/or reforming sections relevant to fuel cell.

It is optionally possible to change fuel excess rate to take into account fuel from anode output and be recycled to the case where anode inputs. As fuel (such as H2, CO and/or do not reform or the hydrocarbon of partial conversion) from anode output be recycled to anode input when, it is such again The fuel that circulating fuel component does not represent the reformable of the excess quantity that can be used for other purposes or reforms.On the contrary, such follow again Ring fuel element only indicates to reduce the demand of the fuel availability in fuel cell.

Reformable fuel excess rate: calculating reformable fuel excess rate is one for taking into account such recycled fuel component Option, the constriction definition of excess fuel, only to include the LHV of reformable fuel in anode input stream.It is used herein " reformable fuel excess rate " be defined as being sent to the low level of the reformable fuel of anode and/or reforming sections relevant to anode Calorific capacity and the relative value of the low heat value of hydrogen reacted due to anode of fuel cell and aoxidized in the anode.Reformable It does not include any H in anode feed under the definition of fuel excess rate2Or the LHV of CO.This LHV of reformable fuel still may be used Enter the actual composition measurement of anode of fuel cell by characterizing, therefore needs not distinguish between recyclable component and fresh components. It is not reformed or partial conversion fuel is also recyclable although some, most of combustion of anode is recycled in most of aspects Material can be equivalent to reformate, such as H2Or CO.It is expressed with mathematical way, reformable fuel excess rate (RRFS)=LHVRF/LHVOH, Wherein LHVRFIt is the low heat value (LHV) and LHV of reformable fuelOHIt is the low heat value of the hydrogen aoxidized in the anode (LHV).It can be by subtracting the LHV of anode export stream from the LHV of anode inlet stream (for example, LHV (anode_in)-LHV (anode_out)) LHV of the hydrogen aoxidized in the anode is calculated.In aspects of the present invention, solid oxidation can be run Object fuel cell is to have at least about 0.25, such as at least about 0.5, or at least about 1.0, or at least about 1.5, or at least About 2.0, or at least about 2.5, or at least about 3.0, or at least about 4.0 reformable fuel excess rate.In addition or or Person, reformable fuel excess rate can be about 25.0 or lower.It is to be noted, that based on being sent to relative to the amount of oxidation in anode This relatively narrow definition of the reformable fuel quantity of anode can distinguish the fortune of the two kinds of fuel cell with low fuel utilization rate Row method.Some fuel cells realize low fuel benefit and significant component of anode output is recirculated back to anode input With rate.This recycling can make anode input in any hydrogen be further used as the input of anode.This can reduce reformation amount, because i.e. Keep the fuel availability when one way is by fuel cell low, the unused fuel of at least part is also recycled for stream later Journey.Therefore, the fuel cell with diversified fuel utilization value having the same can be sent to the reformable of anode reforming sections The ratio of fuel and the hydrogen aoxidized in anode reaction.In order to change in the reformable fuel and anode that are sent to anode reforming sections Amount of oxidation ratio, need to identify the anode feed of the non-reformable fuel with original content, or need to take out anode defeated Unused fuel in out to be used for other purposes, or both.

Reformable hydrogen excess rate: another option for characterizing fuel cell operation is based on " reformable hydrogen excess rate ".On The reformable fuel excess rate of text definition is that the low heat value based on reformable fuel element defines.Reformable hydrogen excess rate It is defined as being sent to the reformable hydrogen content of the reformable fuel of anode and/or reforming sections relevant to anode and due to fuel electricity Pond anode reaction and the ratio of hydrogen reacted in the anode.Therefore, " reformable hydrogen excess rate " can be used as (RFC (reformable_anode_in)/(RFC (reformable_anode_in)-RFC (anode_out)) it calculates, wherein RFC (reformable_anode_in) the reformable hydrogen content of the reformable fuel in referring to anode inlet stream or flowing, and RFC (anode_out) refer to anode inlet and export fuel element (such as H in stream or stream2、CH4And/or CO) reformable hydrogen contain Amount.RFC can with mole/second, mol/hr or similar unit indicate.In the reformable fuel and sun for being sent to anode reforming sections An example of the method for fuel cell operation, which can be, under the big ratio of amount of oxidation in extremely carries out excess reformer to balance combustion Expect the method that the heat in battery occurs and consumes.Reformable fuel reforming is formed into H2It is an endothermic process with CO.It can pass through Electric current in fuel cell, which generates, fights this endothermic reaction, and the electric current generation also can produce excessive heat, and (substantially) is corresponding In by anodic oxidation reactions and cathode reaction generation heat and as an electrical current leave fuel cell energy difference.Anodic oxygen The excessive heat for changing every moles of hydrogen involved in reaction/cathode reaction can be greater than by reforming the heat for generating 1 moles of hydrogen and absorbing.Cause This, the fuel cell run under conventional conditions can express heating from the inlet to the outlet.Instead of such tradition fortune Row, can be improved the fuel quantity reformed in reforming sections relevant to anode.For example, additional fuel can be reformed in order to logical The heat that heat (substantially) the balance exothermic fuel cell reaction consumed in reforming generates is crossed, or reforming the heat of consumption even can be more than combustion The excessive heat that material oxidation generates, so that the temperature across fuel cell declines.This can lead to compared with the amount needed for electric power generates Hydrogen is significantly excessive.As an example, the charging for being sent into the anode inlet or related reforming sections of fuel cell can be substantially by can Fuel reforming, such as substantially pure methane feed are constituted.It, can be with about in traditional operational process using this fuel power generation function 75% fuel availability runs solid oxide fuel cell.This means that being sent to about the 75% of the fuel content of anode (or 3/4) is used to form hydrogen, then reacts to form H with oxonium ion in the anode2O.In conventional operation, residue is about 25% fuel content can be reformatted into H in fuel cell2(or can be for any CO or H in fuel2For unreacted Ground passes through fuel cell), then burn outside fuel cell to form H2O is with the cathode inlet heat supply to fuel cell.It can weigh Whole hydrogen excess rate can be 4/ (4-1)=4/3 in this case.

Electrical efficiency: the term as used herein " electrical efficiency " (" EE ") is defined as the electrochemical kinetics generated by fuel cell Divided by the rate for the low heat value (" LHV ") that the fuel of fuel cell inputs.The fuel input of fuel cell includes being sent to sun The fuel of pole and any fuel for keeping the temperature of fuel cell, are such as sent to the combustion of burner relevant to fuel cell Material.In the present specification, the power generated by the fuel can be described with LHV (el) fuel rate (fuel rate).

Electrochemical kinetics: the term as used herein " electrochemical kinetics " or LHV (el) are by connecting yin in fuel cell The power that the circuit and oxonium ion of pole and anode are generated through the transfer of fuel-cell electrolyte.Electrochemical kinetics do not include fuel The equipment in battery upstream or downstream generates or the power of consumption.For example, not by the thermogenetic electricity in fuel cell exhaust stream It is considered as a part of electrochemical kinetics.Similarly, the power generated by the gas turbine of fuel cell upstream or other equipment It is not a part of the electrochemical kinetics generated." electrochemical kinetics " do not consider the electric power consumed in fuel cell operation or As DC conversion at any loss caused by alternating current.In other words, use is not subtracted from the direct current power that fuel cell generates In supply fuel cell operation or the electric power of fuel cell operation in other ways.Power density used herein is current density Multiplied by voltage.Total fuel battery power used herein is power density multiplied by fuel cell area.

Fuel input: the term as used herein " anode fuel input " is referred to as LHV (anode_in), is anode inlet Fuel quantity in stream.Term " fuel input " is referred to as LHV (in), is intended for the total amount of fuel of fuel cell, including anode Fuel quantity in entrance stream and the fuel quantity for keeping the temperature of fuel cell.Based on reformable fuel provided herein Definition, which may include reformable and non-reformable fuel.Fuel input is different from fuel availability.

Total fuel cell efficiency: the term as used herein " total fuel cell efficiency " (" TFCE ") is defined as: by fuel The electrochemical kinetics that battery generates add the rate (rate of LHV) of the LHV of the synthesis gas generated by fuel cell, divided by sun The rate of the LHV of the fuel input of pole.In other words, TFCE=(LHV (el)+LHV (sg net))/LHV (anode_in), wherein LHV (anode_in) refers to fuel element (such as H for being sent to anode2、CH4And/or CO) LHV rate, and LHV (sg net) Refer to generation synthesis gas (H in the anode2, CO) rate, be that the synthesis gas input of anode exports it with the synthesis gas of anode Difference.The electrochemical kinetics that LHV (el) describes fuel cell generate.Total fuel cell efficiency does not include being generated by the fuel cell The beneficial heat utilized outside for the fuel cell.It in operation, may be beneficial by upstream device by the heat that fuel cell generates It utilizes.For example, the heat can be used for generating additional electric power or for heating water.When using the term in this application, firing These purposes implemented outside material battery are not a part of total fuel cell efficiency.Total fuel cell efficiency is only for fuel cell Operation, and do not include the power generation or consumption in fuel cell upstream or downstream.

Chemical efficiency: the term as used herein " chemical efficiency " is defined as the H in the anode exhaust of fuel cell2And CO Low heat value or LHV (sg out) divided by fuel input or LHV (in).

Electrical efficiency and overall system efficiency do not consider the efficiency of upstream or downstream process.For example, whirlpool can be advantageously used O of the turbine exhaust as fuel battery negative pole2Source.In this arrangement, the efficiency of turbine is not considered as electrical efficiency or total combustion Expect a part that battery efficiency calculates.Similarly, the output from fuel cell can be used as input object and be recycled to fuel electricity Pond.Recirculation circuit is not considered when calculating electrical efficiency or total fuel cell efficiency with single pass mode.

The synthesis gas of generation: the term as used herein " synthesis gas of generation " is the conjunction of the synthesis gas input and anode of anode The difference exported at gas.Synthesis gas can at least partly be used as input or the fuel of anode.For example, system may include anode recirculation Back to anode inlet is sent the synthesis gas from anode exhaust in circuit, at this to its supplemental natural gas or other suitable fuel. The synthesis gas LHV (sg net) of generation=(LHV (sg out)-LHV (sg in)), wherein LHV (sg in) and LHV (sg out) Refer respectively to the LHV of the synthesis gas and anode export stream or the synthesis gas in stream in anode inlet.It is to be noted, that by anode Reforming reaction generate at least part synthesis gas can usually be used to generate electricity in the anode.Hydrogen for power generation do not include In the definition of " synthesis gas of generation ", because it is without departing from anode.The term as used herein " syngas ratio " is to generate The LHV or LHV (sg net)/LHV (anode in) that the LHV of net synthesis gas is inputted divided by the fuel of anode.Synthesis can be used Mole flow velocity of gas and fuel replaces LHV to indicate the synthesis gas of the generation of mole base syngas ratio and mole base.

Vapor carbon ratio (S/C): vapor carbon ratio (S/C) used herein is rubbing for the reformable carbon in steam and stream in stream That ratio.CO and CO2The carbon of form is not calculated as the reformable carbon in this definition.Can within the system difference measurement and/ Or control vapor carbon ratio.For example, can control the composition of anode inlet stream to realize the S/C of the reformation in suitable anode.S/C can Using as H2Mole flow velocity of O is divided by (mole flow velocity of fuel multiplies multiplied by carbon atom number (such as methane is 1) in fuel Product) it provides.Therefore, S/C=fH20/(fCH4X#C), wherein fH20It is mole flow velocity of water, wherein fCH4It is methane (or other combustions Material) mole flow velocity and #C be carbon number in fuel.In in all respects, S/C can be about 2, or about 1-3, Huo Zhe great About 0.5-5.It may be desirable that only enough steam is to meet reforming reaction stoichiometry and prevent fouling for offer, because excessive Steam dilution anode reactant and production consumption energy.

Fuel cell and fuel cell component: in this discussion, fuel cell can be equivalent to monocell, Anodic and Cathode is separated by an electrolyte.Solid oxide fuel cell takes flat type or form of tubes.As used herein, fuel cell can To refer in the form of one form of them or two kinds.Anode and cathode can receive input air-flow to promote respective anode and cathode anti- It answers, charge is transmitted across electrolyte and generates electricity.Fuel cell pack can represent multiple batteries in integrated unit.Although fuel Battery pile may include multiple fuel cells, but fuel cell usually can be in parallel and can (substantially) behave like their collectives and represent ruler Very little bigger single fuel cell.When conveying inlet flow to the anode or cathode of fuel cell pack, which may include being used for The flow channel of inlet flow is distributed between each battery in the heap and the flowing for merging the output stream from each battery is led to Road.In this discussion, fuel cell array can be used for indicating series, parallel or (such as go here and there in any other convenient way Connection and combination in parallel) arrangement multiple fuel cells (such as multiple fuel cell packs).Fuel cell array may include fuel electricity One or more sections of pond and/or fuel cell pack, wherein the output of the anode/cathode from first segment may act as the sun of second segment Pole/cathode input.It is to be noted, that the anode in fuel cell array need not be connected in a manner of identical with the cathode in the array. For convenience, the anode that the input of the first anode section of fuel cell array can be referred to as the array inputs, and fuel electricity The cathode that the input of first cathode section of pond array can be referred to as the array inputs.Similarly, final anode/cathode section is defeated The anode/cathode that can be referred to as the array out exports.

It using fuel cell typically refers to be made of multiple single fuel cells it should be understood that mentioning herein " fuel cell pack " more generally refers to using the one or more fuel cell packs being in fluid communication.Usually will can individually it fire Expect that cell device (plate or cylinder) with rectangular array " stacking ", is referred to as " fuel cell pack " together.This fuel cell pack is logical Feeding flow can often be obtained and by reactant distribution between all individual fuel cell components, then can collect and produce from each element Object.When being considered as a unit, fuel cell pack can be taken as entirety in operation, although by it is many (it is usually tens of or It is hundreds of) individually fuel cell component constitute.These independent fuel cell components could generally have similar voltage (because reactant and Production concentration is similar), when these elements are electrically coupled in series, total electricity output may be from the total of all electric currents in all cell devices With.Battery pile can also be with arranged in series to generate high voltage.Parallel arrangement can promote electric current.If can provide enough large volumes For fuel cell pack to process given stream, system and method described herein can be with single solid-oxide fuel cell stack one It rises and uses.In in terms of other of the invention, since many reasons may desirable or it is desirable that multiple fuel cell packs.

For the purpose of the present invention, unless specifically stated, term " fuel cell " should be understood to also refer to and/or be defined as Including being related to having the fuel cell pack of single input and output being made of the combination of one or more individually fuel cell components, Because this is the usually used mode of fuel cell in practice.Similarly, unless specifically stated, term fuel cell (plural number) It should be understood to also refer to and/or be defined to include multiple independent fuel cell packs.In other words, unless stated otherwise, originally All refer in text interchangeably refers to that fuel cell pack is run as " fuel cell ".For example, commercial-scale burning hair The exhaust volume that motor generates may be too big so that can not be processed by the fuel cell (for example, cell stack) of stock size. In order to process entire exhaust, multiple fuel cells (i.e. two or more independent fuel cells or fuel can be arranged in parallel Battery pile) so that the burning and gas-exhausting of (substantially) moiety can be processed in each fuel cell.Although multiple fuel electricity can be used Pond, but consider the burning and gas-exhausting of its (substantially) moiety, each fuel cell can usually be run in a substantially similar manner.

" inside reforming " and " outside reform ": fuel cell or fuel cell pack may include one or more inside reformings Section.The term as used herein " inside reforming " refer to fuel cell, fuel cell pack main body in or in other ways firing Expect the fuel reforming occurred in battery component.External reform usually being used in combination with fuel cell is being located at outside fuel cell pack Autonomous device part in carry out.In other words, the main body of external reformer is not direct with the main body of fuel cell or fuel cell pack Physical contact.In typical arrangement, the output from external reformer can be sent into the anode inlet of fuel cell.Unless It especially explains separately, the reformation described in the application is inside reforming.

Inside reforming can carry out in anode of fuel cell.Additionally or alternatively, inside reforming can be integrated in fuel It is carried out in inside reforming element in battery component.Integrated reforming element can be located at the fuel cell component in fuel cell pack Between.In other words, one of the plate in battery pile can be reforming sections rather than fuel cell component.On the one hand, in fuel cell pack Flow arrangement by fuel be oriented to inside reforming element, be then introduced into the anode part of fuel cell.Therefore, from flowing angle It sees, inside reforming element and fuel cell component can be disposed in series in fuel cell pack.The term as used herein " anode weight It is whole " it is the fuel reforming occurred in anode.The term as used herein " inside reforming " be in integrated reforming element rather than The reformation occurred in anode segment.

In certain aspects, the reforming sections in fuel cell module may be considered that and the anode in fuel cell module It is related.In in terms of other, for can reforming sections in the fuel cell pack of (such as with multiple anodes related) related to anode, It can provide the flow path that the output stream from reforming sections is sent at least one anode.This can be equivalent to fuel cell plate Initial segment, the Duan Buyu electrolyte contact but function only as reforming catalyst.Another option of related reforming sections, which can be, to be had Individually integrated reforming sections are as one of the element in fuel cell pack, wherein the output from integrated reforming sections is sent back to The input side of one or more fuel cells in fuel cell pack.

From being thermally integrated in terms of angle, the feature height in fuel cell pack can be the height of independent fuel cell Nuclear fuel. It is to be noted, that independent reforming sections or independent endothermic reaction section can have the height different from fuel cell in the heap.At this In the case of kind, the height of fuel cell component can be used as feature height.In certain aspects, integrated endothermic reaction section It can be defined as the section being thermally integrated with one or more fuel cells, so that the integrated endothermic reaction section can utilize and carry out spontaneous combustion Expect the heat of battery as the heat source reformed.This integrated endothermic reaction section, which can be defined as, integrates appointing for section heat supply with to this What fuel cell is at less than 5 times of a Nuclear fuel height.For example, integrated endothermic reaction section (such as reforming sections) can be with Any fuel cell being thermally integrated is at 5 times less than a Nuclear fuel height, 3 times of such as less than one Nuclear fuel height. In this discussion, the integrated reforming sections or integrated endothermic reaction section for representing the adjacent Nuclear fuel of fuel cell component can be with It is defined as with adjacent fuel cell element at a distance of about Nuclear fuel height or less.

In certain aspects, the independent reforming sections being thermally integrated with fuel cell component can be also equivalent to and fuel cell component Relevant reforming sections.In such aspect, integrated fuel cell component can provide at least part to related reforming sections Heat, and at least part reforming sections can be exported and be supplied to integrated fuel cell as fuel streams by related reforming sections.Another In some aspects, independent reforming sections can be integrated to conduct heat with fuel cell but not related to fuel cell.Such In situation, which can receive heat from fuel cell, but the output of reforming sections is not used as to the input of fuel cell. On the contrary, another purposes can be used for for the output of this reforming sections, such as the output is directly appended in anode exhaust stream or shape At the independent output stream from fuel cell module.

More generally, it the independent Nuclear fuel in fuel cell pack that can be used can mention using integrated fuel cell Nuclear fuel Any endothermic reaction for facilitating type of the waste heat of confession.Instead of being suitable for carrying out hydrocarbon fuel stream the plate of reforming reaction, individually Nuclear fuel can have the plate for being suitable for being catalyzed the another type of endothermic reaction.It can be led in a fuel cell stack using manifold or entrance Other arrangements of pipe provide inlet flow appropriate to each Nuclear fuel.Other arrangements of similar manifold or delivery channel can also be used in Output stream is taken out from each Nuclear fuel.It is optionally possible to from the defeated of the endothermic reaction section taken out in fuel cell pack in heap It is flowed out without making the output stream by anode of fuel cell.In such optional aspect, the product of exothermic reaction is not therefore Fuel cell pack is left in the case where by anode of fuel cell.It can carry out in Nuclear fuel in a fuel cell stack other The example of the endothermic reaction of type includes that ethanol dehydration forms ethylene and ethane cracking.

Recycling: as defined herein, the output of a part of fuel cell (such as anode exhaust or is separated or is taken from anode exhaust Stream out) it is recycled to fuel cell inlet, this can be equivalent to direct or indirect recycle stream.Stream is recycled directly to Fuel cell inlet is defined as recycling without the stream of pilot process, and indirect recycling is related to making stream by one Or the recycling after multiple pilot process.For example, if anode exhaust passes through CO before being recycled2Segregation section, this is considered as The indirect recycling of anode exhaust.If by a part of anode exhaust, the H that is such as taken out from anode exhaust2Stream, which is sent into, to be used In converting coal into the gasifier for being adapted for introduction into the fuel of fuel cell, this is also regarded as indirect recycling.

Anode is output and input

In aspects of the present invention, it can feed to SOFC array in the received fuel of anode inlet, it includes for example Hydrogen and hydrocarbon, such as methane (alternatively, the heteroatomic hydrocarbonaceous or class hydrocarbon compound different from C and H may be contained).It is sent into anode Most of methane (or other hydrocarbonaceous or class hydrocarbon compound) usually can be fresh methane.In the present specification, fresh fuel, such as It is not the fuel recycled from another fuel cell process that fresh methane, which refers to,.For example, being recycled from anode export stream Methane to anode inlet can not be considered as " fresh " methane, but can be described as regenerating methane.Fuel used source can be with Share with other components, such as turbine.Fuels sources input may include the water proportional with the fuel, and the ratio is suitable for Reforming hydrocarbon (or class hydrocarbon) compound generates hydrogen in reforming sections.For example, if methane is for reforming to generate H2Fuel it is defeated Entering, the molar ratio of water and fuel can be about 1 to 1 to about 10 to 1, and such as at least about 2 to 1.4 to 1 or higher ratio It is typical to outside reformation, but lower value may be typical to inside reforming.In H2A part as fuels sources In degree, in some optional aspects, additional water may not be needed in fuel, because of the H at anode2Oxidation can be tended to Generate the H that can be used for reforming the fuel2O.Fuels sources optionally also with the subsidiary component of the fuels sources (for example, natural gas into Material contains the CO of certain content2As annexing ingredient).For example, natural gas feed can contain CO2、N2And/or other inertia are (dilute Having) gas is as annexing ingredient.Optionally, in certain aspects, which can also contain CO, such as again from anode exhaust The CO of cyclic part.It can be into the additional or alternative possibility source of the CO in the fuel of fuel cell module and fired by entering The CO that the hydrocarbon fuel steam reformation that fuel carries out is generated before expecting battery component.

More generally, various types of fuel streams can be suitable as the input material of the anode of solid oxide fuel cell Stream.Some fuel streams can be equivalent to containing hydrocarbon and/or may also include the material of the heteroatomic class hydrocarbon compound different from C and H Stream.In this discussion, unless specifically stated, the referring to of hydrocarbon containing fuels stream for SOFC anode be defined to include containing The fuel streams of such class hydrocarbon compound.The example of hydrocarbon (including class hydrocarbon) fuel streams includes natural gas, carbon compound containing C1-C4 The stream of object (such as methane or ethane) and stream and their combination containing heavier C5+ hydrocarbon (including class hydrocarbon compound). Other additional or alternative examples for the possible fuel streams in anode input may include the stream of biogas type, The methane generated is such as decomposed by natural (biology) of organic material.

In certain aspects, solid oxide fuel cell can be used for processing due to there are dilution immunomodulator compounds and having low The input fuel streams of energy content, such as natural gas and/or hydrocarbon stream.For example, some sources of methane and/or natural gas are can to wrap Include the CO of significant quantity2Or other inert molecules, such as the source of nitrogen, argon or helium.Since there are the CO of raising amount2And/or inert material, The energy content of the fuel streams based on the source can be reduced.The fuel of low energy content is for combustion reaction (as being combustion Burn the turbine energy supply of energy supply) it will cause difficulty.But solid oxide fuel cell can be based on the fuels sources of low energy content It generates electricity and there is influence reduce or the smallest on the efficiency of fuel cell.The presence of additional gas volume can need additional heat Fuel temperature is risen to the temperature for being used for reformation and/or anode reaction.In addition, due to the Water gas shift/WGS in anode of fuel cell The equilibrium property of reaction adds CO2Presence can influence anode output present in H2With the relative quantity of CO.But it is in addition, lazy Property compound to reforming and anode reaction can only have and minimum directly affect.In the fuel streams of solid oxide fuel cell CO2And/or the amount of inert compound (when it is present) can be at least about 1 volume %, such as at least about 2 volume %, or extremely Few about 5 volume %, or at least about 10 volume %, or at least about 15 volume %, or at least about 20 volume %, or at least About 25 volume %, or at least about 30 volume %, or at least about 35 volume %, or at least about 40 volume %, or at least About 45 volume %, or at least about 50 volume %, or at least about 75 volume %.Additionally or alternatively, solid oxide fuel CO in the fuel streams of battery2And/or the amount of inert compound can be about 90 volume % or lower, such as about 75 volume % Or it is lower, or about 60 volume % or lower, or about 50 volume % or lower, or about 40 volume % or lower, or about 35 volume % or lower.

Other examples in the possibility source of anode input stream can be equivalent to oil refining and/or the output of other industrial technologies Stream.For example, coking is in many oil plants for heavy compounds to be converted to the common technology of lower boiling range.Coking is logical It often generates containing the multiple compounds for being at room temperature gas, the exhaust gas including CO and various C1-C4 hydrocarbon.This exhaust gas can be used as At least part of anode input stream.Additionally or alternatively, other refinery flares streams can be suitable for inclusion in anode input In stream, the light fraction (C1-C4) that is such as generated during cracking or other refinery processes.Additionally or alternatively, other are closed Suitable oil plant stream may include containing CO or CO2Oil plant stream, also contain H2And/or reformable fuel compound.

Additionally or alternatively, other possible sources of anode input may include the stream with the water content improved.Example Such as, the ethyl alcohol output stream from ethyl alcohol factory (or another type of zymotechnique) may include suitable one before final distillation The H divided2O.Such H2O usually can only cause minimum influence to the operation of fuel cell.Therefore, alcohol (or other fermentations produce Object) and water fermenting mixture can be used as anode input stream at least part.

Biogas or biogas are another additional or alternative possibility sources of anode input.Biogas may mainly include first Alkane and CO2And it is usually generated by the decomposition of organic matter or digestion.Anaerobic bacteria can be used for digestion of organic matter and generate biogas.It can To remove impurity, such as sulfur-containing compound from biogas before being used as anode input.

Output stream from SOFC anode may include H2O、CO2, CO and H2.Optionally, anode output stream can also have There is unreacted fuel (such as H in charging2Or CH4) or the additional output component of inert compound conduct.Expect instead of using this output Stream as the fuels sources to reforming reaction heat supply or as the burning fuel for heating battery, can to anode output stream into The one or many separation of row are with by CO2With the component with the potential value inputted as another technique, such as H2Or CO separation.H2 And/or CO can be used as chemically synthesized synthesis gas, as the hydrogen source for chemical reaction and/or as with reduced temperature The fuel of room gas discharge.

In in all respects, the composition of the output stream of anode can be influenced by a number of factors.It can influence anode output composition Factor may include the temperature of the composition of the input stream of anode, the magnitude of current and/or anode export that are generated by fuel cell.Due to The equilibrium property of water gas shift reaction, the temperature of anode export can be related.In typical anode, anode wall is constituted At least one plate be applicable to catalytic water shift conversion reaction.Therefore, if a) composition of anode input stream is it is known that b) positive Pole inputs the reformation degree of the reformable fuel in stream it is known that and c) amount of the oxonium ion from cathode transport to anode (corresponds to In the magnitude of current of generation) it is known that can then determine the composition of anode output based on the equilibrium constant of water gas shift reaction.

Keq=[CO2][H2]/[CO][H2O]

In above-mentioned equation, KeqIt is the equilibrium constant of the reaction under given temperature and pressure, and [X] is point of component X Pressure.Based on water gas shift reaction, it can be noted that, the CO improved in anode input2Concentration can tend to lead to additional CO shape At (with H2For cost), and the H improved2O concentration can tend to lead to additional H2It is formed (using CO as cost).

In order to measure the composition of anode output, the composition of anode input can be used as starting point.Then it can change this Kind is formed to be reflected in the reformation degree for any reformable fuel that may occur in anode.This reformation can reduce anode input Hydrocarbon content, be transformed into increased hydrogen and CO2.Then, based on the magnitude of current of generation, the H in anode input can be reduced2Amount, It is transformed into additional H2O and CO2.The equilibrium constant that may then based on water gas shift reaction adjusts this composition to measure H2、 CO、CO2And H2The exit concentration of O.

In in all respects, the operation temperature of SOFC may be selected to realize H in synthesis gas output2, CO and CO2Required ratio. Running temperature may be selected to generate the synthesis gas output with the ratio for being suitable for expected method.On the one hand, running temperature can be with Be about 700 DEG C to about 1200 DEG C, for example, running temperature can be about 800 DEG C, about 900 DEG C, about 1000 DEG C or About 1100 DEG C.

Optionally, if it is desired, can include one or more water gas shift reaction sections after anode output with by anode CO and H in output2O is converted to CO2And H2.It can be for example by using water-gas shift will be positive at a lower temperature H present in the output of pole2O and CO are converted to H2And CO2To improve H present in anode output2Amount.Because SOFC can be big It is run at about 700 DEG C to about 1200 DEG C, so especially desirable may be the rush when cooling anode output is for subsequent technique Water inlet gas shift reaction.Alternatively, temperature can be improved and water gas shift reaction can be reversed, by H2And CO2It generates more CO and H2O.Water be at anode occur reaction anticipated output, therefore the anode output could generally have with anode output in Existing CO amount compares excessive H2O.Alternatively, can be after anode export but before water gas shift reaction by H2O is added to material In stream.Due to the incomplete carbon conversion in reforming process and/or due to existing in the condition of reorganization or during anode reaction Under conditions of H2O、CO、H2And CO2Between balanced reaction (i.e. water gas shift equilibrium), anode output in CO may be present.Water Shift reactor can be with CO and H2O is cost further towards formation CO2And H2Direction drive the balance under conditions of Operation.Higher temperature often advantageously forms CO and H2O.Therefore, an option for running water-gas shift can be So that anode output stream is exposed to suitable catalyst in suitable temperature, such as at about 190 DEG C to about 210 DEG C, such as wraps Under the catalyst for including iron oxide, zinc oxide, copper/zinc oxide etc..The water-gas shift optionally may include for reducing sun Pole exports two sections of the CO concentration in stream, wherein temperature of the first higher temperatures section at least about 300 DEG C to about 375 DEG C Lower operation, second compared with low-temperature zone at about 225 DEG C or lower, as run at a temperature of about 180 DEG C to about 210 DEG C.Except mentioning H present in high anode output2Amount is outer, and additionally or alternatively, water gas shift reaction can improve CO by cost of CO2Amount.This can Carbon dioxide is transformed into the carbon monoxide (CO) for removing hardly possible, and carbon dioxide more easily passes through condensation, and (such as deep cooling takes off Except), chemical reaction (such as amine removal) and/or other CO2Removal method removes.Additionally or alternatively, anode may desirably be improved CO content present in exhaust is to realize required H2/ CO ratio.

Anode output after optional water gas shift reaction section, can be made by one or more segregation sections with from sun Pole, which exports, removes water and/or CO in stream2.For example, can be exported using one or more methods to anode by independent or combined Carry out CO2Separation is to form one or more CO2Export stream.These methods, which can be used for generating, has 90 volume % or higher, such as At least 95% volume %CO2Or at least 98 volume %CO2CO2The CO of content2Export stream.It is defeated that anode can be recycled in these methods CO out2About at least about the 70% of content, the CO exported such as anode2At least about the 80% of content, or at least about 90%.Or Person may desirably recycle the only a part CO in anode output stream in certain aspects2, the CO of recycling2Part is anode CO in output2About 33% to about 90%, such as at least about 40%, or at least about 50%.For example, it may be possible to desirable It is to make some CO2It stays in anode output stream so that required form can be achieved in subsequent water gas shift stage.Suitable separation Method may include using physical solvent (for example, SelexolTMOr RectisolTM);Amine or other alkali (for example, MEA or MDEA); Freeze (for example, cryogenic separation);Pressure-variable adsorption;Vacuum Pressure Swing Adsorption;And their combination.Deep cooling CO2Separator can be conjunction One example of suitable separator.It is cooled down with anode is exported, most of water in anode output can be used as condensation (liquid) phase It isolates.The further cooling and/or pressurization of poor-water anode output stream then can separate high-purity CO2, because in anode output stream Other remaining ingredient (such as H2、N2、CH4) it is not easily formed condensation phase.Depending on service condition, deep cooling CO2Separator is recyclable CO present in stream2About 33% to about 90%.

From anode exhaust remove water with formed one or more water output stream material be also it is beneficial, no matter this is to carry out CO2Before separation, among or after.Water in anode output can become with selected service condition.For example, in anode inlet Vapour/carbon ratio of foundation can influence the water content in anode exhaust, and high vapour/carbon ratio typically results in a large amount of water, can be with unreacted Ground is by anode and/or merely due to the water gas shift equilibrium in anode is reacted.According to this aspect, the water in anode exhaust contains Measure up to about the 30% or bigger of the volume that can be equivalent in anode exhaust.Additionally or alternatively, water content can be arranged for anode About the 80% or smaller of air volume.Although such water, this water can be removed by compressing and/or cooling down and condense therewith Removing can need additional compressor horsepower and/or heat exchange surface area and a large amount of cooling water.Remove a part of this mistake A kind of beneficial manner for measuring water can capture moisture based on adsorbent bed is used from wet Anode effluent, then available Dry anode feed gas " regeneration ", to provide additional water to anode feed.HVAC- type (heating, ventilation and air conditioning) Sorption wheel design can be it is applicable because anode exhaust and entrance can be similar in pressure, and from a stream to another material The minor leakage of stream can have minimum influence to entire technique.CO is being carried out using Deep Cooling Method2In the embodiment of removing, CO2Water removal may be desirable before or during removing, including be removed water by triethylene glycol (TEG) system and/or desiccant.Phase Instead, if removing CO using amine washout2, then can be in CO2Removing section downstream is removed water from anode exhaust.

Instead of or in addition to CO2It exports outside stream and/or water output stream, anode output can be used to form one or more and contain The product stream of chemistry or fuel Products needed for having.Such product stream can be equivalent to synthesis gas stream, hydrogen stream or conjunction At both gas product and hydrogen gas product stream.For example, can be formed containing at least about 70 volume %H2, such as at least about 90 bodies Product %H2Or at least about 95 volume %H2Hydrogen gas product stream.Additionally or alternatively, it can be formed containing at least about 70 bodies in total The H of product %2And CO, such as at least about H of 90 volume %2With the synthesis gas stream of CO.One or more of product streams can have There is the total H being equivalent in anode output2With at least about the 75% of CO gas volume, such as total H2It is at least big with CO gas volume About 85% or at least about 90% gas volume.It is to be noted, that based on being carried out between product using water gas shift reaction section It converts, H in product stream2Relative quantity with CO may be different from the H in anode output2/ CO ratio.

In certain aspects, it desirably may remove or separate a part of H present in anode output2.For example, one H in a little aspect Anodic exhausts2/ CO ratio can be at least about 3.0:1.On the contrary, using the technique of synthesis gas, as Fischer-Tropsch closes At can with different ratios, such as close to 2:1 ratio consume H2And CO.One alternative can be anti-using Water gas shift/WGS The content of anode output should be changed to have the H formed closer to required synthesis gas2/ CO ratio.Another alternative can be benefit A part of H present in anode output is removed with UF membrane2To realize required H2/ CO ratio, or use UF membrane and Water gas shift/WGS The combination of reaction.The only a part H in anode output is removed using UF membrane2An advantage can be can be in relatively mild item Separation needed for being carried out under part.Still there is significant H since a target can be generation2The retentate of content can pass through UF membrane The penetrant of High Purity Hydrogen is generated without exacting terms.For example, penetrant side can under the pressure higher than environmental pressure, Still there is the driving force for being sufficient for UF membrane simultaneously, rather than there is about 100kPaa or lower (such as ring on film penetrant side Border pressure) pressure.Additionally or alternatively, purge gas such as methane can be used, the driving force of UF membrane is provided.This can reduce H2 The purity of penetrant stream, but depend on the required purposes of the penetrant stream, it may be possible to it is advantageous.

In aspects of the present invention, at least part anode exhaust stream is (preferably in separation CO2And/or H2After O) it is available Make the charging of fuel cell and the technique outside related reforming sections.In in all respects, anode exhaust may have about 1.5:1 to about 10:1, such as at least about 3.0:1, or at least about 4.0:1, or the H of at least about 5.0:12/ CO ratio.It can be by anode exhaust Generate or take out synthesis gas stream.Anode exhaust, optionally in separation CO2And/or H2After O and optionally in progress Water gas shift/WGS Reaction and/or UF membrane to remove excess hydrogen after, can be equivalent to containing quite a few H2And/or the stream of CO.For Stream with relatively low CO content, such as H2/ CO ratio is that at least about stream of 3:1, anode exhaust can be suitable as H2Into Material.It may benefit from H2The example of the technique of charging may include, but be not limited to, refinery processes, ammonia synthesizer or (difference) hair Turbine in electric system or combinations thereof.Depending on the application, still lower CO2Content may be desirable.It is less than greatly for having About 2.2 to the 1 and H greater than about 1.9 to 12The stream of/CO ratio, the stream can be suitable as synthesis gas charging.It may benefit from closing Example at the technique of gas charging may include, but be not limited to, and gas-to-liquid plant is (as used the fischer tropsch process by non-shifting catalyst Device) and/or methanol synthesizer.The amount of the anode exhaust of charging as external process can be any convenient amount. Optionally, when using charging of a part of anode exhaust as external process, the anode exhaust of second part is recyclable to be arrived Anode inputs and/or is recycled to the combustion zone of burning energy supply generator.

The input stream that can be used for different types of fischer-tropsch synthesis process can provide the difference for being suitble to be generated by anode output One example of the product stream of type.It, should such as the Fischer-Tropsch synthesis system of ferrum-based catalyst for using transformation catalyst The required input stream of reaction system removes H2It may also include CO outside with CO2.If enough CO are not present in input stream2, tool There are the active fischer-tropsch catalysts of Water gas shift/WGS that can consume CO to generate additional CO2, causing may the insufficient synthesis gas of CO.For This Fischer-tropsch process and SOFC fuel cell are integrated, the segregation section of anode output can be run to keep in syngas product Required CO2(and optional H2O it) measures.On the contrary, appointing present in product stream to the fischer-tropsch catalysts based on non-shifting catalyst What CO2It may act as the inert component in Fischer-Tropsch reaction system.

With purge gas, in terms of methane purge gas purging film, methane purge gas, which can be equivalent to, is used as sun Pole fuel or for different low pressure process, such as the methane stream of boiler, furnace, gas turbine or other fuel consumers.? In this aspect, across the low-level CO of the film2Infiltration can have minimum consequence.This CO of film may be penetrated2To in anode Reaction can have minimal effects, and this CO2It can be retained in anodic product.Therefore, because infiltration and cross-film loss CO2(if any) it does not need to retransfer through SOFC electrolyte.The separation selectivity to hydrogen permeation membrane can be significantly reduced in this It is required that.This allows that for example lower pressure and/or drop can be used using the higher permeability film having compared with low selectivity Low film surface product is possibly realized.In this aspect of the invention, the volume of purge gas can be the hydrogen in anode exhaust The big multiple of air volume, this can be such that effective density of hydrogen on penetrant side keeps close to 0.Thus the hydrogen separated may be incorporated into whirlpool In the charging methane of turbine, it can enhance turbine combustion feature as described above herein.

It is to be noted, that the excessive H generated in the anode2The fuel of separated greenhouse gases out can be represented.In anode output Any CO2It can easily separate, such as be washed by using amine, deep cooling CO from anode output2Separator and/or transformation or vacuum become Press absorption method.Several component (H of anode output2、CO、CH4) be not easy to remove, and CO2And H2O can usually be easy to remove.According to The embodiment can isolate the CO in anode output2At least about 90 volume %, form relatively high-purity CO2Output material Stream.Therefore, any CO generated in the anode can be efficiently separated out2To form high-purity CO2Output stream.After isolation, anode is defeated Remainder out can mainly be equivalent to the CO of component and reduction amount with chemistry and/or fuel value2And/or H2O.By In quite a few CO generated by original fuel (before reformation)2It can be separated, the sun by remainder can be reduced The CO of pole output generated with after-combustion2Amount.Particularly, the fuel in the anode output of remainder is H2Degree on, lead to Often additional greenhouse gases cannot be formed by the burning of this fuel.

The processing selection of various gases can be imposed to anode exhaust, it is disconnected from each other including Water gas shift/WGS and component.Two The general Anode machining scheme of kind is shown in fig 1 and 2.

Fig. 1 is schematically shown and the fuel cell array of chemical synthesis process combined operating solid oxide fuel cell One example of reaction system.In Fig. 1, to fuel cell 120 (as the fuel cell pack in fuel cell array The fuel cell of a part) 127 relevant (or multiple) reforming sections 110 of anode fuel streams 105 are provided.With fuel electricity The relevant reforming sections 110 in pond 120 can be in fuel cell module.In some optional aspects, external reformation also can be used Section (not shown) reforms a part of reformable fuel in input stream before it will input stream and be sent into fuel cell module.Combustion Material stream 105 preferably such as contains carbon-hydrogen link such as methane, other hydrocarbon and/or other class hydrocarbon compounds including reformable fuel Organic compound.Fuel streams 105 are optionally also with H2And/or CO, such as provided by optional anode recirculation stream 185 H2And/or CO.It is to be noted, that anode recirculation stream 185 is optional, and in many aspects in, not directly or by With fuel streams 105 or fuel reforming stream 115 in conjunction with and the recycling material of anode 127 is returned to from anode exhaust 125 indirectly Stream.In the reformed, fuel reforming stream 115 can be sent into the anode 127 of fuel cell 120.It can also will contain O2Stream 119 are sent into cathode 129.122 (the O of flux of oxygen ions of cathode portion 129 from fuel cell2 2-) it can provide anode fuel cell Remaining reaction object needed for reaction.Based on the reaction in anode 127, gained anode exhaust 125 may include H2O, it is equivalent to endless One or more component (H of the fuel of full response2、CO、CH4Or other components corresponding with reformable fuel) and choose any one kind of them Or a variety of additional non-reactive components, such as CO2、N2And/or other pollutants of a part as fuel streams 105.Then may be used Anode exhaust 125 is sent into one or more segregation sections.For example, CO2Removing section 140 can be equivalent to deep cooling CO2Removing system, For removing sour gas, such as CO2Amine wash section or for separating CO from anode exhaust2Another suitable type of output stream 143 CO2Segregation section.Optionally, anode exhaust can first pass around water-gas shift 130 with will be present in anode exhaust Any CO is (with some H2O is together) it is converted to the CO in the anode exhaust 135 of optional Water gas shift/WGS2And H2.Depending on CO2It is de- Except the property of section, water condensation or removing section 150 may be desirable to remove water output stream 153 from anode exhaust.Although It is shown in Fig. 1 in CO2After segregation section 140, but it can be optionally located at CO2Before segregation section 140.In addition, workable Optional is used to separate H2UF membrane section 160 to generate H2High-purity penetrant stream 163.Gained retentate stream 166 can be with It is used as the input of chemical synthesis process afterwards.Additionally or alternatively, stream 166 can become in the second water-gas shift 131 It changes with by H2, CO and CO2Content is adjusted to different ratios, generates the output stream 168 for being further used for chemical synthesis process.? It, but additionally or alternatively, can be from various it is shown that take out anode recirculation stream 185 from retentate stream 166 in Fig. 1 In segregation section or between other convenient positions take out anode recirculation streams 185.Additionally or alternatively, segregation section and transformation are anti- Answer device that can configure in different order and/or with parallel construction.Finally, the output that can be used as cathode 129, which generates, has reduction O2The stream 139 of content.For the sake of simplicity, the various compressions to come in handy in this method and heat supply/except hot arc are not explicitly shown And steam adds or removing section.

As described above, can be carried out to various types of separation that anode exhaust carries out with any convenient sequence.Fig. 2 is aobvious Show the example of another sequence separated to anode exhaust.In fig. 2 it is possible to which anode exhaust 125 is sent into segregation section first 260 from anode exhaust 125 to remove a part of 263 hydrogen contents.This can for example reduce the H of anode exhaust2Content is to mention For having the H close to 2:12The retentate 266 of/CO ratio.Then H can further be adjusted in water gas shift stage 2302/ CO ratio To realize desirable value.Then the output 235 of Water gas shift/WGS can pass through CO2Segregation section 240 and water removal section 250 are suitble to use to generate The output stream 275 of the charging of chemical synthesis process needed for making.Optionally additional Water gas shift/WGS can be imposed to output stream 275 Section (not shown).A part output stream 275 can optionally recycle (not shown) and input to anode.Certainly, required based on having The anode of composition exports, and the other combinations and sequence that can use segregation section are to generate stream.For the sake of simplicity, it is not explicitly shown The various compressions and heat supply to come in handy in this method/except hot arc and steam addition or removing section.

Cathode is output and input

It traditionally, can be based on load needed for being extracted while a part of fuel in the fuel streams that anode is sent in consumption To run solid oxide fuel cell.Then the air and O that can be inputted by the fuel of the load, anode, be provided to cathode2 The voltage of fuel cell is determined with the interior resistance of fuel cell.By eliminating between anode inlet flow and the composition of cathode inlet flow Any direct connection, it is possible to provide for the additional option of fuel cell operation, for example to generate excess syngas and/or improvement Gross efficiency (electricity+chemomotive force) of fuel cell etc..

Cathode inputs O present in stream2Oxygen needed for amount can advantageously be enough to provide the cathode reaction in fuel cell. Therefore, O2Percent by volume can be advantageously the O in the cathode exhaust gas2At least 0.5 times of amount.Optionally, if necessary, Additional air is added to provide enough oxidants to cathode reaction in can inputting to cathode.When some form of air of use N when as oxidant, in cathode exhaust gas2Amount can be at least about 78 volume %, for example, at least about 88 volume %, and/ Or about 95 volume % or lower.In certain aspects, cathode input stream can additionally or alternatively contain and be generally viewed as The compound of pollutant, such as H2S or NH3.In in terms of other, cathode input stream can be purified to reduce or by such dirt The content of dye object reduces to minimum.

Additionally or alternatively, the condition in cathode is applicable to unburned hydrocarbon (with the O in cathode input stream2In conjunction with) conversion At typical combustion product, such as CO2And H2O。

Fuel cell arrangement

, can be with fuel cell operation array to improve or make the energy of fuel cell to export in all respects, such as gross energy Output, power output, the output of syngas chemistry energy or combinations thereof maximize.For example, can be in each case with excessive Reformable operating fuel solid oxide fuel cell, such as generates be used for chemical synthesizer synthesis gas stream and/or For generating high-purity hydrogen stream.The synthesis gas stream and/or hydrogen stream can be used as synthesis gas source, hydrogen source, cleaning Fuels sources and/or be used for any other convenient purposes.O in such aspect, in cathode exhaust gas2Amount can be defeated with cathode Enter the O in stream2Amount and the O under required service condition2Utilization rate is associated to improve or make fuel cell energy output maximum Change.

Solid oxide fuel cell operation

On the one hand, the running temperature of SOFC can be about 700 DEG C to about 1200 DEG C, such as running temperature can be big About 800 DEG C, about 900 DEG C, about 1000 DEG C, or about 1100 DEG C.On the one hand, running temperature may be selected to promote in anode WGS react to required ratio.

In certain aspects, mode operation fuel cell can be passed through with one way or once.It, will not be positive in single pass mode Reformate in the exhaust of pole sends anode inlet back to.Therefore, not by synthesis gas, hydrogen or some other products in one way operation Anode inlet is recycled directly to from anode output.More generally, in one way operation, reformate in anode exhaust also not between Pick back anode inlet, such as fuel streams by the way that anode inlet is subsequently introduced using reformate processing.Additionally or alternatively, come It can be recycled in single pass mode from anode exhaust or the heat of output.For example, anode output stream can be through over-heat-exchanger, heat is handed over Anode is exported cooling and heats another stream, such as the input stream of anode and/or cathode by parallel operation.Again by the heat from anode Fuel cell is recycled to be consistent in one way or once by running use.Optionally but unpreferably, in one way mould The ingredient of the anode that can burn in formula output is with to fuel cell heat supply.

Fig. 3 shows an illustrative example of the operation of the SOFC for power generation.In Fig. 3, the anode portion of fuel cell Divide receivable fuel and steam (H2O) as input, and water and optional excess H are exported2、CH4(or other hydrocarbon) and/or CO.Fuel The cathode portion of battery can receive O2(such as air) is equivalent to the oxidant (air) of oxygen deprivation as input, output.In fuel In battery, in the O that cathode side is formed2 2-Oxygen needed for ion can provide the reaction occurred at the anode across electrolyte transport from Son.

In solid oxide fuel cell, if dry reaction can occur in example fuel cell as shown in Figure 3.It reforms Reaction can be optional and if directly provide enough H to anode2, then can reduce or save reforming reaction.It is following Reaction is based on CH4, but when using other fuel in a fuel cell, similar reaction can occur.

(1)<anode reformation>CH4+H2O=> 3H2+CO

(2)<Water gas shift/WGS>CO+H2O=> H2+CO2

(3)<combination>CH with Water gas shift/WGS is reformed4+2H2O=> 4H2+CO2

(4) < anode H2Oxidation > H2+O2 2-=> H2O+2e-

(5)<cathode>1/2O2+2e-=> O2 2-

Reaction (1) represents basic hydrocarbon reforming reaction to generate the H of the anode for fuel cell2.It reacts in (1) and is formed CO H can be converted to by water gas shift reaction (2)2.The combination of reaction (1) and (2) is shown as reaction (3).React (1) and (2) it can be carried out outside fuel cell, and/or reform and can be carried out in anode.

The reaction at anode and cathode (4) and (5) represent the reaction for causing the electric power in fuel cell to occur respectively.Instead (4) are answered to will be present in the H in charging or optionally by reacting (1) and/or (2) generation2Merge with oxonium ion to form H2O、CO2With It is sent to the electronics of the circuit.Reaction (5) makes O2、CO2Merge to form oxonium ion with the electronics from the circuit.It is generated by reacting (5) Oxonium ion can the electrolyte transport across fuel cell with provide reaction (4) needed for oxonium ion.With oxonium ion across electrolyte Transmission combines, and then can be electrically connected to form closed current loop by providing between the anode and cathode.

In various embodiments, the target of fuel cell operation can be the gross efficiency and/or combustion for improving fuel cell Expect battery+integrated chemical synthesis technology gross efficiency.This is typically different than the tradition operation of fuel cell, and wherein target can be For the fuel power generation function using supply battery with high electrical efficiency fuel cell operation.It as defined above, can be by by fuel cell Electricity output is determined divided by the low heat value of the input component of fuel cell again plus the low heat value of fuel cell output Total fuel cell efficiency.In other words, TFCE=(LHV (el)+LHV (sg out))/LHV (in), wherein LHV (in) and LHV (sg Out fuel element (such as H for being sent to fuel cell) is referred respectively to2、CH4And/or CO) and anode export stream or stream in synthesis Gas (H2, CO and/or CO2) LHV.This can provide electric energy+chemical energy amount of fuel cell and/or integrated chemical Process Production Degree.It is to be noted, that under this definition of gross efficiency, fuel cell/chemical synthesis system used in fuel cell and/or integrated The thermal energy used in system can contribute gross efficiency.But this definition does not include from fuel cell or integrated fuel cell/change Learn any excessive heat for exchanging in synthesis system or taking out in other ways.Therefore, if the excessive heat example from fuel cell It does not then include such excessive heat in the definition of gross efficiency such as generating steam to generate electricity by steam turbine.

Some operating parameters be can control with excessive reformable operating fuel fuel cell.Some parameters can be similar to mesh The preceding parameter that fuel cell operation is recommended.In certain aspects, the cathode conditions of fuel cell and temperature input can be similar to Those of recommend in document.For example, can be real within the scope of the typical temperature of fuel cell operation of solid oxide fuel cell Electrical efficiency needed for existing and required total fuel cell efficiency.In typical operations, temperature can across fuel cell improve.

In in terms of other, the operating parameter of fuel cell can be away from representative condition to which fuel cell operation is so that temperature Degree is reduced from anode inlet to anode export and/or from cathode inlet to cathode outlet.For example, converting hydrocarbons to H2With the weight of CO Whole reaction is the endothermic reaction.If carried out in anode of fuel cell enough relative to the amount of oxidation of the hydrogen for generating electric current It reforms, then the net thermal balance in the fuel cell can be heat absorption.This can lead between the entrance of fuel cell and outlet Cooling.In heat absorption operational process, the temperature that can control in fuel cell is reduced so that the electrolyte in fuel cell is kept Molten state.

Can to be different from it is presently recommended that in a manner of the parameter that controls may include the fuel quantity provided to anode, mention to anode The composition of the fuel of confession, and/or significantly it is recycled to from anode exhaust anode input without synthesis gas or the case where cathode inputs The separation and trapping of synthesis gas in lower anode output.In certain aspects, synthesis gas or hydrogen has not been allowed to arrange from anode Gas is directly or indirectly recycled to anode input or cathode input.In in terms of additionally or alternatively, it can occur limited amount Recycling.In such aspect, the recirculation volume of input and/or cathode input is smaller than anode row from anode exhaust to anode About 10 volume % of gas, such as less than about 5 volume % are less than about 1 volume %.

It in some embodiments, can be with the fuel cell in fuel arranged cell array in order to which there is only single section Fuel cell (such as fuel cell pack).In such embodiment, which can be represented The anode fuel utilization rate of the array.Another option, which can be fuel cell array, can contain multiple anode segments and multiple cathodes Section, wherein each anode segment has the fuel availability in same range, such as each anode segment has within the 10% of specified value, Such as the fuel availability within the 5% of specified value.Another option, which can be each anode segment, can have equal to specified value or ratio The low a certain amount of fuel availability below of specified value such as makes each anode segment be equal to specified value or smaller than specified value 10% or lower, Such as 5% or lower.Property example as an example, the fuel cell array with multiple anode segments can make each anode segment exist Within about the 10% of 50% fuel availability, this is equivalent to the fuel utilization that each anode segment has about 40% to about 60% Rate.As another example, the fuel cell array with multiple sections can make each anode segment no more than 60% anode fuel benefit With rate, maximum deviation be it is small by about 5%, this is equivalent to the fuel availability that each anode segment has about 55% to about 60%. In another example, one or more Fuel cell segments in fuel cell array can be with the combustion of about 30% to about 50% Expect utilization rate operation, multiple Fuel cell segments in the array are such as run with the fuel availability of about 30% to about 50%. More generally, the range of any of above type can utilize value pairing with any anode anode fuel defined herein.

Another additional or alternative option can be the fuel utilization of all fuel cells in specified fuels cell array The overall average of rate.In in all respects, the overall average of the fuel availability of fuel cell array can be about 65% or more It is low, such as about 60% or lower, about 55% or lower, about 50% or lower, or about 45% or lower (in addition or or Person, the overall average fuel availability of fuel cell array can be at least about 25%, for example, at least about 30%, at least about 35%, or at least about 40%).This average fuel utilization rate not have to limit the fuel availability in any single hop, As long as the fuel cell array meets required fuel availability.

The purposes of synthesis gas output after trapping

The component for exporting stream and/or cathode output stream from anode can be used for various uses.One option can be Use anode output as hydrogen source as described above.For the SOFC integrated or in the same place with oil plant, which can be used as respectively Kind refinery processes, such as the hydrogen source of hydrotreating.Such hydrogen can be used as in oil plant or other industrial plants boiler, The fuel and/or the hydrogen of furnace and/or fired heater can be used as generator, such as the charging of turbine.From SOFC fuel electricity The hydrogen in pond, which can also additionally or alternatively be used as, needs hydrogen other types of fuel cell as input (to may include combustion Expect battery-powered vehicle) input stream.Another option can be additionally or alternatively used as SOFC fuel cell Output generate synthesis gas as fermentation input.

Another option can be the synthesis gas for additionally or alternatively using and being generated by anode output.Of course, it is possible to use Synthesis gas is as fuel, although synthesis gas base fuel can still result in when as fuel combustion generates some CO2.In other sides In face, synthesis gas output stream can be used as the input of chemical synthesis process.One option, which can be, will additionally or alternatively close Another technique of bigger hydrocarbon molecule is formed for fischer-tropsch technique and/or inputted by synthesis gas at gas.Another option can be separately Intermediate product, such as methanol are formed using synthesis gas outside or alternatively.Methanol can be used as final product, but in terms of other in It can be used for generating more large compound by the methanol that synthesis gas generates, such as gasoline, alkene, aromatic hydrocarbons and/or other products.It is to be noted, that In the synthesis gas charging of methanol synthesizing process and/or the Fischer-tropsch process for using transformation catalyst, a small amount of CO2It is acceptable. Hydroformylation is an additional or alternative example using the another synthesis technology of synthesis gas input.

It is to be noted, that using SOFC fuel cell as adding to using a change of SOFC generation synthesis gas can be Work offshore oil platform take out methane and/or natural gas system or away from the quite remote other production systems of its final market A part.Come gas phase output or the long term storage gas-phase product of artesian well rather than attempt to transport, but the gas for carrying out artesian well can be used Mutually input of the output as SOFC fuel cell array.This can bring various benefits.Firstly, by the fuel cell array column-generation Electric power can be used as the power supply of the platform.In addition, the synthesis gas output from the fuel cell array can be used as the expense of production scene Hold in the palm the input of technique.This can be formed more easily by pipeline, ship or railcar from production scene transport to such as shore facilities or The liquid hydrocarbon product of bigger terminal.

Other integrated options can additionally or alternatively include using cathode output as the heating nitrogen of higher purity The source of gas.Cathode input usually may include most air, it means that cathode input in may include quite a few Nitrogen.Fuel cell can convey O to anode from cathode across electrolyte2, and cathode outlet can have the O lower than in air2Concentration With therefore higher N2Concentration.Residual O is removed subsequent2In the case where, the output of this nitrogen can be used as producing ammonia or other Nitrogenous chemicals, such as the charging of urea, ammonium nitrate and/or nitric acid.It is to be noted, that urea synthesis can be used additionally or alternatively from sun The CO separated in the output of pole2It is fed as input.

Additional embodiment

Embodiment 1. produces electricity and hydrogen or synthesis using the solid oxide fuel cell with anode and cathode The method of gas, the method includes will include reformable fuel fuel streams introduce solid oxide fuel cell anode, Reforming sections (including inside reforming element) relevant to the anode of solid oxide fuel cell, or combinations thereof in;It will include O2 Cathode inlet stream be introduced into the cathode of solid oxide fuel cell;It generates electricity in solid oxide fuel cell;From sun Take out in the exhaust of pole includes H2Air-flow, include H2With the air-flow or a combination thereof of CO, wherein solid oxide fuel cell Electrical efficiency is about 10% to about 50%, and total fuel cell manufacture rate of solid oxide fuel cell is at least about 150mW/cm2

The method of 2. embodiment 1 of embodiment, wherein operation solid oxide fuel cell with about 0.25 to big About 1.3, perhaps about 1.15 or lower perhaps about 1.0 or lower or about 0.75 or lower thermal ratio under generate Electricity.

The method of any one of 3. embodiments above of embodiment, wherein comprising reformable fuel fuel streams can Fuel reforming excess rate is at least about 2.0, or at least about 2.5.

The method of any one of 4. embodiments above of embodiment, wherein the electrical efficiency of solid oxide fuel cell be About 45% or lower, or about 35% or lower.

The method of any one of 5. embodiments above of embodiment, wherein total fuel of solid oxide fuel cell is electric Pond efficiency is at least about 65%, perhaps at least about 70% perhaps at least about 75% or at least about 80%.

The method of any one of 6. embodiments above of embodiment, wherein total fuel of solid oxide fuel cell is electric Pond productivity is at least about 150mW/cm2, or at least about 300mW/cm2, or at least about 350mW/cm2, Huo Zhe great About 800mW/cm2Or it is lower.

The method of any one of 7. embodiments above of embodiment, wherein solid oxide fuel cell is total reformable Fuel production rate is at least about 75mW/cm2, or at least about 100mW/cm2, or at least about 150mW/cm2, or At least about 200mW/cm2, or about 600mW/cm2Or it is lower.

The method of any one of 8. embodiments above of embodiment, wherein introducing the sun of solid oxide fuel cell Weighing in pole, reforming sections relevant to the anode of solid oxide fuel cell (including inside reforming element) or a combination thereof The reformable hydrogen content of whole fuel is higher by least about 75% than the amount for the hydrogen that reaction generates electricity, such as height at least about 100%.

The method of any one of 9. embodiments above of embodiment, wherein fuel streams include at least about 10 volume % Inert compound, at least about 10 volume %CO2, or a combination thereof.

The method of any one of 10. embodiments above of embodiment, wherein at about 0.67 volt or lower, Huo Zhe great About 0.5 volt or lower voltage VALower fuel cell operation.

The method of any one of 11. embodiments above of embodiment, wherein anode exhaust has about 1.5:1 to about The H of 10:12/ CO ratio.

The method of any one of 12. embodiments above of embodiment, wherein anode exhaust is at least about 3.0:1's H2/ CO ratio.

The method of any one of 13. embodiments above of embodiment, wherein solid oxide fuel cell is solid for tubulose Oxide body fuel cell.

The method of any one of 14. embodiments above of embodiment, wherein solid oxide fuel cell is further wrapped Include one or more integrated endothermic reaction sections.

The method of 15. embodiment 14 of embodiment, the integrated endothermic reaction section of wherein at least one includes integrated weight Whole section, be introduced into fuel streams in the anode of solid oxide fuel cell the anode for entering solid oxide fuel cell it It is preceding to pass through integrated reforming sections.

The method of any one of 16. embodiment 1-15 of embodiment, wherein the temperature of anode export is than anode inlet About 40 DEG C of warmer or less.

The method of any one of 17. embodiment 1-15 of embodiment, the wherein temperature of anode inlet and anode export About 20 DEG C of temperature difference or less.

The method of any one of 18. embodiment 1-15 of embodiment, wherein the temperature of anode export is than anode inlet Temperature is about 10 DEG C to about 80 DEG C low.

The method of any one of 19. embodiment 1-15 of embodiment, wherein thermal ratio is about 0.85 or lower, described Method further comprises supplying heat to fuel cell, to keep the temperature of anode export about 5 DEG C lower than the temperature of anode inlet To about 50 DEG C.

The method of any one of 20. embodiments above of embodiment, the method further includes reforming reformable combustion Material, wherein introducing the anode of solid oxide fuel cell, reforming sections relevant to the anode of solid oxide fuel cell (packet Include inside reforming element) or a combination thereof in reformable fuel at least about 90% passing through solid oxide fuel cell Anode one way in reform.

Although the present invention has been described with reference to specific embodiments, however, the present invention is not limited thereto.It runs in specific circumstances Suitable change/modification should be apparent to those skilled in the art.Therefore following claims are intended to be interpreted Cover all such change/modifications fallen in true spirit/range of the invention.

Claims (35)

1. the method for producing electricity and hydrogen or synthesis gas using the solid oxide fuel cell with anode and cathode, described Method includes:
The anode and solid oxide fuel electricity of solid oxide fuel cell will be introduced comprising the fuel streams of reformable fuel The relevant reforming sections of the anode in pond, or combinations thereof in, wherein comprising reformable fuel fuel streams reformable fuel excess Rate is at least 2.0;
It will include O2Cathode inlet stream be introduced into the cathode of solid oxide fuel cell;
It generates electricity in solid oxide fuel cell;With
Take out from anode exhaust includes H2Air-flow, include H2With the air-flow or a combination thereof of CO,
Wherein the electrical efficiency of solid oxide fuel cell is 10% to 50%, total reformable combustion of solid oxide fuel cell Expect that productivity is at least 75mW/cm2, total fuel cell manufacture rate of solid oxide fuel cell is at least 150mW/cm2
2. the method for claim 1 wherein operation solid oxide fuel cell to generate under 0.25 to 1.3 thermal ratio Electricity.
3. the method for claim 1 wherein operation solid oxide fuel cell to generate under 0.25 to 1.15 thermal ratio Electricity.
4. the method for claim 1 wherein operation solid oxide fuel cell to generate under 0.25 to 1.0 thermal ratio Electricity.
5. the method for claim 1 wherein operation solid oxide fuel cell to generate under 0.25 to 0.75 thermal ratio Electricity.
6. or more the method for claim 1 wherein the reformable fuel excess rate of the fuel streams comprising reformable fuel be extremely Few 2.5.
7. or more any one of claim 1-6 method, wherein the electrical efficiency of solid oxide fuel cell is 45% or more It is low.
8. or more method for claim 7, wherein the electrical efficiency of solid oxide fuel cell be 35% or lower.
9. or more any one of claim 1-6 method, wherein total fuel cell efficiency of solid oxide fuel cell be At least 65%.
10. or more method for claim 9, wherein total fuel cell efficiency of solid oxide fuel cell is at least 70%.
11. or more method for claim 9, wherein total fuel cell efficiency of solid oxide fuel cell is at least 75%.
12. or more method for claim 9, wherein total fuel cell efficiency of solid oxide fuel cell is at least 80%.
13. or more any one of claim 1-6 method, wherein total fuel cell manufacture rate of solid oxide fuel cell It is at least 150mW/cm2
14. or more claim 13 method, wherein total fuel cell manufacture rate of solid oxide fuel cell is at least 300mW/cm2
15. or more claim 13 method, wherein total fuel cell manufacture rate of solid oxide fuel cell is at least 350mW/cm2
16. or more claim 13 method, wherein total fuel cell manufacture rate of solid oxide fuel cell be 800mW/ cm2Or it is lower.
17. or more any one of claim 1-6 method, wherein total reformable fuel production of solid oxide fuel cell Rate is at least 100mW/cm2
18. or more claim 17 method, wherein total reformable fuel production rate of solid oxide fuel cell is at least 150mW/cm2
19. or more claim 17 method, wherein total reformable fuel production rate of solid oxide fuel cell is at least 200mW/cm2
20. or more claim 17 method, wherein total reformable fuel production rate of solid oxide fuel cell be 600mW/cm2Or it is lower.
21. or more any one of claim 1-6 method, wherein introducing the anode and solid of solid oxide fuel cell The reformable hydrogen content of reformable fuel in relevant reforming sections of the anode of oxide fuel cell or a combination thereof is than reaction Generate the amount height at least 75% of the hydrogen of electricity.
22. or more claim 21 method, wherein introduce solid oxide fuel cell anode and solid oxide fuel The reformable hydrogen content of reformable fuel in relevant reforming sections of the anode of battery or a combination thereof generates the hydrogen of electricity than reaction Amount height at least 100%.
23. or more any one of claim 1-6 method, wherein fuel streams include at least 10 volume % inert compounds, At least 10 volume %CO2, or a combination thereof.
24. or more any one of claim 1-6 method, wherein at 0.67 volt or lower voltage VALower operation fuel electricity Pond.
25. or more claim 24 method, wherein at 0.5 volt or lower voltage VALower fuel cell operation.
26. or more any one of claim 1-6 method, wherein anode exhaust has the H of 1.5:1 to 10:12/ CO ratio.
27. or more any one of claim 1-6 method, wherein anode exhaust has the H of 3.0:1 to 10:12/ CO ratio.
28. or more any one of claim 1-6 method, wherein solid oxide fuel cell is tubular solid-oxide combustion Expect battery.
29. or more any one of claim 1-6 method, wherein solid oxide fuel cell further comprises one or more A integrated endothermic reaction section.
30. the method for claim 29, the integrated endothermic reaction section of wherein at least one includes integrated reforming sections, solid is introduced Fuel streams in the anode of oxide fuel cell pass through integrated before the anode for entering solid oxide fuel cell Reforming sections.
31. the method for any one of claim 1-6, wherein the temperature of anode export is 40 DEG C or higher than the temperature of anode inlet It is few.
32. the method for any one of claim 1-6, wherein 20 DEG C of the temperature difference of the temperature of anode inlet and anode export or Less.
33. the method for any one of claim 1-6, wherein the temperature of anode export is 10 DEG C to 80 lower than the temperature of anode inlet ℃。
34. the method for any one of claim 1-6, wherein thermal ratio is 0.85 or lower, the method further includes to Fuel cell supply heat, to keep the temperature of anode export 5 DEG C to 50 DEG C lower than the temperature of anode inlet.
35. or more any one of claim 1-6 method, the method further includes reforming reformable fuel, wherein drawing Enter in the anode of solid oxide fuel cell, reforming sections relevant to the anode of solid oxide fuel cell or a combination thereof Reformable fuel at least 90% reformed in the one way by the anode of solid oxide fuel cell.
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US201361884376P true 2013-09-30 2013-09-30
US201361884605P true 2013-09-30 2013-09-30
US201361884586P true 2013-09-30 2013-09-30
US201361884635P true 2013-09-30 2013-09-30
US201361884565P true 2013-09-30 2013-09-30
US201361884545P true 2013-09-30 2013-09-30
US61/884,565 2013-09-30
US61/884,605 2013-09-30
US61/884,586 2013-09-30
US61/884,635 2013-09-30
US61/884,545 2013-09-30
US61/884,376 2013-09-30
US201361889757P true 2013-10-11 2013-10-11
US61/889,757 2013-10-11
US14/197,391 2014-03-05
US14/197,391 US20140272613A1 (en) 2013-03-15 2014-03-05 Integrated power generation and carbon capture using fuel cells
US14/197,613 US9774053B2 (en) 2013-03-15 2014-03-05 Integrated power generation and carbon capture using fuel cells
US14/197,551 US20140272615A1 (en) 2013-03-15 2014-03-05 Integrated power generation and carbon capture using fuel cells
US14/197,430 US20140272614A1 (en) 2013-03-15 2014-03-05 Integrated power generation and carbon capture using fuel cells
US14/197,430 2014-03-05
US14/197,613 2014-03-05
US14/197,551 2014-03-05
US14/207,708 2014-03-13
US14/207,706 US9455463B2 (en) 2013-03-15 2014-03-13 Integrated electrical power and chemical production using fuel cells
US14/207,710 2014-03-13
US14/207,712 US9343763B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells for synthesis of nitrogen compounds
US14/207,712 2014-03-13
US14/207,710 US9362580B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in a refinery setting
US14/207,728 US20140261090A1 (en) 2013-03-15 2014-03-13 Integration of Molten Carbonate Fuel Cells in Cement Processing
US14/207,706 2014-03-13
US14/207,690 US9553321B2 (en) 2013-03-15 2014-03-13 Integrated power generation and carbon capture using fuel cells
US14/207,691 2014-03-13
US14/207,697 US9923219B2 (en) 2013-03-15 2014-03-13 Integrated operation of molten carbonate fuel cells
US14/207,687 2014-03-13
US14/207,693 2014-03-13
US14/207,690 2014-03-13
US14/207,728 2014-03-13
US14/207,687 US9941534B2 (en) 2013-03-15 2014-03-13 Integrated power generation and carbon capture using fuel cells
US14/207,691 US9257711B2 (en) 2013-03-15 2014-03-13 Integrated carbon capture and chemical production using fuel cells
US14/207,726 US9263755B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in iron and steel processing
US14/207,721 US9520607B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells with fermentation processes
US14/207,708 US9647284B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
US14/207,714 2014-03-13
US14/207,699 2014-03-13
US14/207,698 2014-03-13
US14/207,686 US20140272633A1 (en) 2013-03-15 2014-03-13 Integrated power generation and carbon capture using fuel cells
US14/207,698 US9419295B2 (en) 2013-03-15 2014-03-13 Integrated power generation and chemical production using fuel cells at a reduced electrical efficiency
US14/207,693 US9786939B2 (en) 2013-03-15 2014-03-13 Integrated power generation and chemical production using fuel cells
US14/207,699 US20140272635A1 (en) 2013-03-15 2014-03-13 Mitigation of NOx in Integrated Power Production
US14/207,721 2014-03-13
US14/207,686 2014-03-13
US14/207,711 2014-03-13
US14/207,726 2014-03-13
US14/207,697 2014-03-13
US14/207,711 US9735440B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US14/207,714 US9343764B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in methanol synthesis
US14/315,419 US9178234B2 (en) 2013-03-15 2014-06-26 Integrated power generation using molten carbonate fuel cells
US14/315,419 2014-06-26
US14/315,479 2014-06-26
US14/315,479 US9077006B2 (en) 2013-03-15 2014-06-26 Integrated power generation and carbon capture using fuel cells
US14/315,527 2014-06-26
US14/315,439 US9077005B2 (en) 2013-03-15 2014-06-26 Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
US14/315,527 US9077008B2 (en) 2013-03-15 2014-06-26 Integrated power generation and chemical production using fuel cells
US14/315,439 2014-06-26
US14/315,507 2014-06-26
US14/315,507 US9077007B2 (en) 2013-03-15 2014-06-26 Integrated power generation and chemical production using fuel cells
US14/486,159 US9755258B2 (en) 2013-09-30 2014-09-15 Integrated power generation and chemical production using solid oxide fuel cells
US14/486,159 2014-09-15
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