CN105580179A - Integrated power generation and chemical production using solid oxide fuel cells - Google Patents

Integrated power generation and chemical production using solid oxide fuel cells Download PDF

Info

Publication number
CN105580179A
CN105580179A CN201480053460.9A CN201480053460A CN105580179A CN 105580179 A CN105580179 A CN 105580179A CN 201480053460 A CN201480053460 A CN 201480053460A CN 105580179 A CN105580179 A CN 105580179A
Authority
CN
China
Prior art keywords
fuel cell
anode
fuel
solid oxide
reformable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201480053460.9A
Other languages
Chinese (zh)
Other versions
CN105580179B (en
Inventor
P·J·贝洛维茨
T·A·巴尔克霍尔兹
A·S·李
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/197,430 external-priority patent/US20140272614A1/en
Priority claimed from US14/207,728 external-priority patent/US20140261090A1/en
Priority claimed from US14/315,527 external-priority patent/US9077008B2/en
Priority claimed from US14/486,159 external-priority patent/US9755258B2/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of CN105580179A publication Critical patent/CN105580179A/en
Application granted granted Critical
Publication of CN105580179B publication Critical patent/CN105580179B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production 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
    • C01B3/34—Production 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
    • C01B3/38—Production 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637—Direct internal reforming at the anode of the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/243—Grouping of unit cells of tubular or cylindrical configuration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C01B2203/067—Integration with other chemical processes with fuel cells the reforming process taking place in the fuel cell
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/84—Energy production
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

In various aspects, systems and methods are provided for operating a solid oxide fuel cell at conditions that can improve or optimize the combined electrical efficiency and chemical efficiency of the fuel cell. Instead of selecting conventional conditions for maximizing the electrical efficiency of a fuel cell, the operating conditions can allow for output of excess synthesis gas and/or hydrogen in the anode exhaust of the fuel cell. The synthesis gas and/or hydrogen can then be used in a variety of applications, including chemical synthesis processes and collection of hydrogen for use as a fuel.

Description

Use integrated generation and the chemical production of Solid Oxide Fuel Cell
Invention field
In every respect, the present invention relates to and the chemical production and/or the electrification technique as well as that use Solid Oxide Fuel Cell to produce electric power integration.
background of invention
Solid Oxide Fuel Cell utilizes hydrogen and/or other fuel power generation function.Hydrogen is provided by reforming methane in the steam reformer in fuel cell upstream or fuel cell or other reformable fuel.Reformable fuel can comprise and can react the hydrocarbon material of the gaseous products producing hydrogen 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, described fuel cell can be run to create the condition being applicable to fuel reforming in the anode.Or or in addition, can reform in the outside of fuel cell and inside.
Traditionally, run the Energy Maximization that Solid Oxide Fuel Cell inputs to make per unit fuel, this can be referred to as the electrical efficiency of fuel cell.This maximization can based on fuel cell alone or in the heat and power application combined.In order to the energy output realizing improving generates heat with management, the fuel availability in fuel cell remains on 70% to 85% usually.
U.S. Patent Application Publication No.2005/0123810 describes a kind of system and method for hydrogen and electric energy coproduction.This co-generation system comprises fuel cell and is configured to receive anode exhaust stream and the separative element of separating hydrogen gas.Part anode exhaust is also recycled to anode inlet.The range of operation provided during ' 810 are open seems based on molten carbonate fuel cell.Solid Oxide Fuel Cell is described to substitute.
summary of the invention
On the one hand, the method using the Solid Oxide Fuel Cell with anode and negative electrode to produce electricity and hydrogen or synthesis gas is provided.The fuel streams comprising reformable fuel is introduced the anode of Solid Oxide Fuel Cell, the inside reforming element relevant to the anode of Solid Oxide Fuel Cell or during it combines by the method; O will be comprised 2cathode inlet stream introduce Solid Oxide Fuel Cell negative electrode in; Generate electricity in Solid Oxide Fuel Cell; Take out from anode exhaust and comprise H 2air-flow, comprise H 2with air-flow or their combination of CO, wherein the electrical efficiency of Solid Oxide Fuel Cell is about 10% to about 50%, and total fuel cell manufacture rate of Solid Oxide Fuel Cell is at least about 150mW/cm 2.
accompanying drawing is sketched
Fig. 1 schematically shows an example of the configuration of Solid Oxide Fuel Cell and relevant reforming sections and segregation section.
Fig. 2 schematically shows another example of the configuration of Solid Oxide Fuel Cell and relevant reforming sections and segregation section.
Fig. 3 schematically shows an example of the operation of Solid Oxide Fuel Cell.
embodiment describes in detail
summary
In every respect, provide the system and method also being produced a large amount of hydrogen or synthesis gas by Solid Oxide Fuel Cell (SOFC) with the total fuel cell efficiency of height except producing electricity.Each side of the present invention can use flat plate cell or tubular cell.Total fuel cell efficiency is commonly referred to as comprehensive electrical efficiency and the chemical efficiency of fuel cell.The more complete definition of total fuel cell efficiency is provided subsequently.
Can with any other parameter for the typical fuel cell system of design and running under cost is for optimizing electrical efficiency.The heat that can utilize original position and/or produce due to burnt gas and anodic product to maintain fuel cell to run with limit required for degree.The same with most of electricity-generating method, conventional fuel cell system mainly payes attention to electric product.It is produce in the application of efficient electrical power, as in distributed power generation or generating for subsequent use that conventional fuel cell system can be used in main purpose.
Each side of the present invention can be set up fuel cell operation parameter and exceed conventional fuel cell efficiency to cause total fuel cell efficiency.In addition or or, the invention provides and improve total fuel cell manufacture rate and maintain the method for very high overall system efficiency simultaneously.On the one hand, productivity ratio is: for the fuel cell capacity of design flow, and the total amount of the useful products (as synthesis gas, heat, electricity) that time per unit produces, as the cross-sectional area by fuel cell is measured.Selection is replaced to make the maximized conventional conditions of fuel-cell electrical efficiency, service conditions can produce total fuel cell efficiency and/or the productivity ratio of much higher whole system, if allow that electrical efficiency is down to below the best electrical efficiency of seeking in above-mentioned typical fuel cells system.As described in more detail below, total fuel cell efficiency be the amount of the energy produced by fuel cell relative to the measuring of amount of energy being delivered to fuel cell, and productivity ratio is the measuring of size (as annode area) of amount relative to fuel cell of the energy (total chemistry, electricity and heat energy) produced by fuel cell.Excess syngas and/or hydrogen in the anode exhaust of the condition tolerable fuel cell of high total fuel cell efficiency and/or productivity ratio can be realized export and realize to allow the excessive production of some products by making the input and output of anode and negative electrode separate (decoupling) wholly or in part.This excessive heat that can such as be produced by the electrical efficiency (such as by running at the lower voltage) and/or use original position that reduce battery is used for effectively producing the realization of (such as synthesis gas form) chemical energy.Therefore, compared with known in the art, fuel cell can be processed much bigger to the total fuel input of anode, maintains similar or higher total delivery efficiency (chemistry, electricity and useful heat energy sum) simultaneously.Higher productivity ratio is allowed that fuel cell is more effective and is used in integrated system.
The electrochemical method occurred in anode can cause anode to export synthesis air-flow and comprise at least H 2, CO and CO 2combination.Then water gas shift reaction can be used to produce the composition of required synthesis gas and/or make H 2output increases relative to other synthesis gas components or maximizes.Then can use synthesis gas and/or hydrogen in various applications, include but not limited to chemical synthesis process and/or collect hydrogen be used as " cleaning " fuel.
As used herein, term " electrical efficiency " (" EE ") is defined as the speed of the low heat value (" LHV ") that the electrochemical kinetics that produced by fuel cell inputs divided by fuel-cell fuel.The fuel input of fuel cell comprises the fuel that is sent to anode and for keeping any fuel of the temperature of fuel cell, as being sent to the fuel of the burner relevant to fuel cell.In this manual, the power produced by this fuel can describe with LHV (el) fuel rate (fuelrate).
As used herein, term " electrochemical kinetics " or LHV (el) are circuit by connecting negative electrode and positive electrode in fuel cell and oxonium ion through the transfer of fuel-cell electrolyte and the power generated.The power that the equipment that electrochemical kinetics does not comprise fuel cell upstream or downstream produces or consumes.Such as, a part for electrochemical kinetics is not regarded as by the thermogenetic electricity in fuel cell exhaust stream.Similarly, the power generated by gas turbine or the miscellaneous equipment of fuel cell upstream is not a part for the electrochemical kinetics generated." electrochemical kinetics " does not consider the electric power consumed in fuel cell operation or any loss becoming alternating current to cause by DC conversion.In other words, from the direct current power that fuel cell produces, do not deduct the electric power for supplying fuel cell operation or otherwise fuel cell operation.Power density used herein is that current density is multiplied by voltage.Current density used herein is the electric current of per unit area.Total fuel battery power used herein is that power density is multiplied by fuel cell area.
Term used herein " anode fuel input ", being referred to as LHV (anode_in), is the fuel quantity in anode inlet stream.Term " fuel input ", being referred to as LHV (in), is the total amount of fuel being sent to fuel cell, comprises fuel quantity in anode inlet stream and for keeping the fuel quantity of the temperature of fuel cell.Based on the definition of reformable fuel provided herein, this fuel can comprise reformable and not reformable fuel.Fuel input is different from fuel availability.
Term used herein " total fuel cell efficiency " (" TFCE ") is defined as: the electrochemical kinetics generated by fuel cell adds the speed (rateofLHV) of the LHV of the synthesis gas generated by fuel cell, the speed of the LHV that the fuel divided by anode inputs.In other words, TFCE=(LHV (el)+LHV (sgnet))/LHV (anode_in), wherein LHV (anode_in) refers to that the fuel element being sent to anode is (as H 2, CH 4and/or CO) the speed of LHV, and LHV (sgnet) refers to and produces synthesis gas (H in the anode 2, CO) speed, it is the difference that the synthesis gas input of anode exports with the synthesis gas of anode.The electrochemical kinetics that LHV (el) describes fuel cell generates.Total fuel cell efficiency does not comprise the heat for the useful utilization outside this fuel cell generated by this fuel cell.Be in operation, the heat generated by fuel cell may by the useful utilization of upstream device.Such as, this heat can be used for generating extra electric power or for heating water.When using this term in this application, these purposes implemented outward at fuel cell are not parts for total fuel cell efficiency.Total fuel cell efficiency is only for fuel cell operation, and the power not comprising fuel cell upstream or downstream generates or consumes.
Term used herein " chemical efficiency " is defined as the H in the anode exhaust of fuel cell 2with the low heat value of CO or LHV (sgout) divided by fuel input or LHV (in).
Term used herein " total fuel cell manufacture rate " (" TFCP ") is defined as the conversion owing to inputting fuel, and per unit fuel cell cross-section amasss the total energy value of the product that time per unit produces.Fuel can transform in oxidation reaction, reforming reaction and/or water gas shift reaction.The gross energy of product can with any unit easily as mW/cm 2represent.The product that fuel cell produces can comprise electrochemical kinetics, synthesis gas and/or hydrogen and heat.The heat produced is measured by the temperature difference measured between anode inlet and anode export.Such as, the productivity ratio of fuel cell can with mW/cm 2the cross-sectional area of anode of fuel cell represents.Fuel cell operating conditions can be selected arbitrarily to produce high total fuel cell manufacture rate and high total fuel cell efficiency.
Term used herein " total reformable fuel production rate " (" TRFP ") is based on per unit 2the LHV of the reformable fuel input of the anode that fuel cell cross-section amasss and the difference of LHV being exported the reformable fuel received by anode.The amount that anode inlet and the difference of the reformable fuel in outlet can approximate greatly the reformable fuel changing into synthesis gas and/or hydrogen deducts the synthesis gas of new generation and/or the amount of hydrogen that consume in the oxidation reaction of final generation electricity.The synthesis gas of new generation and/or hydrogen are in the anode or be to produce in the integrated relevant reforming sections of fuel cell heat.The synthesis gas and/or the hydrogen that feed anode inlet are not new generations.Fuel cell operating conditions can be selected arbitrarily to produce high total reformable fuel production rate and high total fuel cell efficiency.
In certain aspects, the operation of fuel cell can be characterized based on electrical efficiency.When fuel cell operation is to have low electrical efficiency (EE), Solid Oxide Fuel Cell can be run to have about 50% or lower, the electrical efficiency of such as about 45%EE or lower, 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.In addition or or, EE can be at least about 5%, or at least about 10%, or at least about 15%, at least about 20%, at least about 25%, or at least about 30%.Again in addition or or, can based on total fuel cell efficiency (TFCE), as the comprehensive electrical efficiency of fuel cell and chemical efficiency characterize the operation of fuel cell.If fuel cell operation is to have high total fuel cell efficiency, Solid Oxide Fuel Cell can be run 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 the TFCE of about 85% or higher (and/or comprehensive electrical efficiency and chemical efficiency).Point out, for total fuel cell efficiency and/or comprehensive electrical efficiency and chemical efficiency, any additional power of the excessive heat generation utilizing fuel cell to generate can not be comprised in efficiency calculation.
In each side of the present invention, the operation of fuel cell can be characterized based on total fuel cell efficiency needed for electrical efficiency and 55% or higher needed for about 50% or lower.When fuel cell operation is to have required electrical efficiency and required total fuel cell efficiency, Solid Oxide Fuel Cell can be run to have the electrical efficiency of 50% or lower and the TFCE of about 55% or higher, the EE of such as about 40% or the lower and TFCE of about 60% or higher, the EE of about 35% or the lower and TFCE of about 65% or higher, the EE of about 30% or the lower and TFCE of about 70% or higher, or the TFCE of the EE of about 20% or lower and about 75% or higher, or the TFCE of the EE of about 15% or lower and about 80% or higher, or the TFCE of the EE of about 10% or lower and about 85% or higher.
In each side of the present invention, can based on about 150mW/cm 2or higher required total fuel cell manufacture rate (" TFCP ") and 55% or higher required total fuel cell efficiency characterize the operation of fuel cell.When fuel cell is to have about 150mW/cm 2when above required TFCP and required total fuel cell efficiency are run, Solid Oxide Fuel Cell can be run with the TFCE with about 55% or higher, such as about 60% or higher, about 65% or higher, about 70% or higher, or about 75% or higher, or about 80% or higher, or about 85% or higher.When fuel cell is to have total fuel cell efficiency operation needed for 55% or higher, Solid Oxide Fuel Cell can be run to have at least approximately 150mW/cm 2tFCP, or at least about 200mW/cm 2, or at least about 250mW/cm 2, or at least about 300mW/cm 2, or at least about 350mW/cm 2.In every respect, TFCP can be about 800mW/cm 2or lower, or about 700mW/cm 2or lower, or about 600mW/cm 2or lower, or about 500mW/cm 2or lower, or about 400mW/cm 2or it is lower.
In each side of the present invention, can based on about 75mW/cm 2or higher required total reformable fuel production rate and 55% or higher required total fuel cell efficiency characterize the operation of fuel cell.When fuel cell operation is to have about 75mW/cm 2when above required reformable fuel production rate and required total fuel cell efficiency, Solid Oxide Fuel Cell can be run with the TFCE with about 55% or higher, such as about 60% or higher, about 65% or higher, about 70% or higher, or about 75% or higher, or about 80% or higher, or about 85% or higher, or about 90% or higher.When fuel cell operation is to have total fuel cell efficiency needed for 55% or higher, Solid Oxide Fuel Cell can be run to have at least approximately 75mW/cm 2reformable fuel production rate, or at least about 100mW/cm 2, or at least about 125mW/cm 2, or at least about 150mW/cm 2, or at least about 175mW/cm 2, or at least about 200mW/cm 2, or at least about 300mW/cm 2.In these areas, reformable fuel production rate can be about 600mW/cm 2lower, or about 500mW/cm 2lower, or about 400mW/cm 2lower, or about 300mW/cm 2lower, or about 200mW/cm 2lower.
Run Solid Oxide Fuel Cell can realize in every way to have required electrical efficiency, chemical efficiency and/or total fuel cell efficiency.In some respects, the chemical efficiency of Solid Oxide Fuel Cell can improve for producing the relative value of the amount of the hydrogen that electricity is oxidized in the amount of the reformation that (and/or relevant reforming sections in) in fuel cell module carries out by improving in fuel cell and anode.Traditionally, run Solid Oxide Fuel Cell and maintain suitable heat balance to keep total system temperature to make power generation efficiency maximize relative to the amount of fuel consumption simultaneously.Under this kind of service conditions, be desirable at the fuel availability of anode about 70% to about 85%, to make electrical efficiency maximize under voltage electricity being exported to desirable (namely high) and to maintain the heat balance in fuel cell.Under high fuel availability value, only the hydrogen (or synthesis gas) of appropriate amount is retained in anode exhaust for the formation of synthesis gas.Such as, under the fuel availability of about 75%, enter the fuel in anode about 25% can leave as the combination of synthesis gas and/or unreacted fuel.Enough hydrogen concentrations that the hydrogen of appropriate amount or synthesis gas can be enough to maintain anode are usually to promote anodic oxidation reactions and to provide enough fuel to heat reactant and/or entrance stream until suitable temperature of fuel cell operation.
Run different from this tradition, Solid Oxide Fuel Cell can be run with low fuel utilance and higher fuel flow rate, and less or there is no fuel from anode off-gas recirculation to anode inlet.The fuel simultaneously making to be recycled to anode inlet by running under low fuel utilance reduces or minimizes, and can obtain more substantial H in anode exhaust 2and/or CO.This excessive H 2can take out as syngas product and/or hydrogen gas product with CO.In every respect, the fuel availability in fuel cell can be at least about 5%, as at least about 10%, or at least about 15%, or at least about 20%.In addition or or, in low fuel utilance, fuel availability can be about 60% or lower, or about 50% or lower, or about 40% or lower.
The option improving the chemical efficiency of fuel cell improves the reformable hydrogen content being delivered to the fuel of fuel cell.Such as, the reformable hydrogen content being delivered to the reformable fuel in the input stream of anode and/or the reforming sections relevant to anode can than the net amount height at least about 50% of the hydrogen reacted at anode place, as height at least about 75%, or height at least about 100%.In addition or or, being sent to anode and/or being sent to the reformable hydrogen content of the fuel in the input stream of the reforming sections relevant to anode can than the net amount height at least about 50% of the hydrogen reacted at anode place, as height at least about 75% or high at least about 100%.In every respect, in fuel streams, the reformable hydrogen content of reformable fuel can be at least about 1.5:1 relative to the ratio of the amount of the hydrogen reacted in anode, or at least about 2.0:1, or at least about 2.5:1, or at least about 3.0:1.In addition or or, in fuel streams, the reformable hydrogen content of reformable fuel can for about 20:1 or less relative to the ratio of the amount of the hydrogen reacted in anode, as about 15:1 or less, or about 10:1 or less.On the one hand, estimate that being less than of the reformable hydrogen content in anode inlet stream 100% can change into hydrogen.Such as, at least about 80% of the reformable hydrogen content in anode inlet stream can change into hydrogen in the anode and/or in relevant reforming sections, as at least about 85%, or at least about 90%.
Hydrogen or synthesis gas can be used as chemical energy output and take out from anode exhaust.Hydrogen can be used as the clean fuel not generating greenhouse gas when burning.In addition, hydrogen can be the valuable charging for various refinery processes and/or other synthesis technique.Synthesis gas also can be for polytechnic valuable charging.Except having fuel value, synthesis gas also can be used as the raw material for the production of other more high-value product, such as, by using synthesis gas as the charging of F-T synthesis and/or methanol synthesizing process.
In every respect, anode exhaust can have the H of about 1.5:1 to about 10:1 2/ CO ratio, as at least about 3.0:1, or at least about 4.0:1, or at least about 5.0:1, and/or about 8.0:1 or less, or about 6.0:1 or less.Synthesis gas stream can be taken out from anode exhaust.In every respect, the synthesis gas stream taken out from anode exhaust can have at least approximately 0.9:1, as at least about 1.0:1, or at least approximately 1.2:1, or at least about 1.5:1, or at least about 1.7:1, or at least approximately 1.8:1, or the H of at least about 1.9:1 2/ CO mol ratio.In addition or or, the H in the synthesis gas taken out from anode exhaust 2/ CO mol ratio can be about 3.0:1 or less, as about 2.7:1 or less, or about 2.5:1 or less, or about 2.3:1 or less, or about 2.2:1 or less, or about 2.1:1 or less.But, permitted the H that the application of eurypalynous synthesis gas benefits to have at least approximately 1.5:1 to about 2.5:1 or less 2the synthesis gas of/CO mol ratio, so form H 2the mol ratio of/CO content is the synthesis gas stream of such as approximately 1.7:1 to about 2.3:1 may be desirable for some application.
Synthesis gas can be taken out from anode exhaust by any method easily.In certain aspects, can be vented by antianode the H carrying out being separated to remove in anode exhaust 2from anode exhaust, synthesis gas is taken out with being different from component at least partially of CO.Such as, anode exhaust can first be made through optional water gas shift stage to regulate H 2with the relative quantity of CO.Then one or more segregation section can be used from anode exhaust to remove H 2o and/or CO 2.Therefore the remainder of anode exhaust can be equivalent to synthesis gas stream, and it can take out for use subsequently in any convenient manner.In addition or or, the synthesis gas stream of taking-up can be made through one or more water gas shift stage and/or through one or more segregation section.
Point out, change the H in the synthesis gas taken out 2additional or the substituting mode of/CO mol ratio can be isolate H from anode exhaust and/or synthesis gas 2stream, such as, undertaken by implementing UF membrane.Form independent H 2export stream this separation can in office what carry out position easily, as made anode exhaust before or after water gas shift reaction section, and make anode exhaust be different from H to remove in anode exhaust through one or more segregation section 2before or after the component of CO.Optionally, H can be separated from anode exhaust 2all water gas shift stage is used before and after stream.Add at one or in substituting embodiment, optionally can be separated H from the synthesis gas stream taken out 2.In certain aspects, the H of separation 2stream can be equivalent to high-purity H 2stream, as the H containing at least about 90 volume % 2, as the H of at least about 95 volume % 2or the H of at least about 99 volume % 2h 2stream.
As fuel cell operation strategy described herein increase, supplement and/or substitute, the reformable operating fuel that Solid Oxide Fuel Cell (as fuel cell module) can be excessive relative to the amount of the hydrogen reacted in anode of fuel cell.Replace selecting the service conditions of fuel cell to improve or the electrical efficiency of maximize fuel cell, excessive reformable fuel can be sent into the anode of fuel cell to improve the chemical energy output of fuel cell.Optionally but preferably, this can cause improving based on the comprehensive electrical efficiency of fuel cell and the fuel cell gross efficiency of chemical efficiency.
In certain aspects, being sent to anode and/or being sent to the reformable hydrogen content of the reformable fuel in the input stream of the reforming sections relevant to anode can than the hydrogen amount height at least about 50% be oxidized in the anode, as height at least about 75% or high at least about 100%.In every respect, in fuel streams, the reformable hydrogen content of reformable fuel can be at least about 1.5:1 relative to the ratio of the amount of the hydrogen reacted in anode, or at least about 2.0:1, or at least about 2.5:1, or at least about 3.0:1.In addition or or, in fuel streams, the reformable hydrogen content of reformable fuel can for about 20:1 or lower relative to the ratio of the amount of the hydrogen reacted in anode, as about 15:1 or lower or about 10:1 or lower.On the one hand, estimate that being less than of the reformable hydrogen content in anode inlet stream 100% can change into hydrogen.Such as, at least about 80% of the reformable hydrogen content in anode inlet stream can change into hydrogen in the anode and/or in relevant reforming sections, as at least about 85%, or at least about 90%.
In addition or or, the amount being sent to the reformable fuel of anode can characterize based on the relative value of the low heat value of reformable fuel (LHV) with the LHV of the hydrogen to be oxidized in the anode.This can be referred to as reformable fuel excess rate.In this alternative, reformable fuel excess rate can be at least about 2.0, as at least about 2.5, or at least about 3.0, or at least about 4.0.In addition or or, reformable fuel excess rate can be about 25.0 or lower, as about 20.0 or lower, or about 15.0 or lower, or about 10.0 or lower.
In each side of the present invention, can based at least about 150mW/cm 2required total fuel cell manufacture rate (" TFCP ") and required reformable fuel excess rate characterize the operation of fuel cell.Such as, Solid Oxide Fuel Cell can be run to have at least approximately 150mW/cm 2the reformable fuel excess rate of TFCP and at least about 2.0, as at least about 2.5, or at least about 3.0, or at least about 4.0.In addition or or, TFCP can be about 150mW/cm 2above, reformable fuel excess rate can be about 25.0 or less, as about 20.0 or less, or about 15.0 or less, or about 10.0 or less.When fuel cell operation with have at least about 2.0 reformable fuel excess rate time, Solid Oxide Fuel Cell can be run to have at least approximately 150mW/cm 2tFCP, or at least about 200mW/cm 2, or at least about 250mW/cm 2, or at least about 300mW/cm 2, or at least about 350mW/cm 2.In this, TFCP can be about 800mW/cm 2or less, or about 700mW/cm 2or less, or about 600mW/cm 2or less, or about 500mW/cm 2or less, or about 400mW/cm 2or it is less.
In each side of the present invention, can based on about 75mW/cm 2or the operation of higher required total reformable fuel production rate and required reformable fuel excess rate sign fuel cell.In certain aspects, can fuel cell operation to have about 75mW/cm 2above required reformable fuel production rate and at least about 2.0, as at least about 2.5, or at least about 3.0, or the reformable fuel excess rate of at least about 4.0.In addition or or, total reformable fuel production rate can be about 75mW/cm 2above, reformable fuel excess rate can be about 25.0 or less, as about 20.0 or less, or about 15.0 or less, or about 10.0 or less.When fuel cell operation with have at least about 2.0 reformable fuel excess rate time, Solid Oxide Fuel Cell can be run to have at least approximately 75mW/cm 2reformable fuel production rate, or at least about 100mW/cm 2, or at least about 125mW/cm 2, or at least about 150mW/cm 2, or at least about 175mW/cm 2, or at least about 200mW/cm 2, or at least about 300mW/cm 2.In these areas, reformable fuel production rate can be about 600mW/cm 2or lower, or about 500mW/cm 2or lower, or about 400mW/cm 2or lower, or about 300mW/cm 2or lower, or about 200mW/cm 2or it is lower.
As the increase to fuel cell operation strategy described herein, supplement and/or substitute, can Solid Oxide Fuel Cell be run so that can relative to amount of oxidation selectoforming amount to realize thermal ratio needed for fuel cell." thermal ratio " used herein is defined as by the heat absorption demand of the heat of the exothermic reaction generation in fuel cell module divided by the reforming reaction occurred in fuel cell module.Express with mathematical way, thermal ratio (TH)=Q eX/ Q eN, wherein Q eXthe heat summation and Q that are generated by exothermic reaction eNit is the heat summation that the endothermic reaction occurred in fuel cell consumes.Point out, the heat generated by exothermic reaction is equivalent to any heat owing to the reforming reaction in this battery, water gas shift reaction and electrochemical reaction.The actual output voltage that can deduct fuel cell based on the desired electrochemical gesture striding across electrolytical fuel cell reaction calculates the heat generated by electrochemical reaction.Such as, based on the clean reaction occurred in the battery, the desired electrochemical gesture of the reaction thought in SOFC is about 1.04V.In the running of SOFC, due to various loss, this battery has the output voltage being less than 1.1V usually.Such as, common output/operating voltage can be about 0.65V, or about 0.7V, or about 0.75V, or about 0.8V.The electrochemical potential (such as, ~ 1.04V) that the heat generated equals this battery deducts operating voltage.Such as, when output voltage be ~ 0.7V time, by battery electrochemical reaction generate heat be ~ 0.34V.Therefore, in this case, the electricity of electrochemical reaction generation ~ 0.7V and the heat energy of ~ 0.34V.In such instances, the electric energy of ~ 0.7V is not as Q eXa part.In other words, heat energy is not electric energy.
In every respect, the operational factor of SOFC can be set to realize the operating voltage of at least below 0.7V, such as at least below 0.65V, or such as at least below 0.6V, or such as at least below 0.5V, or such as at least below 0.4V, or such as at least below 0.3V.
In every respect, can to any fuel cell structure easily, as the individual fuel cell in fuel cell pack, fuel cell pack, the fuel cell pack with integrated reforming sections, the fuel cell pack with integrated endothermic reaction section or its combine measured thermal ratio.Also can to the different units in fuel cell pack, as the Assembly calculation thermal ratio of fuel cell or fuel cell pack.Such as, thermal ratio can be calculated to the anode segment in the single anode in single fuel cell, the anode segment in fuel cell pack or the fuel cell pack together with integrated reforming sections and/or integrated endothermic reaction segment element (enough closely near wanting integrated anode segment viewed from hot integrated angle)." anode segment " used herein is included in multiple anodes of share common entrance in fuel cell pack 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 is to have required thermal ratio, then can run Solid Oxide Fuel Cell to have about 1.5 or lower, such as about 1.3 or 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 the thermal ratio of about 0.75 or lower.In addition or or, thermal ratio can be at least about 0.25, or at least about 0.35, or at least about 0.45, or at least about 0.50.
In each side of the present invention, can based on about 75mW/cm 2or the operation of higher required total reformable fuel production rate and required thermal ratio sign fuel cell.In certain aspects, can fuel cell operation to have about 75mW/cm 2above required reformable fuel production rate and about 1.5 or less, such as about 1.3 or less, or about 1.15 or less, or about 1.0 or less, or about 0.95 or less, or about 0.90 or less, or about 0.85 or less, or about 0.80 or less, or the thermal ratio of about 0.75 or less.In addition or or, total reformable fuel production rate can be about 75mW/cm 2above, thermal ratio can be at least about 0.25, or at least about 0.35, or at least about 0.45, or at least about 0.50.When fuel cell operation is to have the thermal ratio of about 0.25 to about 1.3, Solid Oxide Fuel Cell can be run to have at least approximately 75mW/cm 2, or at least about 100mW/cm 2, or at least about 125mW/cm 2, or at least about 150mW/cm 2, or at least about 175mW/cm 2, or at least about 200mW/cm 2, or at least about 300mW/cm 2reformable fuel production rate.In these areas, reformable fuel production rate can be about 600mW/cm 2or lower, or about 500mW/cm 2or lower, or about 400mW/cm 2or lower, or about 300mW/cm 2or lower, or about 200mW/cm 2or it is lower.
In each side of the present invention, can based on about 150mW/cm 2or the operation of higher required total fuel cell manufacture rate and required thermal ratio sign fuel cell.In one aspect, can fuel cell operation to have about 150mW/cm 2above required total fuel cell manufacture rate, with about 1.5 or less, such as about 1.3 or less, or about 1.15 or less, or about 1.0 or less, or about 0.95 or less, or about 0.90 or less, or about 0.85 or less, or about 0.80 or less, or the thermal ratio of about 0.75 or less.In addition or or, total fuel cell manufacture rate can be about 150mW/cm 2above, thermal ratio can be at least about 0.25, or at least about 0.35, or at least about 0.45, or at least about 0.50.When fuel cell operation is to have the thermal ratio of about 0.25 to about 1.3, Solid Oxide Fuel Cell can be run to have at least approximately 150mW/cm 2, or at least about 200mW/cm 2, or at least about 250mW/cm 2, or at least about 300mW/cm 2, or at least about 350mW/cm 2tFCP.In these areas, TFCP can be about 800mW/cm 2or lower, or about 700mW/cm 2or lower, or about 600mW/cm 2or lower, or about 500mW/cm 2or lower, or about 400mW/cm 2or it is lower.
In addition or or, in certain aspects, can fuel cell operation to have about 40 DEG C or less, as about 20 DEG C or less, or about 10 DEG C or less anode input and anode export between intensification.Again in addition or or, can fuel cell operation with the anode export temperature with lower than anode inlet temperature about 10 DEG C paramount about 10 DEG C.Again in addition or or, can fuel cell operation to have the anode inlet temperature higher than anode export temperature, as at least about in height 5 DEG C, or at least about 10 DEG C of height, or at least about 20 DEG C of height, or at least about 25 DEG C of height.Again in addition or or, can fuel cell operation higher than anode export temperature about 100 DEG C or lower to have, as about in height 80 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 the anode inlet temperature of about 10 DEG C or lower.Make the minimize variability between anode inlet temperature and outlet temperature can help to keep the mechanical integrity of ceramic component in Solid Oxide Fuel Cell.
As the increase to fuel cell operation strategy described herein, supplement and/or substitute, Solid Oxide Fuel Cell (as fuel cell module) can be run under the condition of power density that raising can be provided.The power density of fuel cell is equivalent to real work voltage V abe multiplied by current density I.For at voltage V athe Solid Oxide Fuel Cell of lower operation, this fuel cell also tends to generate used heat, used heat is defined as (V 0– V a) * I, it is based on V awith the desired voltage V of fuel cell providing current density I 0difference.The reformation of reformable fuel in the anode of fuel cell can consume a part of this used heat.This used heat of remainder can be absorbed by the fuel cell structure of surrounding and air-flow, causes the temperature difference across fuel cell.Under traditional service conditions, the power density of fuel cell can be restricted based on fuel cell permissible waste heat when not damaging fuel cell integrality.
In every respect, by carrying out the endothermic reaction of effective dose in fuel cell, the permissible waste heat of fuel cell can be improved.An example of the endothermic reaction comprises reformable fuel in anode of fuel cell and/or in relevant reforming sections, as the steam reformation in the integrated reforming sections in fuel cell pack.There is provided extra reformable fuel by the anode (or to integrated/relevant reforming sections) to fuel cell, can extra reformation be carried out extra used heat can be consumed.This can reduce the amount of the temperature difference across fuel cell, allows fuel cell to run under the service conditions of waste heat with raising thus.The loss of electrical efficiency is offset by producing the additional product stream that can be used for various uses (comprising extra generating), and described additional product stream is such as synthesis gas and/or H 2, to expand the power bracket of this system further.
In every respect, the waste heat that fuel cell generates, as defined above (V 0– V a) * I can be at least about 30mW/cm 2, as at least about 40mW/cm 2, or at least about 50mW/cm 2, or at least about 60mW/cm 2, or at least about 70mW/cm 2, or at least about 80mW/cm 2, or at least about 100mW/cm 2, or at least about 120mW/cm 2, or at least about 140mW/cm 2, or at least about 160mW/cm 2, or at least about 180mW/cm 2, or at least about 200mW/cm 2, or at least about 220mW/cm 2, or at least about 250mW/cm 2, or at least about 300mW/cm 2.In addition or or, fuel cell generate waste heat can be less than about 400mW/cm 2, as being less than about 300mW/cm 2, or be less than about 200mW/cm 2, or be less than about 175mW/cm 2, or be less than about 150mW/cm 2.
Although the waste heat generated may be relatively high, such used heat does not necessarily represent fuel cell and runs to differ from efficiency.On the contrary, can due to fuel cell operation and generate used heat under the power density improved.The part of power density improving fuel cell can be included in fuel cell operation under sufficiently high current density.In every respect, the current density that fuel cell generates can be at least about 150mA/cm 2, as at least about 160mA/cm 2, or at least about 170mA/cm 2, or at least about 180mA/cm 2, or at least about 190mA/cm 2, or at least about 200mA/cm 2, or at least about 300mA/cm 2, or at least about 400mA/cm 2, or at least about 800mA/cm 2.In addition or or, fuel cell generate current density can be about 800mA/cm 2or lower, as 450mA/cm 2or lower, or 300mA/cm 2or lower, or 250mA/cm 2or lower, or 200mA/cm 2or it is lower.
In every respect, in order to can improve generating and raising used heat generate under fuel cell operation, the endothermic reaction (as reforming reaction) of effective dose can be carried out.Or, use other endothermic reaction running with anode and have nothing to do to utilize used heat by arranging " plate " that with male or female thermal communication but not fluid is communicated with or section in fuel cell array.The endothermic reaction of effective dose can in relevant reforming sections, integrated reforming sections, carry out in the integrated Nuclear fuel of the endothermic reaction or its combination for carrying out.The endothermic reaction of effective dose can be equivalent to be enough to the intensification from fuel cell inlet to fuel exit is decreased to about 100 DEG C or lower, 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 amount.In addition or or, the endothermic reaction of effective dose can be equivalent to be enough to make the cooling from fuel cell inlet to fuel exit be about 100 DEG C or lower, 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 lower amount.When the endothermic reaction of effective dose exceedes the used heat of generation, the cooling from fuel cell inlet to fuel exit can be there is.In addition or or, this can be equivalent at least about 40% of the used heat that the endothermic reaction (as reformation and the combination of another endothermic reaction) consume fuel battery generates, as consumed the used heat of at least about 50%, or the used heat of at least about 60%, or the used heat of at least about 75%.Again in addition or or, the endothermic reaction can consume about 95% or less used heat, as about 90% or less used heat, or about 85% or less used heat.
additional definitions
Synthesis gas: in this manual, synthesis gas is defined as H 2with the mixture of any ratio of CO.Optionally, H 2o and/or CO 2can be present in synthesis gas.Optionally, inert compound (as nitrogen) and residual reformable fuel compound can be present in synthesis gas.If H 2be present in synthesis gas with the component beyond CO, H in synthesis gas 2with at least 25 volume % that the total volume percent of CO can be synthesis gas cumulative volume, as at least 40 volume %, or at least 50 volume %, or at least 60 volume %.In addition or or, H in synthesis gas 2can be 100 volume % or lower with the total volume percent of CO, as 95 volume % or lower or 90 volume % or lower.
Reformable fuel: reformable fuel is defined as containing reformable generation H 2the fuel of carbon-hydrogen link.Hydrocarbon is the example of reformable fuel, and other hydrocarbon matter compound, as alcohol is also.Although CO and H 2o can participate in water gas shift reaction to form hydrogen, and CO is not regarded as the reformable fuel under this definition.
Reformable hydrogen content: the reformable hydrogen content of fuel is defined as can then ordering about water gas shift reaction completely to make H by fuel by this fuel of reforming 2generate and maximize and the H of formation 2molecular number.Point out, H 2there is the reformable hydrogen content of 1, although H by definition 2itself be not defined as reformable fuel herein.Similarly, CO has the reformable hydrogen content of 1.Although CO is not reformable strictly, orders about water gas shift reaction and CO can be caused completely to be exchanged into H 2.As the example of the reformable hydrogen content of reformable fuel, the reformable hydrogen content of methane is 4 H 2molecule, and the reformable hydrogen content of ethane is 7 H 2molecule.More briefly, if fuel consist of CxHyOz, then this fuel 100% reform and Water gas shift/WGS under reformable hydrogen content be n (H 2maximum reformation)=2x+y/2 – z.Based on this definition, the fuel availability in battery can be expressed as n (H thereupon 2ox)/n (H 2maximum reformation).Certainly, can based on the reformable hydrogen content of the reformable hydrogen content determination component mixture of each component.Also can calculate in a similar manner containing other hetero-atom, as the reformable hydrogen content of oxygen, sulphur or nitrogen compound.
Oxidation reaction: in this discussion, the oxidation reaction in the anode of fuel cell be defined as be equivalent to by with O 2-reaction and by H 2oxidation forms H 2the reaction of O.Point out, do not comprise the reforming reaction in anode in this definition of oxidation reaction in the anode, the compound containing carbon-hydrogen link in reforming reaction is converted to H 2with CO or CO 2.Water gas shift reaction is similarly outside this definition of oxidation reaction.Point out further, combustion reaction mentioned that being defined is to H 2or containing the compound of carbon-hydrogen link at non-electrochemical burner, as in the combustion zone of burning energy supply generator with O 2reaction forms H 2mentioning of the reaction of O and oxycarbide.
The adjustable anode fuel parameter in aspect of the present invention is to realize range of operation needed for fuel cell.Anode fuel parameter can directly and/or with other fuel cell process relatively, characterize with the form of one or more ratios.Such as, anode fuel parameter can be controlled to realize one or more ratios, comprise fuel availability, fuel cell utilization rate of heat value, fuel excess rate, reformable fuel excess rate, reformable hydrogen content fuel ratio and combination thereof.
Fuel availability: fuel availability is the option run for characterizing anode, its fuel quantity based on the oxidation of the reformable hydrogen content relative to input stream can be used for the fuel availability determining fuel cell.In this discussion, " fuel availability " is defined as being the hydrogen amount (as mentioned above) be oxidized in the anode for generating inputs the reformable hydrogen content of (comprising any relevant reforming sections) ratio to anode.Reformable hydrogen content has been defined as above and can have then ordered about water gas shift reaction completely to make H by fuel by this fuel of reforming 2generate and maximize and the H of formation 2molecular number.Such as, anode is introduced and each methane under being exposed to steam reforming conditions causes generating 4H under maximum production 2molecular equivalency.(depend on reformation and/or anode condition, reformate can be equivalent to non-Water gas shift/WGS product, wherein one or more H 2molecule instead exists with the form of CO molecule).Therefore, methane is defined as 4 H 2the reformable hydrogen content of molecule.As another example, under this definition, ethane has 7 H 2the reformable hydrogen content of molecule.
Fuel availability in anode also can by based on the low heat value of hydrogen be oxidized in the anode due to anode of fuel cell reaction to be sent to anode and/or the ratio of the low heat value of all fuel of the reforming sections relevant with anode defines utilization rate of heat value to characterize.The flow velocity of the fuel element entering and leave anode of fuel cell and low heat value (LHV) can be used to calculate " fuel cell utilization rate of heat value " used herein.Therefore, fuel cell utilization rate of heat value can be used as, and (LHV (anode_in) – LHV (anode_out))/LHV (anode_in) calculates, and wherein LHV (anode_in) and LHV (anode_out) refers to that anode inlet and fuel element in outlet stream or stream are (as H respectively 2, CH 4and/or CO) LHV.In this definition, can be used as input and/or export the numerical value summation calculating stream of each fuel element in stream or the LHV of stream.The flow velocity (such as mol/hr) that the share of each fuel element in this summation can be equivalent to fuel element is multiplied by the LHV (such as joule/mole) of fuel element.
Low heat value: low heat value is defined as fuel element and burns into gas phase complete oxidation product (such as, gas phase CO 2and H 2o product) enthalpy.Such as, any CO existed in anode input stream 2do not form the fuel content of anode input, because CO 2complete oxidation.For this definition, the amount of oxidation occurred in the anode due to anode fuel cell reaction is defined as the H in the anode of a part for the electrochemical reaction in anode as defined above 2oxidation.
Pointing out, is H for the sole fuel in anode inlet flow 2special circumstances, the generable unique reaction relating to fuel element is H in the anode 2change into H 2o.In this special circumstances, fuel availability is simplified to (H 2-speed-enter-H 2-speed-go out)/H 2-speed-enter.In this case, H 2unique fuel element, therefore H 2lHV can cancellation from this equation.When more common, anode feed may contain the CH of such as various amount 4, H 2and CO.Because these thing classes can different amount be present in anode export usually, summation as mentioned above may be needed to measure fuel availability.
As substituting or supplementing fuel availability, the utilance of other reactant in fuel cell can be characterized.Such as, in addition or or, just " oxidant " utilance can characterize the operation of fuel cell.The value of oxidant utilization can be specified in a similar manner.
Fuel excess rate: the another way characterizing the reaction in Solid Oxide Fuel Cell is by defining utilance based on the low heat value of all fuel being sent to anode and/or the reforming sections relevant to anode with the ratio of the low heat value of the hydrogen be oxidized in the anode because anode of fuel cell reacts.This amount is referred to as fuel excess rate.Therefore, fuel excess rate can be used as, and (LHV (anode_in)/(LHV (anode_in)-LHV (anode_out)) calculates, and wherein LHV (anode_in) and LHV (anode_out) refers to that anode inlet and fuel element in outlet stream or stream are (as H respectively 2, CH 4and/or CO) LHV.In aspects of the present invention, Solid Oxide Fuel Cell can be run to have at least about 1.0, 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 the fuel excess rate of at least about 4.0.In addition or or, fuel excess rate can be about 25.0 or lower.
Point out, all reformable fuel not in anode input stream all can be reformed.Preferably, enter in the input stream of anode (and/or entering relevant reforming sections) at least about 90% reformable fuel reformable before leaving anode, as at least about 95% or at least about 98%.In in other, the reformation amount of reformable fuel can be about 75% to about 90%, as at least about 80%.
The above-mentioned definition of fuel excess rate is provided to a kind of method of the amount being characterized in the reformation occurred in anode and/or the reforming sections relevant to fuel cell relative to the consumed fuel quantity that generates electricity in anode of fuel cell.
Optionally, fuel excess rate can be changed and export to take into account fuel the situation being recycled to anode input from anode.When fuel is (as H 2, CO and/or do not reform or the hydrocarbon of partial conversion) from anode export be recycled to anode input time, the fuel that such recycled fuel component does not represent the reformable of the excess quantity that can be used for other purposes or reforms.On the contrary, such recycled fuel component only indicates the demand of the fuel availability reduced in fuel cell.
Reformable fuel excess rate: calculating reformable fuel excess rate is the option taking into account such recycled fuel component, the definition of excess fuel of its constriction, only to comprise the LHV of reformable fuel in anode input stream." reformable fuel excess rate " used herein is defined as the low heat value of the reformable fuel being sent to anode and/or the reforming sections relevant to anode and the relative value of the low heat value of the hydrogen be oxidized in the anode because anode of fuel cell reacts.Under the definition of reformable fuel excess rate, do not comprise any H in anode feed 2or the LHV of CO.This LHV of reformable fuel still measures by characterizing the actual composition entering anode of fuel cell, does not therefore need to distinguish recyclable component and fresh components.Although some are not reformed or partial conversion fuel also can recirculation, the most of fuel being recycled to anode in most of can be equivalent to reformate, as H 2or CO.Express with mathematical way, reformable fuel excess rate (R rFS)=LHV rF/ LHV oH, wherein LHV rFbe the low heat value (LHV) of reformable fuel and LHV oHit is the low heat value (LHV) of the hydrogen be oxidized in the anode.LHV (such as, LHV (anode_in)-LHV (anode_out)) by deducting anode export stream in the LHV from anode inlet stream calculates the LHV of the hydrogen be oxidized in the anode.In aspects of the present invention, Solid Oxide Fuel Cell can be run to have at least about 0.25, 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 the reformable fuel excess rate of at least about 4.0.In addition or or, reformable fuel excess rate can be about 25.0 or lower.Point out, the fuel cell operation method of two types with low fuel utilance can be distinguished based on this narrower definition being sent to the reformable fuel quantity of anode relative to the amount of oxidation in anode.Some fuel cells realize low fuel utilance by the anode output recirculation of quite a few being returned anode input.Any hydrogen during this recirculation can make anode input is used as the input of anode again.This can reduce reformation amount, even if because low through the fuel availability of fuel cell in one way, fuel non-at least partially also recirculation is used for flow process after a while.Therefore, the fuel cell with diversified fuel utilization value can have the ratio of the identical reformable fuel being sent to anode reforming sections and the hydrogen be oxidized in anode reaction.In order to change be sent to anode reforming sections reformable fuel and anode in the ratio of amount of oxidation, need to identify there is original content can not the anode feed of fuel reforming, or need to take out anode export in do not use fuel for other purposes, or both.
Reformable hydrogen excess rate: for characterizing another option of fuel cell operation based on " reformable hydrogen excess rate ".Reformable fuel excess rate defined above defines based on the low heat value of reformable fuel element.Reformable hydrogen excess rate is defined as the reformable hydrogen content of the reformable fuel being sent to anode and/or the reforming sections relevant to anode and the ratio of the hydrogen reacted in the anode because anode of fuel cell reacts.Therefore, " reformable hydrogen excess rate " can be used as, and (RFC (reformable_anode_in)/(RFC (reformable_anode_in)-RFC (anode_out)) calculates, wherein RFC (reformable_anode_in) refers to the reformable hydrogen content of the reformable fuel in anode inlet stream or stream, and RFC (anode_out) refers to that anode inlet and outlet stream or the fuel element in flowing are (as H 2, CH 4and/or CO) reformable hydrogen content.RFC can with mole/second, mol/hr or similar unit representation.Under the large ratio of the amount of oxidation in the reformable fuel being sent to anode reforming sections and anode, an example of the method for fuel cell operation can be carry out the method that excess reformer occurs with the heat in balancing fuel cell and consume.Reformable fuel reforming is formed H 2an endothermic process with CO.This endothermic reaction of antagonism is generated by the electric current in fuel cell, described electric current generates also can produce excessive heat, and its (roughly) corresponds to the difference of the heat generated by anodic oxidation reactions and cathode reaction and the energy leaving fuel cell as an electrical current.The excessive heat of the every moles of hydrogen related in anodic oxidation reactions/cathode reaction can be greater than the heat absorbed by reformation generation 1 moles of hydrogen.Therefore, the fuel cell run under conventional conditions can show intensification from the inlet to the outlet.Replace such tradition to run, the fuel quantity reformed in the reforming sections relevant to anode can be improved.Such as, extra fuel can be reformed so that heat (roughly) the balance exothermic fuel cell by consuming in reformation reacts the heat generated, or the heat of consumption of reforming even can exceed the excessive heat of oxidized generation, so that the temperature striding across fuel cell declines.This can cause generating with electric power needed for amount compared with hydrogen significantly excessive.As an example, the charging sending into the anode inlet of fuel cell or relevant reforming sections can substantially by reformable fuel, as substantially pure methane feed formation.In the traditional running using this fuel power generation function, Solid Oxide Fuel Cell can be run with the fuel availability of about 75%.This means that about 75% (or 3/4) of the fuel content being sent to anode is for the formation of hydrogen, it reacts with oxonium ion in the anode subsequently and forms H 2o.In conventional operation, the fuel content remaining about 25% can be reformatted into H in fuel cell 2(or can for any CO or H in fuel 2pass fuel cell unreacted), then burn outward to form H at fuel cell 2o is with the cathode inlet heat supply to fuel cell.Reformable hydrogen excess rate can be 4/ (4-1)=4/3 in this case.
Electrical efficiency: term used herein " electrical efficiency " (" EE ") is defined as the speed of the low heat value (" LHV ") that the electrochemical kinetics that produced by fuel cell inputs divided by the fuel of fuel cell.The fuel input of fuel cell comprises the fuel that is sent to anode and for keeping any fuel of the temperature of fuel cell, as being sent to the fuel of the burner relevant to fuel cell.In this manual, the power produced by this fuel can describe with LHV (el) fuel rate (fuelrate).
Electrochemical kinetics: term used herein " electrochemical kinetics " or LHV (el) are circuit by connecting negative electrode and positive electrode in fuel cell and oxonium ion through the transfer of fuel-cell electrolyte and the power generated.The power that the equipment that electrochemical kinetics does not comprise fuel cell upstream or downstream produces or consumes.Such as, a part for electrochemical kinetics is not regarded as by the thermogenetic electricity in fuel cell exhaust stream.Similarly, the power generated by gas turbine or the miscellaneous equipment of fuel cell upstream is not a part for the electrochemical kinetics generated." electrochemical kinetics " does not consider the electric power consumed in fuel cell operation or any loss becoming alternating current to cause by DC conversion.In other words, from the direct current power that fuel cell produces, do not deduct the electric power for supplying fuel cell operation or otherwise fuel cell operation.Power density used herein is that current density is multiplied by voltage.Total fuel battery power used herein is that power density is multiplied by fuel cell area.
Fuel inputs: term used herein " anode fuel input ", being referred to as LHV (anode_in), is the fuel quantity in anode inlet stream.Term " fuel input ", being referred to as LHV (in), is the total amount of fuel being sent to fuel cell, comprises fuel quantity in anode inlet stream and for keeping the fuel quantity of the temperature of fuel cell.Based on the definition of reformable fuel provided herein, this fuel can comprise reformable and not reformable fuel.Fuel input is different from fuel availability.
Total fuel cell efficiency: term used herein " total fuel cell efficiency " (" TFCE ") is defined as: the electrochemical kinetics generated by fuel cell adds the speed (rateofLHV) of the LHV of the synthesis gas generated by fuel cell, the speed of the LHV that the fuel divided by anode inputs.In other words, TFCE=(LHV (el)+LHV (sgnet))/LHV (anode_in), wherein LHV (anode_in) refers to that the fuel element being sent to anode is (as H 2, CH 4and/or CO) the speed of LHV, and LHV (sgnet) refers to and produces synthesis gas (H in the anode 2, CO) speed, it is the difference that the synthesis gas input of anode exports with the synthesis gas of anode.The electrochemical kinetics that LHV (el) describes fuel cell generates.Total fuel cell efficiency does not comprise the heat for the useful utilization outside this fuel cell generated by this fuel cell.Be in operation, the heat generated by fuel cell may by the useful utilization of upstream device.Such as, this heat can be used for generating extra electric power or for heating water.When using this term in this application, these purposes implemented outward at fuel cell are not parts for total fuel cell efficiency.Total fuel cell efficiency is only for fuel cell operation, and the power not comprising fuel cell upstream or downstream generates or consumes.
Chemical efficiency: term used herein " chemical efficiency " is defined as the H in the anode exhaust of fuel cell 2with the low heat value of CO or LHV (sgout) divided by fuel input or LHV (in).
Electrical efficiency and overall system efficiency do not consider the efficiency of upstream or downstream process.Such as, can advantageously use gas turbine exhaust as the O of fuel battery negative pole 2source.In this arrangement, the efficiency of turbine is not regarded as a part for electrical efficiency or total fuel cell efficiency calculating.Similarly, can be used as input from the output of fuel cell and be recycled to fuel cell.Recirculation circuit is not considered when calculating electrical efficiency or total fuel cell efficiency with single pass mode.
The synthesis gas generated: term used herein " synthesis gas of generation " is the difference that the synthesis gas input of anode exports with the synthesis gas of anode.Synthesis gas can be used as input or the fuel of anode at least partly.Such as, system can comprise anode recirculation loop, and it sends the synthesis gas from anode exhaust back to anode inlet, at this to its supplemental natural gas or other suitable fuel.Synthesis gas LHV (sgnet)=(LHV (the sgout)-LHV (sgin)) generated, wherein LHV (sgin) and LHV (sgout) refers to the LHV of synthesis gas in anode inlet and anode export stream or the synthesis gas in flowing respectively.Point out, the synthesis gas at least partially generated by the reforming reaction in anode usually can in the anode for generating.For the hydrogen that generates electricity not included in the definition of " synthesis gas of generation ", because it does not leave anode.Term used herein " syngas ratio " is LHV or LHV (sgnet)/LHV (anodein) that the LHV of the clean synthesis gas generated inputs divided by the fuel of anode.Mole flow velocity of synthesis gas and fuel can be used to replace LHV to represent the synthesis gas of the generation of mole base syngas ratio and mole base.
Vapor carbon ratio (S/C): vapor carbon ratio used herein (S/C) is the mol ratio of the steam in stream and the reformable carbon in stream.CO and CO 2the carbon of form does not count the reformable carbon in this definition.Can measure and/or control vapor carbon ratio by difference within the system.Such as, the composition of anode inlet stream can be controlled to realize the S/C of the reformation in applicable anode.S/C can as H 2mole flow velocity of O provides divided by (mole flow velocity of fuel is multiplied by the product of the carbon number (such as methane is 1) in fuel).Therefore, S/C=f h20/ (f cH4x#C), wherein f h20mole flow velocity of water, wherein f cH4be mole flow velocity of methane (or other fuel) and #C is the carbon number in fuel.In every respect, S/C can be about 2, or about 1-3, or about 0.5-5.May it is desirable to provide only enough steam to meet reforming reaction stoichiometry and to prevent fouling, because excess steam dilution anode reactant and produce consumed energy.
Fuel cell and fuel cell component: in this discussion, fuel cell can be equivalent to monocell, and its Anodic and negative electrode are separated by an electrolyte.Solid Oxide Fuel Cell takes flat type or form of tubes.As used herein, fuel cell can refer to wherein a kind of form or two kinds of forms.Anode and negative electrode can receive input air-flow to promote respective anode and cathode reaction, transferring charge crossed electrolyte and to generate electricity.Fuel cell pack can represent the multiple batteries in integrated unit.Although fuel cell pack can comprise multiple fuel cell, fuel cell usually can be in parallel and can (roughly) show represent the larger single fuel cell of size as their collectives.When carrying inlet flow to the male or female of fuel cell pack, this fuel assembly can comprise for distributing the flow channel of inlet flow and the flow channel for merging the output stream from each battery between each battery in this heap.In this discussion, fuel cell array can be used for representing series, parallel or (combination of such as series and parallel connections) multiple fuel cells (as multiple fuel cell pack) of arranging in any other convenient way.Fuel cell array can comprise one or more sections of fuel cell and/or fuel cell pack, and the anode/cathode wherein from first paragraph exports the anode/cathode input can serving as second segment.Point out, the anode in fuel cell array need not connect in the mode identical with the negative electrode in this array.For simplicity, the input of the first anode section of fuel cell array can be referred to as the anode input of this array, and the input of the first negative electrode section of fuel cell array can be referred to as the negative electrode input of this array.Similarly, the output of final anode/cathode section can be referred to as the anode/cathode output of this array.
It should be understood that to mention in this article uses fuel cell to typically refer to " fuel cell pack " that be made up of multiple single fuel cell, more generally refers to the one or more fuel cell packs using fluid to be communicated with.Usually by independent fuel cell component (plate or cylinder) together with rectangular array " stacking ", can be referred to as " fuel cell pack ".This fuel cell pack can obtain incoming flow and usually by reactant distribution between all independent fuel cell components, then can from each component collection product.When being regarded as a unit, fuel cell pack is in operation and can be taken as entirety, although be made up of many (usually tens of or hundreds of) independent fuel cell component.These independent fuel cell components can have similar voltage (because reactant similar to production concentration) usually, and when these elements electricity series connection, total electricity exports can from the summation of all electric currents in all cell devices.Battery pile also can arranged in series to produce high voltage.Being arranged in parallel can motor current.If the fuel cell pack of enough large volumes can be provided to process given stream, system and method described herein can use together with single solid-oxide fuel cell stack.Of the present invention in other in, because many reasons may desirable or it is desirable that multiple fuel cell pack.
For the purpose of the present invention, unless specifically stated so, term " fuel cell " should be understood to also refer to and/or be defined as to comprise the fuel cell pack be made up of the combination of one or more independent fuel cell component relating to and have single input and output, because this is fuel cell usual occupation mode in practice.Similarly, unless specifically stated so, term fuel cell (plural number) should be understood to also refer to and/or be defined as to comprise multiple independently fuel cell pack.In other words, unless stated otherwise, all the mentioning in this paper refers to that fuel cell pack runs as " fuel cell " interchangeably.Such as, the exhaust volume that commercial-scale burning generators generates may consequently cannot be processed by the fuel cell of stock size (such as, cell stack) too greatly.In order to process whole exhaust, multiple fuel cell (i.e. two or more independently fuel cell or fuel cell pack) can be arranged in parallel, with the burning and gas-exhausting making each fuel cell can process (roughly) moiety.Although can use multiple fuel cell, consider the burning and gas-exhausting of its (roughly) moiety, each fuel cell can run usually in a substantially similar manner.
" inside reforming " and " outside reformation ": fuel cell or fuel cell pack can comprise one or more inside reforming section.Term used herein " inside reforming " refers in the main body of fuel cell, fuel cell pack or the fuel reforming otherwise occurred in fuel cell module.Usually and the outside of fuel cell conbined usage reform and to carry out being arranged in the autonomous device part outside fuel cell pack.In other words, the main body of external reformer does not contact with the main body direct physical of fuel cell or fuel cell pack.In typical layout, the output from external reformer can be sent into the anode inlet of fuel cell.Except non-specifically illustrates separately, the reformation described in the application is inside reforming.
Inside reforming can carry out in anode of fuel cell.In addition or or, inside reforming can carry out being integrated in the inside reforming element in fuel cell module.Integrated reforming element can between the fuel cell component in fuel cell pack.In other words, one of plate in battery pile can be reforming sections but not fuel cell component.On the one hand, fuel leads inside reforming element by the flow arrangement in fuel cell pack, then imports the anode part of fuel cell.Therefore, from flowing angle, inside reforming element and fuel cell component can be disposed in series in fuel cell pack.Term used herein " anode reformation " is the fuel reforming occurred in anode.Term used herein " inside reforming " is the reformation occurred in integrated reforming element but not in anode segment.
In certain aspects, the reforming sections in fuel cell module can be considered to relevant to the anode in fuel cell module.In in other, for can reforming sections in the fuel cell pack of relevant to anode (as being correlated with multiple anode), the flow path output stream from reforming sections being sent at least one anode can be provided.This can be equivalent to have fuel cell plate initial segment, and this Duan Buyu electrolyte contacts but only serves as reforming catalyst.Another option of relevant reforming sections can be have independent integrated reforming sections as one of element in fuel cell pack, wherein the output from integrated reforming sections is sent back to the input side of the one or more fuel cells in fuel cell pack.
From hot integrated angle, the feature height in fuel cell pack can be the height of independent fuel cell Nuclear fuel.Point out, independently reforming sections or independently endothermic reaction section can have the height different from fuel cell in this heap.In this case, the height of fuel cell component can be used as feature height.In certain aspects, integrated endothermic reaction section can be defined as the section integrated with one or more fuel cell heat, can utilize the thermal source of hotwork for reforming from fuel cell with the endothermic reaction section making this integrated.This integrated endothermic reaction section can be defined as being less than with any fuel cell to this integrated section of heat supply 5 times of a Nuclear fuel height apart and locate.Such as, any fuel cell that integrated endothermic reaction section (as reforming sections) can be integrated with heat is less than 5 times of a Nuclear fuel height apart, as being less than 3 times of places of a Nuclear fuel height.In this discussion, the integrated reforming sections or the integrated endothermic reaction section that represent the adjacent Nuclear fuel of fuel cell component can be defined as with adjacent fuel cell element at a distance of an about Nuclear fuel height or less.
In certain aspects, integrated to fuel cell component heat independent reforming sections also can be equivalent to the reforming sections relevant with fuel cell component.In in such, integrated fuel cell component can provide heat at least partially to relevant reforming sections, and reforming sections at least partially can export and is supplied to integrated fuel cell as fuel streams by relevant reforming sections.In in other, independent reforming sections can be integrated to conduct heat with fuel cell, but not relevant to fuel cell.In such situation, this independent reforming sections can receive heat from fuel cell, but the output of reforming sections is not used as the input of fuel cell.On the contrary, the output of this reforming sections can be used for another purposes, as this output directly added in anode exhaust stream or the independent output stream formed from fuel cell module.
More generally, the independent Nuclear fuel in fuel cell pack can be used to carry out any endothermic reaction facilitating type of the used heat that integrated fuel cell Nuclear fuel can be utilized to provide.Replace being applicable to plate hydrocarbon fuel stream being carried out to reforming reaction, independent Nuclear fuel can have the plate of the endothermic reaction being applicable to catalysis another type.Other layout of manifold or entry conductor can be used in a fuel cell stack to provide suitable inlet flow to each Nuclear fuel.Other layout of similar manifold or delivery channel also can be used for taking out output stream from each Nuclear fuel.Optionally, the output stream of the endothermic reaction section in heap can be taken out from fuel cell pack and not make this output stream through anode of fuel cell.So optional in, the product of exothermic reaction is therefore when leaving fuel cell pack without when anode of fuel cell.The example of the endothermic reaction of other type can carried out in Nuclear fuel in a fuel cell stack comprises ethanol dehydration and forms ethene, and ethane cracking.
Recirculation: as defined herein, a part of fuel cell exports, and (as anode exhaust or the stream that is separated from anode exhaust or takes out) is recycled to fuel cell inlet, and this can be equivalent to direct or indirect recycle stream.Stream is directly recycled to the stream recirculation that fuel cell inlet is defined as without pilot process, and indirect recycling relates to and makes the recirculation of stream after one or more pilot process.Such as, if anode exhaust is before being recycled through CO 2segregation section, this is regarded as the indirect recycling of anode exhaust.If by a part for anode exhaust, as the H taken out from anode exhaust 2stream is sent into and is used for coal being changed into the gasifier being applicable to the fuel introducing fuel cell, and this is also regarded as indirect recycling.
anode input and output
In aspects of the present invention, can feed to SOFC array the fuel received in anode inlet, it comprises such as hydrogen and hydrocarbon, as methane (or, may containing heteroatomic hydrocarbon matter or the class hydrocarbon compound being different from C and H).The most of methane (or other hydrocarbon matter or class hydrocarbon compound) sending into anode can be fresh methane usually.In this manual, fresh fuel is not the fuel come from another fuel cell process recirculation as fresh methane refers to.Such as, the methane being recycled to anode inlet from anode export stream can not be regarded as " fresh " methane, but can be described to regenerate methane.Fuel used source can be shared with other parts, as turbine.The input of this fuels sources can comprise the water proportional with this fuel, and described ratio is suitable for reforming hydrocarbon in reforming sections (or class hydrocarbon) compound and generates hydrogen.Such as, if methane is for reforming to generate H 2fuel input, water can be about 1 to 1 to about 10 to 1 with the mol ratio of fuel, as at least about 2 to 1.It is typical that the ratio of 4 to 1 or higher is reformed to outside, but lower value may be typical to inside reforming.At H 2in degree as a part for fuels sources, in some are optional, extra water may not be needed in fuel, because the H at anode place 2oxidation can be tended to produce and to be can be used for reforming the H of this fuel 2o.Fuels sources also optionally can contain the subsidiary component of this fuels sources, and (such as, natural gas feed can contain the CO of certain content 2as annexing ingredient).Such as, natural gas feed can contain CO 2, N 2and/or other inertia (rare) gas is as annexing ingredient.Optionally, in certain aspects, this fuels sources also can contain CO, as the CO of the recycle sections from anode exhaust.Entering the additional of the CO in the fuel of fuel cell module or may originating of substituting can be the CO generated by the hydrocarbon fuel steam reformation carried out fuel before entering fuel cell module.
More generally, various types of fuel streams can be suitable as the input stream of the anode of Solid Oxide Fuel Cell.Some fuel streams can be equivalent to containing hydrocarbon and/or the stream that also can comprise the heteroatomic class hydrocarbon compound being different from C and H.In this discussion, unless specifically stated so, the mentioning of hydrocarbon containing fuels stream for SOFC anode is defined as comprising the fuel streams containing such class hydrocarbon compound.The example of hydrocarbon (comprising class hydrocarbon) fuel streams comprises natural gas, containing the stream of C1-C4 carbon compound (as methane or ethane) and the stream containing heavier C5+ hydrocarbon (comprising class hydrocarbon compound) and their combination.Other examples that are additional or that substitute for the possible fuel streams in anode input can comprise the stream of biogas type, as decomposed by natural (biology) of organic material the methane produced.
In certain aspects, Solid Oxide Fuel Cell can be used for processing the input fuel streams owing to there is diluent compound with low energy content, as natural gas and/or hydrocarbon stream.Such as, some sources of methane and/or natural gas are the CO that can comprise significant quantity 2or other inert molecule, as the source of nitrogen, argon or helium.Owing to there is the CO of increasing amount 2and/or inert material, the energy content of the fuel streams based on this source can be reduced.The fuel of low energy content is used for combustion reaction (as the turbine energy supply for energy supply of burning) and can causes difficulty.But Solid Oxide Fuel Cell can generate electricity based on the fuels sources of low energy content and have reduction or minimum impact to the efficiency of fuel cell.The existence of additional gas volume can need the heat of adding to be risen to by fuel temperature for reforming and/or the temperature of anode reaction.In addition, due to the equilibrium property of the water gas shift reaction in anode of fuel cell, additional CO 2existence can affect anode export in exist H 2with the relative quantity of CO.But in addition, inert compound only can have minimum direct impact to reformation and anode reaction.CO in the fuel streams of Solid Oxide Fuel Cell 2and/or the amount of inert compound (when it is present) can be at least about 1 volume %, as at least about 2 volume %, or at least 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 %.In addition or or, CO in the fuel streams of Solid Oxide Fuel Cell 2and/or the amount of inert compound can be about 90 volume % or lower, as about 75 volume % or 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 that may originate of anode input stream can be equivalent to the output stream of oil refining and/or other industrial technology.Such as, coking is for heavy compounds being changed into the common technology of lower boiling range in many oil plants.Coking produces usually containing being at room temperature the multiple compounds of gas, comprises the waste gas of CO and various C1-C4 hydrocarbon.This waste gas can be used as anode input stream at least partially.In addition or or, other refinery flares streams can be applicable to being included in anode input stream, as the light fraction (C1-C4) generated in cracking or other refinery processes process.In addition or or, other suitable oil plant streams can comprise containing CO or CO 2oil plant stream, it is also containing H 2and/or reformable fuel compound.
In addition or or, other possible sources of anode input can comprise the stream of the water content with raising.Such as, export from the ethanol of ethanol factory (or zymotechnique of another type) H that stream can comprise quite a few before final distillation 2o.Such H 2o can only cause minimum impact to the operation of fuel cell usually.Therefore, the fermenting mixture of alcohol (or other tunning) and water can be used as anode input stream at least partially.
Biogas or biogas are another additional or substitute may originating of anode input.Biogas may mainly comprise methane and CO 2and usually produced by organic decomposition or digestion.Anaerobic bacteria can be used for digestion of organic matter and produces biogas.Impurity can be removed from biogas, as sulfur-containing compound before being used as anode input.
Output stream from SOFC anode can comprise H 2o, CO 2, CO and H 2.Optionally, this anode exports stream and also can have unreacted fuel in charging (as H 2or CH 4) or inert compound as additional output component.Replacing using this output stream as the fuels sources to reforming reaction heat supply or as being used for the combustion fuel of heating battery, stream can be exported carry out one or many separation with by CO by antianode 2with the component with the potential value inputted as another technique, as H 2or CO is separated.H 2and/or CO can be used as chemical synthesis synthesis gas, be used as chemical reaction hydrogen source and/or as the fuel of greenhouse gas emission with reduction.
In every respect, the composition of the output stream of anode can affect by some questions.The factor that can affect anode output composition can comprise the temperature of the composition of the input stream of anode, the magnitude of current generated by fuel cell and/or anode export.Due to the equilibrium property of water gas shift reaction, the temperature of anode export can be related.In typical anode, at least one plate forming anode wall is applicable to catalytic water shift conversion reaction.Therefore, if a) composition of anode input stream is known, the reformation degree of the reformable fuel b) in anode input stream is known, with the amount of oxonium ion c) from cathode transport to anode (corresponding to the magnitude of current generated) is known, then the composition that can export based on the equilibrium constant determination anode of water gas shift reaction.
K eq＝[CO 2][H 2]/[CO][H 2O]
In above-mentioned equation, K eqbe the equilibrium constant of this reaction under given temperature and pressure, and [X] is the dividing potential drop of component X.Based on water gas shift reaction, can point out, the CO improved in anode input 2concentration can be tended to cause extra CO to be formed (with H 2for cost), and the H improved 2o concentration can be tended to cause extra H 2formed (taking CO as cost).
In order to measure the composition that anode exports, composition that anode inputs can be used as starting point.Then this composition can be changed to be reflected in the reformation degree of contingent any reformable fuel in anode.This reformation can reduce the hydrocarbon content of anode input, is transformed into hydrogen and the CO of increase 2.Then, based on the magnitude of current generated, the H in anode input can be reduced 2amount, is transformed into extra H 2o and CO 2.Then this composition can be regulated to measure H based on the equilibrium constant of water gas shift reaction 2, CO, CO 2and H 2the exit concentration of O.
In every respect, the operating temperature of SOFC can be selected to realize H in synthesis gas output 2, CO and CO 2required ratio.Operating temperature can be selected to export to produce the synthesis gas with the ratio being applicable to expection method.On the one hand, operating temperature can be about 700 DEG C to about 1200 DEG C, and such as operating temperature can be about 800 DEG C, about 900 DEG C, about 1000 DEG C or about 1100 DEG C.
Optionally, if need, can anode export after comprise one or more water gas shift reaction section with by anode export in CO and H 2o changes into CO 2and H 2.Can such as by a lower temperature use water-gas shift will anode export in exist H 2o and CO changes into H 2and CO 2improve during anode exports the H existed 2amount.Because SOFC can run at about 700 DEG C to about 1200 DEG C, may be promote water gas shift reaction when cooling anodes exports for during technique subsequently so desirable especially.Or, temperature can water gas shift reaction be reversed can be improved, with by H 2and CO 2produce more CO and H 2o.Water is that the expection of the reaction occurred at anode place exports, therefore this anode export usually can have export with anode in the CO that exists measure compared with excessive H 2o.Or, can after anode export but by H before water gas shift reaction 2o adds in stream.Due to the incomplete carbon in reforming process transform and/or due to the condition of reorganization or in anode reaction process H under existent condition 2o, CO, H 2and CO 2between balanced reaction (i.e. water gas shift equilibrium), anode export in can there is CO.Water-gas shift can with CO and H 2o is that cost is further towards formation CO 2and H 2direction drive the condition of this balance under run.Higher temperature is often conducive to forming CO and H 2o.Therefore, running an option of water-gas shift can be in suitable temperature, such as, makes anode output stream be exposed to suitable catalyst at about 190 DEG C to about 210 DEG C, as comprise iron oxide, zinc oxide, copper/zinc oxide etc. catalyst under.This water-gas shift optionally can comprise two sections exporting the CO concentration in stream for reducing anode, wherein the first higher temperatures section is run at the temperature of at least about 300 DEG C to about 375 DEG C, second comparatively low-temperature zone at about 225 DEG C or lower, as run at the temperature of about 180 DEG C to about 210 DEG C.Except improving during anode exports the H existed 2outside amount, in addition or or, water gas shift reaction can be that cost improves CO with CO 2amount.The carbon monoxide (CO) that difficulty removes can be transformed into carbon dioxide by this, and carbon dioxide passes more readily condensation (such as deep cooling removes), chemical reaction (as amine removal) and/or other CO 2removal method removes.In addition or or, may desirably improve in anode exhaust the CO content that exists to realize required H 2/ CO ratio.
After optional water gas shift reaction section, anode can be made to export through one or more segregation section to export in stream except anhydrating and/or CO from anode 2.Such as, by independence or combinationally use one or more method antianodes export carry out CO 2be separated and form one or more CO 2export stream.These methods can be used for generation and have 90 volume % or higher, as at least 95% volume %CO 2or at least 98 volume %CO 2cO 2the CO of content 2export stream.The CO that the recyclable anode of these methods exports 2about at least 70% of content, as the CO that anode exports 2at least about 80% of content, or at least about 90%.Or, in certain aspects may desirably reclaim the only a part of CO in anode output stream 2, the CO of recovery 2part is the CO in anode output 2about 33% to about 90%, as at least about 40%, or at least about 50%.Such as, may desirably make some CO 2stay in anode output stream so that required composition can be realized in water gas shift stage subsequently.Suitable separation method can comprise use physical solvent (such as, Selexol tMor Rectisol tM); Amine or other alkali (such as, MEA or MDEA); Refrigeration (such as, cryogenic separation); Pressure-variable adsorption; Vacuum Pressure Swing Adsorption; With their combination.Deep cooling CO 2separator can be an example of suitable separator.Export cooling along with by anode, the most of water during anode exports can be used as condensation (liquid) and is separated out.Further cooling and/or the pressurization of poor-water anode output stream can be separated high-purity CO subsequently 2, because other remaining ingredient in anode output stream is (as H 2, N 2, CH 4) be not easy to form condensation phase.Depend on service conditions, deep cooling CO 2the CO existed in the recyclable stream of separator 2about 33% to about 90%.
It is also useful for dewatering to form one or more water output stream material from anode exhaust, and no matter this is carrying out CO 2before separation, among or after.The water yield during anode exports can become with selected service conditions.Such as, the vapour/carbon ratio set up in anode inlet can affect water content in anode exhaust, and high vapour/carbon ratio causes a large amount of water usually, its can unreacted ground by anode and/or only react due to the water gas shift equilibrium in anode.According to this aspect, the water content in anode exhaust can be equivalent to nearly about 30% or larger of volume in anode exhaust.In addition or or, water content can be about 80% or less of anode exhaust volume.Although by compression and/or cooling and thereupon condensation remove such water, the removing of this water can need extra compressor horsepower and/or a large amount of cooling water of heat exchange surface sum.A kind of beneficial manner removing a part of this excessive water can based on use adsorbent bed, and it can catch moisture from wet Anode effluent, then can utilize dry anode feed gas " regeneration ", provide extra water with anode charging.HVAC-type (heating, ventilation and air conditioning) sorption wheel design can be applicable, because anode exhaust and entrance can be similar on pressure, and can have minimum impact from a stream to the minor leakage of another stream to whole technique.CO is carried out in use Deep Cooling Method 2in the embodiment removed, at CO 2before removing or among to dewater may be desirable, comprise and being dewatered by triethylene glycol (TEG) system and/or drier.On the contrary, if use amine eccysis to remove CO 2, then can at CO 2the section of removing downstream dewaters from anode exhaust.
Replace or except CO 2export outside stream and/or water output stream, anode exports and can be used for forming one or more product stream containing required chemistry or fuel Products.Such product stream can be equivalent to both synthesis gas stream, hydrogen stream or syngas product and hydrogen gas product stream.Such as, can be formed containing at least about 70 volume %H 2, as at least about 90 volume %H 2or at least about 95 volume %H 2hydrogen gas product stream.In addition or or, the H containing at least about 70 volume % altogether can be formed 2and CO, as the H of at least about 90 volume % 2with the synthesis gas stream of CO.Described one or more product stream can have the total H be equivalent in anode output 2with at least about 75% of CO gas volume, as total H 2with at least about 85% of CO gas volume or the gas volume of at least about 90%.Point out, based on utilizing water gas shift reaction section to transform between product, H in product stream 2the H in anode output may be different from the relative quantity of CO 2/ CO ratio.
In certain aspects, may desirably remove or be separated during anode exports a part of H existed 2.Such as, the H in certain aspects in anode exhaust 2/ CO ratio can be at least about 3.0:1.On the contrary, utilize the technique of synthesis gas, as F-T synthesis can with different ratio, as the ratio close to 2:1 consumes H 2and CO.An alternative can be utilize water gas shift reaction to change the content of anode output to have the H formed closer to required synthesis gas 2/ CO ratio.Another alternative can be utilize UF membrane to remove a part of H existed in anode output 2to realize required H 2/ CO ratio, or the combination using UF membrane and water gas shift reaction.Only a part of H in utilizing UF membrane removing anode to export 2an advantage can be can carry out required separation under relatively mild conditions.Because a target can be produce still to have remarkable H 2the retentate of content, generates the penetrant of High Purity Hydrogen by UF membrane and does not need exacting terms.Such as, permeate side under the pressure higher than ambient pressure, still can have the actuating force being enough to carry out UF membrane simultaneously, but not on membrane permeate side, has the pressure of about 100kPaa or lower (as ambient pressure).In addition or or, purge gas such as methane can be used to provide the actuating force of UF membrane.This can reduce H 2the purity of penetrant stream, but the required purposes depending on this penetrant stream may be favourable.
In aspects of the present invention, at least partially anode exhaust stream (preferably at separation of C O 2and/or H 2after O) can be used as the charging of the technique outside fuel cell and relevant reforming sections.In every respect, anode exhaust can have about 1.5:1 to about 10:1, as at least about 3.0:1, or at least about 4.0:1, or the H of at least about 5.0:1 2/ CO ratio.Can be generated by anode exhaust or take out synthesis gas stream.Anode exhaust, optionally at separation of C O 2and/or H 2after O and optionally carrying out water gas shift reaction and/or UF membrane with after remove excess hydrogen, can be equivalent to contain quite a few H 2and/or the stream of CO.For the stream with relatively low CO content, as H 2/ CO is than the stream at least about 3:1, and this anode exhaust can be suitable as H 2charging.H can be benefited from 2the example of the technique of charging can include, but not limited to turbine in refinery processes, ammonia synthesizer or (difference) electricity generation system or its combination.According to purposes, still lower CO 2content may be desirable.For have be less than about 2.2 to 1 and be greater than about 1.9 to 1 H 2the stream of/CO ratio, this stream can be suitable as synthesis gas charging.The example that can benefit from the technique of synthesis gas charging can include, but not limited to gas-to-liquid plant (as used the device by the fischer tropsch process of non-shifting catalyst) and/or methanol synthesizer.Amount as the anode exhaust of the charging of external process can be anyly to measure easily.Optionally, when the charging using a part of anode exhaust as external process, the anode exhaust of Part II can be recycled to anode input and/or be recycled to the combustion zone of burning energy supply generator.
The input stream that can be used for dissimilar fischer-tropsch synthesis process can provide the example being applicable to being exported the dissimilar product stream generated by anode.For use transformation catalyst, as the Fischer-Tropsch synthesis system of ferrum-based catalyst, the required input stream of this reaction system is except H 2also CO can be comprised outward with CO 2.If there is not enough CO in input stream 2, the fischer-tropsch catalysts with Water gas shift/WGS activity can consume CO to generate extra CO 2, cause the synthesis gas of possibility CO deficiency.In order to by this Fischer-tropsch process and SOFC fuel cell integrated, segregation section that anode exports can be run with CO needed for keeping in syngas product 2(with optional H 2o) measure.On the contrary, to the fischer-tropsch catalysts based on non-shifting catalyst, any CO existed in product stream 2the inert component in fischer-tropsch reaction system can be served as.
With purge gas, as methane purge gas purges in the aspect of film, methane purge gas can be equivalent to be used as anode fuel or for different low pressure process, as the methane stream of boiler, stove, gas turbine or other fuel consumers.In this one side, stride across the low-level CO of this film 2infiltration can have minimum consequence.This CO of film may be penetrated 2reaction in antianode can have minimal effects, and this CO 2can be retained in anodic product.Therefore, the CO of the cross-film loss due to infiltration 2(if any) do not need to be displaced through SOFC electrolyte again.This significantly can reduce the separation selectivity requirement to hydrogen permeation membrane.This can allow such as to use has lower optionally higher permeability film, and it film surface area of use lower pressure and/or reduction can become possibility.In this one side of the present invention, the volume of purge gas can be the large multiple of the hydrogen volume in anode exhaust, and this can make the effective density of hydrogen in permeate side keep close to 0.The hydrogen be separated thus can be incorporated in the charging methane of turbine, can strengthen turbine combustion feature as mentioned above this its.
Point out, the excessive H generated in the anode 2the fuel having isolated greenhouse gas can be represented.Any CO during anode exports 2can easily be separated from anode exports, as by using, amine is washed, deep cooling CO 2separator and/or transformation or vacuum pressure swing adsorption process.Several component (H that anode exports 2, CO, CH 4) be not easy removing, and CO 2and H 2o can easily remove usually.According to this embodiment, the CO in anode output can be isolated 2at least about 90 volume %, form relatively high-purity CO 2export stream.Therefore, any CO generated in the anode can effectively be isolated 2to form high-purity CO 2output stream.After isolation, the remainder that anode exports mainly can be equivalent to have the component of chemistry and/or fuel value and the CO of reducing amount 2and/or H 2o.Due to quite a few CO generated by original fuel (before reformation) 2can be separated, the CO generated with after-combustion exported by the anode of remainder can be reduced 2amount.Especially, the fuel in the anode of remainder exports is H 2degree on, usually can not form extra greenhouse gas by the burning of this fuel.
Antianode exhaust can impose the processing of various gas and select, comprise the disconnected from each other of Water gas shift/WGS and component.Two kinds of general Anode machining scheme displays in fig 1 and 2.
Fig. 1 schematically shows an example with the reaction system of the fuel cell array of chemical synthesis process cooperation Solid Oxide Fuel Cell.In FIG, fuel streams 105 is provided to (or multiple) reforming sections 110 relevant to the anode 127 of fuel cell 120 (fuel cell as the part as the fuel cell pack in fuel cell array).The reforming sections 110 relevant to fuel cell 120 can in fuel cell module.In in some are optional, also can use the reformable fuel of a part that outside reforming sections (not shown) was reformed in input stream before input stream is sent into fuel cell module.Fuel streams 105 can preferably include reformable fuel, as methane, other hydrocarbon and/or other class hydrocarbon compound, as the organic compound containing carbon-hydrogen link.Fuel streams 105 also optionally can contain H 2and/or CO, as the H provided by optional anode recirculation stream 185 2and/or CO.Point out, anode recirculation stream 185 is optional, and in many aspects in, not have directly or by being combined with fuel streams 105 or fuel reforming stream 115 and indirectly getting back to the recycle stream of anode 127 from anode exhaust 125.In the reformed, fuel reforming stream 115 can be sent into the anode 127 of fuel cell 120.Also O will can be contained 2stream 119 send into negative electrode 129.From the flux of oxygen ions 122 (O of the cathode portion 129 of fuel cell 2 2-) can provide anode fuel cell react needed for remaining reaction thing.Based on the reaction in anode 127, gained anode exhaust 125 can comprise H 2o, be equivalent to one or more components (H of the fuel of incomplete reaction 2, CO, CH 4or other component corresponding with reformable fuel) and choose any one kind of them or multiple extra non-reactive component, as CO 2, N 2and/or other pollutant of a part as fuel streams 105.Then anode exhaust 125 can be sent into one or more segregation section.Such as, CO 2the section of removing 140 can be equivalent to deep cooling CO 2remove system, for removing sour gas, as CO 2the amine section of washing or for separation of C O from anode exhaust 2the CO of another suitable type of output stream 143 2segregation section.Optionally, anode exhaust can first through water-gas shift 130 with any CO will existed in anode exhaust (with some H 2o is together) change into CO in the anode exhaust 135 of optional Water gas shift/WGS 2and H 2.Depend on CO 2the character of the section of removing, water condensation or the section of removing 150 may be desirable to export stream 153 except anhydrating from anode exhaust.Although what show in FIG is at CO 2after segregation section 140, but it optionally can be positioned at CO 2before segregation section 140.In addition, spendable optionally for separating of H 2uF membrane section 160 to generate H 2high-purity penetrant stream 163.Gained retentate stream 166 can be used as the input of chemical synthesis process subsequently.In addition or or, stream 166 can convert with by H in the second water-gas shift 131 2, CO and CO 2content is adjusted to different ratio, produces the output stream 168 being further used for chemical synthesis process.In FIG, display be take out anode recirculation stream 185 from retentate stream 166, but in addition or or, can in various segregation section or between other take out anode recirculation stream 185 in position easily.In addition or or, segregation section and shift-converter can configure with different order and/or with parallel construction.Finally, the output that can be used as negative electrode 129 generates the O with reduction 2the stream 139 of content.For the sake of simplicity, the various compression come in handy in the method and heat supply/add or the section of removing except hot arc and steam is not shown.
As mentioned above, antianode is vented various types of separation of carrying out and can carries out with any order easily.Fig. 2 shows the example of another order that antianode exhaust is carried out being separated.In fig. 2, first anode exhaust 125 can be sent into segregation section 260 to remove a part of 263 hydrogen contents from anode exhaust 125.This such as can reduce the H of anode exhaust 2content is to provide the H had close to 2:1 2the retentate 266 of/CO ratio.Then in water gas shift stage 230, H can be regulated further 2/ CO ratio is to realize desirable value.Then the output 235 of Water gas shift/WGS can be passed through CO 2segregation section 240 and the section of dewatering 250 are to produce the output stream 275 being suitable as the charging of required chemical synthesis process.Optionally can impose additional water gas shift stage (not shown) to output stream 275.A part exports stream 275 and can optionally recirculation (not shown) input to anode.Certainly, export based on the anode with required composition, other combination of segregation section and sequence can be utilized to generate stream.For the sake of simplicity, the various compression come in handy in the method and heat supply/add or the section of removing except hot arc and steam is not shown.
negative electrode input and output
Traditionally, Solid Oxide Fuel Cell can be run based on extracting while consuming a part of fuel be sent in the fuel streams of anode required load.Then the air that the fuel by this load, anode inputs, provide to negative electrode and O 2with the voltage of resistance determination fuel cell in fuel cell.Contact directly by eliminate between anode inlet flow and the composition of negative electrode inlet flow any, the additional option of fuel cell operation can be provided for, such as to generate excess syngas and/or to improve the gross efficiency (electricity+chemomotive force) etc. of fuel cell.
The O existed in negative electrode input stream 2amount can advantageously be enough to provide the oxygen needed for the cathode reaction in fuel cell.Therefore, O 2percent by volume can be advantageously O in this cathode exhaust gas 2at least 0.5 times that measures.Optionally, if necessary, additional air can be added to provide enough oxidants to cathode reaction in negative electrode input.When using the air of certain form as oxidant, the N in cathode exhaust gas 2amount can be at least about 78 volume %, such as at least about 88 volume %, and/or about 95 volume % or lower.In certain aspects, negative electrode input stream can additionally or alternatively contain the compound being usually regarded as pollutant, as H 2s or NH 3.In in other, negative electrode input stream can be purified to reduce or to be minimized by the content of this pollutant.
In addition or or, the condition in negative electrode is applicable to and unburned hydrocarbon (is inputted the O in stream with negative electrode 2in conjunction with) change into typical combustion product, as CO 2and H 2o.
fuel cell arrangement
In every respect, can fuel cell operation array to improve or to make the Energy transmission of fuel cell, as gross energy export, electric energy exports, syngas chemistry Energy transmission or its combination maximize.Such as, can by excessive reformable operating fuel Solid Oxide Fuel Cell in various situation, as generating for the synthesis gas stream of chemical synthesizer and/or for generating high-purity hydrogen stream.This synthesis gas stream and/or hydrogen stream can be used as synthesis gas source, hydrogen source, clean fuel source and/or for other purposes easily any.In in such, the O in cathode exhaust gas 2amount can input the O in stream with negative electrode 2amount and the O under required service conditions 2utilance is associated to improve or make fuel cell energy to export and maximizes.
solid Oxide Fuel Cell is run
On the one hand, the operating temperature of SOFC can be about 700 DEG C to about 1200 DEG C, and such as operating temperature can be about 800 DEG C, about 900 DEG C, about 1000 DEG C, or about 1100 DEG C.On the one hand, operating temperature can be selected to react to required ratio to advance the WGS in anode.
In certain aspects, can with one way or once by mode operation fuel cell.In single pass mode, do not send the reformate in anode exhaust back to anode inlet.Therefore, in one way is run, synthesis gas, hydrogen or some other products are not directly recycled to anode inlet from anode output.More generally, in one way is run, the reformate in anode exhaust does not also send anode inlet back to indirectly, as the fuel streams by utilizing reformate processing to introduce anode inlet subsequently.In addition or or, the heat from anode exhaust or output can recirculation in single pass mode.Such as, anode output stream can be passed through heat exchanger, and anode is exported cooling with heat exchanger and by another stream, the input stream as anode and/or negative electrode is heated.Heat from anode is recycled to fuel cell and is in one way or once consistent by operating use.Optionally but not preferably, in single pass mode can the composition that exports of combusting anode with to fuel cell heat supply.
Fig. 3 shows an illustrative example of the operation for the SOFC generated electricity.In figure 3, the anode part of fuel cell can receive fuel and steam (H 2o) as input, and water and optional excessive H is exported 2, CH 4(or other hydrocarbon) and/or CO.The cathode portion of fuel cell can receive O 2(such as air), as input, exports the oxidant (air) being equivalent to oxygen deprivation.In fuel cell, at the O that cathode side is formed 2 2-ion can across electrolyte transport be provided in anode place occur reaction needed for oxonium ion.
In Solid Oxide Fuel Cell, in example fuel cell as shown in Figure 3, some reactions can be there is.And if reforming reaction can be optionally provide enough H directly to anode 2, then can reduce or save reforming reaction.Following reaction is based on CH 4, but when using other fuel in a fuel cell, similar reaction can be there is.
(1) < anode reformation >CH 4+ H 2o=>3H 2+ CO
(2) < Water gas shift/WGS >CO+H 2o=>H 2+ CO 2
(3) the combination >CH of < reformation and Water gas shift/WGS 4+ 2H 2o=>4H 2+ CO 2
(4) < anode H 2oxidation >H 2+ O 2 2-=>H 2o+2e -
(5) < negative electrode >1/2O 2+ 2e -=>O 2 2-
Reaction (1) represents basic hydrocarbon reforming reaction to generate the H for the anode of fuel cell 2.The CO formed in reaction (1) changes into H by water gas shift reaction (2) 2.The combination of reaction (1) and (2) is shown as reaction (3).Reaction (1) and (2) can be carried out outside fuel cell, and/or reforms and can carry out in anode.
Reaction (4) respectively at anode and negative electrode place and (5) represent the reaction causing the electric power in fuel cell to occur.Reaction (4) will be present in charging or the H optionally generated by reaction (1) and/or (2) 2merge to form H with oxonium ion 2o, CO 2with the electronics being sent to this circuit.Reaction (5) makes O 2, CO 2merge with the electronics from this circuit and form oxonium ion.The oxonium ion generated by reaction (5) can across the electrolyte transport of fuel cell to provide the oxonium ion needed for reaction (4).Combine across electrolytical transmission with oxonium ion, then by providing electrical connection to form closed path loop between the anode and cathode.
In various embodiments, the target of fuel cell operation can be improve the gross efficiency of fuel cell and/or the gross efficiency of fuel cell+integrated chemical synthesis technique.This tradition being usually different from fuel cell is run, and wherein target can be for utilizing the fuel power generation function of supply battery with high electrical efficiency fuel cell operation.As defined above, by the electricity of fuel cell is exported add low heat value that fuel cell exports again divided by the low heat value of the input component of fuel cell to determine total fuel cell efficiency.In other words, TFCE=(LHV (el)+LHV (sgout))/LHV (in), wherein LHV (in) and LHV (sgout) refers to that the fuel element being sent to fuel cell is (as H respectively 2, CH 4and/or CO) and anode export stream or stream in synthesis gas (H 2, CO and/or CO 2) LHV.This can provide measuring of the electric energy+chemical energy of fuel cell and/or integrated chemical Process Production.Point out, under this definition of gross efficiency, the heat energy used in that use in fuel cell and/or integrated fuel cell/chemical synthesis system can have contribution to gross efficiency.But this definition does not comprise and exchanging or any excessive heat of otherwise taking out from fuel cell or integrated fuel cell/chemical synthesis system.Therefore, if from fuel cell excessive heat such as generating steam to be generated electricity by steam turbine, then do not comprise such excessive heat in the definition of gross efficiency.
Some operational factors can be controlled with excessive reformable operating fuel fuel cell.Some parameters can be similar at present to the parameter that fuel cell operation is recommended.In certain aspects, the cathode conditions of fuel cell and temperature input can be similar to those that recommend in document.Such as, required electrical efficiency and required total fuel cell efficiency can be realized within the scope of the typical temperature of fuel cell operation of Solid Oxide Fuel Cell.In typical operations, temperature can improve across fuel cell.
In in other, the operational factor of fuel cell can deviate from representative condition thus fuel cell operation reduces from anode inlet to anode export and/or from cathode inlet to cathode outlet to make temperature.Such as, hydrocarbon is changed into H 2the endothermic reaction with the reforming reaction of CO.If relative to the amount of oxidation of the hydrogen for generation of electric current, in anode of fuel cell, carry out enough reformations, then the net heat balance in this fuel cell can be heat absorption.This can cause the cooling between the entrance of fuel cell and outlet.In heat absorption running, the temperature that can control in fuel cell reduces to make the electrolyte in fuel cell keep molten state.
The composition of the fuel that the parameter that can control to be different from the mode of recommending at present can comprise fuel quantity that anode provides, anode provides and/or not having synthesis gas to be significantly recycled to anode input or negative electrode input from anode exhaust anode export in the separation of synthesis gas and trapping.In certain aspects, synthesis gas or hydrogen can not have been allowed directly or indirectly to be recycled to anode input or negative electrode input from anode exhaust.In in additional or substituting, limited amount recirculation can be there is.In in such, from anode exhaust to anode, the recirculation volume of input and/or negative electrode input can be less than about 10 volume % of anode exhaust, as being less than about 5 volume % or being less than about 1 volume %.
In some embodiments, can fuel cell in fuel arranged array the fuel cell (as fuel cell pack) of single section only can be there is.In such embodiment, this anode fuel utilance of single section can represent the anode fuel utilance of this array.Another option can be that fuel cell array can contain multiple anode segment and multiple negative electrode section, wherein each anode segment has the fuel availability in same range, as each anode segment has within 10% of setting, such as, fuel availability within 5% of setting.An option can be that each anode segment can have and equals setting or a certain amount of following fuel availability lower than setting again, equals setting or less than setting 10% or lower, such as 5% or lower as made each anode segment.As an illustrative examples, the fuel cell array with multiple anode segment can make each anode segment within about 10% of 50% fuel availability, and this is equivalent to the fuel availability that each anode segment has about 40% to about 60%.As another example, the fuel cell array with multiple sections can make each anode segment for being not more than 60% anode fuel utilance, and maximum deviation is little by about 5%, and this is equivalent to the fuel availability that each anode segment has about 55% to about 60%.In an example again, the one or more Fuel cell segments in fuel cell array can be run with the fuel availability of about 30% to about 50%, as run the multiple Fuel cell segments in this array with the fuel availability of about 30% to about 50%.More generally, the scope of any the above-mentioned type can be matched with any anode anode fuel utilization value specified herein.
Another option that is additional or that substitute can be the overall average of the fuel availability of all fuel cells in specified fuels array.In every respect, the overall average of the fuel availability of fuel cell array can be about 65% or lower, such as about 60% or lower, about 55% or lower, about 50% or lower, or about 45% or lower (in addition or or, the overall average fuel availability of fuel cell array can be at least about 25%, such as at least about 30%, at least about 35%, or at least about 40%).This average fuel utilance does not need to limit the fuel availability in arbitrary single hop, as long as this fuel cell array meets required fuel availability.
the purposes that synthesis gas after trapping exports
The component exporting stream and/or negative electrode output stream from anode can be used for various uses.An option can be use anode to export as hydrogen source as mentioned above.For the SOFC integrated or in the same place with oil plant, this hydrogen can be used as various refinery processes, as the hydrogen source of hydrotreatment.Such hydrogen can be used as the fuel of boiler, stove and/or fired heater in oil plant or other industrial plants, and/or this hydrogen can be used as generator, as the charging of turbine.Hydrogen from SOFC fuel cell also can additionally or alternatively as the input stream needing hydrogen as the fuel cell (may comprise fuel cell powered vehicle) of other type of input.Another option can be that the synthesis gas being additionally or alternatively used as the output of SOFC fuel cell to generate inputs as fermentation.
Another option can be additionally or alternatively use to export by anode the synthesis gas generated.Certainly, synthesis gas can be used as fuel, although synthesis gas base fuel is generating some CO as still causing during fuel combustion 2.In in other, synthesis gas exports the input that stream can be used as chemical synthesis process.An option can be another technique additionally or alternatively synthesis gas being used for fischer-tropsch technique and/or being formed larger hydrocarbon molecule by synthesis gas input.Another option can be additionally or alternatively use synthesis gas to form intermediate product, as methyl alcohol.Methyl alcohol can be used as end product, but in other in the methyl alcohol that generated by synthesis gas can be used for generating more large compound, as gasoline, alkene, aromatic hydrocarbons and/or other product.Point out, methanol synthesizing process and/or use transformation catalyst Fischer-tropsch process synthesis gas charging in, a small amount of CO 2acceptable.Hydroformylation is an example adding or substitute of the another synthesis technique that synthesis gas can be utilized to input.
Point out, generating a change of synthesis gas to using SOFC can be use SOFC fuel cell as the system for processing methane that offshore oil platform takes out and/or natural gas or the part apart from its final market other production system quite far away.Not attempt gas phase output or this gas-phase product of long term storage that transport carrys out artesian well, but can use the input of gas phase output as SOFC fuel cell array of artesian well.This can bring various benefit.First, the power supply of this platform is can be used as by the electric power of this fuel cell array column-generation.In addition, the synthesis gas from this fuel cell array exports the input that can be used as the Fischer-tropsch process of production scene.This can form the liquid hydrocarbon product transporting such as shore facilities or larger terminal more easily by pipeline, boats and ships or railcar from production scene to.
Other integrated options additionally or alternatively can comprise the source using negative electrode output as more highly purified heated nitrogen.Negative electrode input can comprise most air usually, this means can comprise quite a few nitrogen in negative electrode input.Fuel cell can from negative electrode across electrolyte anode conveying O 2, and cathode outlet can have than O low in air 2concentration and therefore higher N 2concentration.Removing residual O subsequently 2when, this nitrogen exports and can be used as the production of ammonia or other nitrogenous chemicals, as the charging of urea, ammonium nitrate and/or nitric acid.Point out, urea synthesis additionally or alternatively can use the CO be separated from anode exports 2as input charging.
additional embodiment
Embodiment 1. uses the Solid Oxide Fuel Cell with anode and negative electrode to produce electricity and the method for hydrogen or synthesis gas, and described method comprises anode, the reforming sections relevant to the anode of Solid Oxide Fuel Cell (comprising inside reforming element) of the fuel streams comprising reformable fuel being introduced Solid Oxide Fuel Cell or during it combines; O will be comprised 2cathode inlet stream introduce Solid Oxide Fuel Cell negative electrode in; Generate electricity in Solid Oxide Fuel Cell; Take out from anode exhaust and comprise H 2air-flow, comprise H 2with air-flow or its combination of CO, wherein the electrical efficiency of Solid Oxide Fuel Cell is about 10% to about 50%, and total fuel cell manufacture rate of Solid Oxide Fuel Cell is at least about 150mW/cm 2.
The method of embodiment 2. embodiment 1, wherein runs Solid Oxide Fuel Cell with about 0.25 to about 1.3, or about 1.15 or lower, or about 1.0 or lower, or produce electricity under the thermal ratio of about 0.75 or lower.
Method any one of embodiment more than 3. embodiment, the reformable fuel excess rate wherein comprising the fuel streams of reformable fuel is at least about 2.0, or at least about 2.5.
Method any one of embodiment more than 4. embodiment, wherein the electrical efficiency of Solid Oxide Fuel Cell is about 45% or lower, or about 35% or lower.
Method any one of embodiment more than 5. embodiment, wherein total fuel cell efficiency of Solid Oxide Fuel Cell is at least about 65%, or at least about 70%, or at least about 75%, or at least about 80%.
Method any one of embodiment more than 6. embodiment, wherein total fuel cell manufacture rate of Solid Oxide Fuel Cell is at least about 150mW/cm 2, or at least about 300mW/cm 2, or at least about 350mW/cm 2, or about 800mW/cm 2or it is lower.
Method any one of embodiment more than 7. embodiment, wherein the total reformable fuel production rate of Solid Oxide Fuel Cell is at least about 75mW/cm 2, or at least about 100mW/cm 2, or at least about 150mW/cm 2, or at least about 200mW/cm 2, or about 600mW/cm 2or it is lower.
Method any one of embodiment more than 8. embodiment, wherein introduce the anode of Solid Oxide Fuel Cell, the reforming sections relevant to the anode of Solid Oxide Fuel Cell (comprising inside reforming element) or its combine in the reformable hydrogen content of reformable fuel than reacting the amount height at least about 75% of hydrogen producing electricity, as height at least about 100%.
Method any one of embodiment more than 9. embodiment, wherein fuel streams comprises at least about 10 volume % inert compounds, at least about 10 volume %CO 2, or its combination.
Method any one of embodiment more than 10. embodiment, wherein at about 0.67 volt or lower, or the voltage V of about 0.5 volt or lower alower fuel cell operation.
Method any one of embodiment more than 11. embodiment, wherein anode exhaust has the H of about 1.5:1 to about 10:1 2/ CO ratio.
Method any one of embodiment more than 12. embodiment, wherein anode exhaust has the H of at least approximately 3.0:1 2/ CO ratio.
Method any one of embodiment more than 13. embodiment, wherein Solid Oxide Fuel Cell is tubular solid-oxide fuel battery.
Method any one of embodiment more than 14. embodiment, wherein Solid Oxide Fuel Cell comprises one or more integrated endothermic reaction section further.
The method of embodiment 15. embodiment 14, wherein at least one integrated endothermic reaction section comprises integrated reforming sections, and the fuel streams introduced in the anode of Solid Oxide Fuel Cell passed integrated reforming sections before entering the anode of Solid Oxide Fuel Cell.
Method any one of embodiment 16. embodiment 1-15, wherein the temperature of anode export is higher than the temperature of anode inlet about 40 DEG C or less.
Method any one of embodiment 17. embodiment 1-15, the wherein temperature of anode inlet and about 20 DEG C or less of the temperature difference of anode export.
Method any one of embodiment 18. embodiment 1-15, wherein the temperature of anode export is lower than the temperature of anode inlet about 10 DEG C to about 80 DEG C.
Method any one of embodiment 19. embodiment 1-15, wherein thermal ratio is about 0.85 or lower, and described method comprises to fuel cell supply heat further, lower than the temperature of anode inlet about 5 DEG C to about 50 DEG C with the temperature of holding anode outlet.
Method any one of embodiment more than 20. embodiment, described method comprises reformable fuel of reforming further, wherein introduce the anode of Solid Oxide Fuel Cell, the reforming sections relevant to the anode of Solid Oxide Fuel Cell (comprising inside reforming element) or its combine at least about 90% the reforming in the one way of the anode by Solid Oxide Fuel Cell of reformable fuel.
Although describe the present invention with reference to specific embodiments, the present invention is not limited thereto.Suitable change/the amendment run in specific circumstances should be obvious to those skilled in the art.Therefore following patent requires to be intended to be interpreted as containing all change/amendments like this dropped in true spirit/scope of the present invention.

Claims (19)

1. use the Solid Oxide Fuel Cell with anode and negative electrode to produce the method for electricity and hydrogen or synthesis gas, described method comprises:
The fuel streams comprising reformable fuel is introduced the anode of Solid Oxide Fuel Cell, the reforming sections relevant to the anode of Solid Oxide Fuel Cell (comprising inside reforming element) or during it combines;
O will be comprised 2cathode inlet stream introduce Solid Oxide Fuel Cell negative electrode in;
Generate electricity in Solid Oxide Fuel Cell; With
Take out from anode exhaust and comprise H 2air-flow, comprise H 2with air-flow or its combination of CO,
Wherein the electrical efficiency of Solid Oxide Fuel Cell is about 10% to about 50%, and total fuel cell manufacture rate of Solid Oxide Fuel Cell is at least about 150mW/cm 2.
2. the process of claim 1 wherein and run Solid Oxide Fuel Cell with about 0.25 to about 1.3, such as about 1.15 or lower, or about 1.0 or lower, or produce electricity under the thermal ratio of about 0.75 or lower.
3. the method for any one of the preceding claims, the reformable fuel excess rate wherein comprising the fuel streams of reformable fuel is at least about 2.0, such as at least about 2.5.
4. the method for any one of the preceding claims, wherein the electrical efficiency of Solid Oxide Fuel Cell is about 45% or lower, such as about 35% or lower.
5. the method for any one of the preceding claims, wherein total fuel cell efficiency of Solid Oxide Fuel Cell is at least about 65%, such as at least about 70%, at least about 75%, or at least about 80%.
6. the method for any one of the preceding claims, wherein total fuel cell manufacture rate of Solid Oxide Fuel Cell is at least about 150mW/cm 2, such as at least about 300mW/cm 2, at least approximately 350mW/cm 2, or about 800mW/cm 2or it is lower.
7. the method for any one of the preceding claims, wherein the total reformable fuel production rate of Solid Oxide Fuel Cell is at least about 75mW/cm 2, such as at least about 100mW/cm 2, at least approximately 150mW/cm 2, at least approximately 200mW/cm 2, or about 600mW/cm 2or it is lower.
8. the method for any one of the preceding claims, wherein introduce the anode of Solid Oxide Fuel Cell, the reforming sections relevant to the anode of Solid Oxide Fuel Cell (comprising inside reforming element) or its combine in the reformable hydrogen content of reformable fuel than reacting the amount height at least about 75% of hydrogen producing electricity, as height at least about 100%.
9. the method for any one of the preceding claims, wherein fuel streams comprises at least about 10 volume % inert compounds, at least about 10 volume %CO 2, or its combination.
10. the method for any one of the preceding claims, wherein at about 0.67 volt or lower, the such as voltage V of about 0.5 volt or lower alower fuel cell operation.
The method of 11. any one of the preceding claims, wherein anode exhaust has the H of about 1.5:1 to about 10:1 2/ CO ratio, such as at least about 3.0:1.
The method of 12. any one of the preceding claims, wherein Solid Oxide Fuel Cell is tubular solid-oxide fuel battery.
The method of 13. any one of the preceding claims, wherein Solid Oxide Fuel Cell comprises one or more integrated endothermic reaction section further.
The method of 14. claims 13, wherein at least one integrated endothermic reaction section comprises integrated reforming sections, and the fuel streams introduced in the anode of Solid Oxide Fuel Cell passed integrated reforming sections before entering the anode of Solid Oxide Fuel Cell.
Method any one of 15. claim 1-14, wherein the temperature of anode export is higher than the temperature of anode inlet about 40 DEG C or less.
Method any one of 16. claim 1-14, the wherein temperature of anode inlet and about 20 DEG C or less of the temperature difference of anode export.
Method any one of 17. claim 1-14, wherein the temperature of anode export is lower than the temperature of anode inlet about 10 DEG C to about 80 DEG C.
Method any one of 18. claim 1-14, wherein thermal ratio is about 0.85 or lower, and described method comprises to fuel cell supply heat further, lower than the temperature of anode inlet about 5 DEG C to about 50 DEG C with the temperature of holding anode outlet.
The method of 19. any one of the preceding claims, described method comprises reformable fuel of reforming further, wherein introduce the anode of Solid Oxide Fuel Cell, the reforming sections relevant to the anode of Solid Oxide Fuel Cell (comprising inside reforming element) or its combine at least about 90% the reforming in the one way of the anode by Solid Oxide Fuel Cell of reformable fuel.
CN201480053460.9A 2013-09-30 2014-09-29 Use the integrated power generation of solid oxide fuel cell and chemical production Expired - Fee Related CN105580179B (en)

Applications Claiming Priority (69)

Application Number Priority Date Filing Date Title
US201361884545P 2013-09-30 2013-09-30
US201361884586P 2013-09-30 2013-09-30
US201361884565P 2013-09-30 2013-09-30
US201361884605P 2013-09-30 2013-09-30
US201361884376P 2013-09-30 2013-09-30
US201361884635P 2013-09-30 2013-09-30
US61/884,565 2013-09-30
US61/884,586 2013-09-30
US61/884,605 2013-09-30
US61/884,545 2013-09-30
US61/884,376 2013-09-30
US61/884,635 2013-09-30
US201361889757P 2013-10-11 2013-10-11
US61/889,757 2013-10-11
US14/197,391 2014-03-05
US14/197,430 US20140272614A1 (en) 2013-03-15 2014-03-05 Integrated power generation and carbon capture using fuel cells
US14/197,551 2014-03-05
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
US14/197,391 US20140272613A1 (en) 2013-03-15 2014-03-05 Integrated power generation and carbon capture using fuel cells
US14/197,613 2014-03-05
US14/197,430 2014-03-05
US14/207,728 US20140261090A1 (en) 2013-03-15 2014-03-13 Integration of Molten Carbonate Fuel Cells in Cement Processing
US14/207,690 US9553321B2 (en) 2013-03-15 2014-03-13 Integrated power generation and carbon capture using fuel cells
US14/207,706 2014-03-13
US14/207,687 US9941534B2 (en) 2013-03-15 2014-03-13 Integrated power generation and carbon capture using fuel cells
US14/207,706 US9455463B2 (en) 2013-03-15 2014-03-13 Integrated electrical power and chemical production using fuel cells
US14/207,712 2014-03-13
US14/207,728 2014-03-13
US14/207,693 2014-03-13
US14/207,691 2014-03-13
US14/207,699 2014-03-13
US14/207,726 2014-03-13
US14/207,710 2014-03-13
US14/207,693 US9786939B2 (en) 2013-03-15 2014-03-13 Integrated power generation and chemical production using fuel cells
US14/207,721 US9520607B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells with fermentation processes
US14/207,698 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
US14/207,686 2014-03-13
US14/207,711 US9735440B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US14/207,711 2014-03-13
US14/207,708 2014-03-13
US14/207,710 US9362580B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in a refinery setting
US14/207,726 US9263755B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in iron and steel processing
US14/207,714 2014-03-13
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
US14/207,721 2014-03-13
US14/207,699 US20140272635A1 (en) 2013-03-15 2014-03-13 Mitigation of NOx in Integrated Power Production
US14/207,697 US9923219B2 (en) 2013-03-15 2014-03-13 Integrated operation of molten carbonate fuel cells
US14/207,687 2014-03-13
US14/207,690 2014-03-13
US14/207,697 2014-03-13
US14/207,708 US9647284B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
US14/207,686 US20140272633A1 (en) 2013-03-15 2014-03-13 Integrated power generation and carbon capture using fuel cells
US14/207,714 US9343764B2 (en) 2013-03-15 2014-03-13 Integration of molten carbonate fuel cells in methanol synthesis
US14/207,691 US9257711B2 (en) 2013-03-15 2014-03-13 Integrated carbon capture and chemical production using fuel cells
US14/315,419 US9178234B2 (en) 2013-03-15 2014-06-26 Integrated power generation using molten carbonate fuel cells
US14/315,439 US9077005B2 (en) 2013-03-15 2014-06-26 Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
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
US14/315,507 2014-06-26
US14/315,527 US9077008B2 (en) 2013-03-15 2014-06-26 Integrated power generation and chemical production using fuel cells
US14/315,419 2014-06-26
US14/315,479 2014-06-26
US14/315,507 US9077007B2 (en) 2013-03-15 2014-06-26 Integrated power generation and chemical production using fuel cells
US14/315,439 2014-06-26
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
PCT/US2014/058015 WO2015048626A1 (en) 2013-09-30 2014-09-29 Integrated power generation and chemical production using solid oxide fuel cells

Publications (2)

Publication Number Publication Date
CN105580179A true CN105580179A (en) 2016-05-11
CN105580179B CN105580179B (en) 2019-03-08

Family

ID=55888358

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480053460.9A Expired - Fee Related CN105580179B (en) 2013-09-30 2014-09-29 Use the integrated power generation of solid oxide fuel cell and chemical production

Country Status (3)

Country Link
JP (1) JP2016533628A (en)
KR (1) KR20160064188A (en)
CN (1) CN105580179B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430753A (en) * 2020-02-25 2020-07-17 国家能源投资集团有限责任公司 Solid oxide fuel cell system, anode off-gas treatment system, and off-gas treatment method
CN113013450A (en) * 2021-02-26 2021-06-22 清华大学 Method for determining self-heating balance of hydrocarbon fuel solid oxide fuel cell stack and application

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4349773A1 (en) * 2022-10-05 2024-04-10 Linde GmbH Method and plant for producing a hydrogen product

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000058090A (en) * 1998-07-31 2000-02-25 Toto Ltd Operation of solid electrolyte fuel battery
US6162556A (en) * 1995-12-04 2000-12-19 Siemens Aktiengesellschaft Method for operating a high-temperature fuel cell installation, and a high-temperature fuel cell installation
JP2004281257A (en) * 2003-03-17 2004-10-07 Japan Atom Energy Res Inst Electric power/hydrogen simultaneous production method using nuclear heat
US20040202914A1 (en) * 2003-04-09 2004-10-14 Ion America Corporation Co-production of hydrogen and electricity in a high temperature electrochemical system
CN1543686A (en) * 2001-06-15 2004-11-03 兹特克公司 Zero/low discharge and co-production type energy supply station

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2569550B2 (en) * 1987-05-08 1997-01-08 石川島播磨重工業株式会社 Fuel cell temperature distribution improvement method
JP2002334714A (en) * 2001-05-09 2002-11-22 Tokyo Gas Co Ltd Hydrogen manufacturing system incorporating fuel cell
JP2006318857A (en) * 2005-05-16 2006-11-24 Honda Motor Co Ltd Fuel cell and fuel cell stack

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162556A (en) * 1995-12-04 2000-12-19 Siemens Aktiengesellschaft Method for operating a high-temperature fuel cell installation, and a high-temperature fuel cell installation
JP2000058090A (en) * 1998-07-31 2000-02-25 Toto Ltd Operation of solid electrolyte fuel battery
CN1543686A (en) * 2001-06-15 2004-11-03 兹特克公司 Zero/low discharge and co-production type energy supply station
JP2004281257A (en) * 2003-03-17 2004-10-07 Japan Atom Energy Res Inst Electric power/hydrogen simultaneous production method using nuclear heat
US20040202914A1 (en) * 2003-04-09 2004-10-14 Ion America Corporation Co-production of hydrogen and electricity in a high temperature electrochemical system

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111430753A (en) * 2020-02-25 2020-07-17 国家能源投资集团有限责任公司 Solid oxide fuel cell system, anode off-gas treatment system, and off-gas treatment method
CN113013450A (en) * 2021-02-26 2021-06-22 清华大学 Method for determining self-heating balance of hydrocarbon fuel solid oxide fuel cell stack and application
CN113013450B (en) * 2021-02-26 2022-05-31 清华大学 Method for determining self-heating balance of hydrocarbon fuel solid oxide fuel cell stack and application

Also Published As

Publication number Publication date
CN105580179B (en) 2019-03-08
KR20160064188A (en) 2016-06-07
JP2016533628A (en) 2016-10-27

Similar Documents

Publication Publication Date Title
CN105122526B (en) Molten carbonate fuel cell is integrated in steel processing
US9755258B2 (en) Integrated power generation and chemical production using solid oxide fuel cells
CN105580179B (en) Use the integrated power generation of solid oxide fuel cell and chemical production
CN105612648B (en) Carbon dioxide is generated electricity and trapped with tandem-compound turbine

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190308

Termination date: 20200929