CN100440596C - Fuel cell, operating method thereof, sintering furnace, and power generator - Google Patents

Fuel cell, operating method thereof, sintering furnace, and power generator Download PDF

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CN100440596C
CN100440596C CNB2005101302531A CN200510130253A CN100440596C CN 100440596 C CN100440596 C CN 100440596C CN B2005101302531 A CNB2005101302531 A CN B2005101302531A CN 200510130253 A CN200510130253 A CN 200510130253A CN 100440596 C CN100440596 C CN 100440596C
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gas
furnace
negative electrode
carbon dioxide
hydrogen
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CN1790788A (en
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藏岛吉彦
本多俊彦
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NGK Insulators Ltd
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NGK Insulators Ltd
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    • 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

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Abstract

A molten carbonate fuel cell, operating method of the fuel cell, sintering furnace equipped with the fuel cell, and power generator, wherein a cathode gas with a high carbon dioxide concentration can be obtained without a process of increasing the carbon dioxide concentration, and the heat of furnace exhaust gas can be effectively reclaimed and the fuel consumption can be reduced. The cathode gas is a gas containing a furnace exhaust gas discharged from an industrial furnace for heating materials. Alternatively, the furnace exhaust gas can be used to pre-heat air to be fed to the cathode of the fuel cell. The carbon dioxide concentration of the cathode gas is 0.1-50 vol%.

Description

Fuel cell, its method of operation, sintering furnace and generator
Technical field
The present invention relates to method of operation, sintering furnace and the generator of fuel cell, fuel cell.More particularly, the present invention relates to molten carbonate fuel cell, the method of operation of this fuel cell, sintering furnace and a kind of generator of this fuel cell be equipped with, wherein, a kind of gas is as the cathode gas of molten carbonate fuel cell, this gas comprises the furnace exhaust as carbon dioxide source that discharges in the industrial furnace of heating material, furnace exhaust and negative electrode are used the mist of preheating gas with gas or negative electrode, perhaps negative electrode preheating gas, this negative electrode preheating gas is a kind of gas that uses furnace exhaust to carry out preheating as thermal source, wherein, be used as under the situation of cathode gas at furnace exhaust or mist, can obtain containing the cathode gas of high concentration carbon dioxide by the method that does not need to improve gas concentration lwevel, using negative electrode with under the situation of preheating gas, the heat of furnace exhaust can be reclaimed effectively, and reduces the consumption to fuel.
Background technology
Usually, oxygen contained in the air and carbon dioxide are used as oxygen and the carbon dioxide that supplies to the fused carbonate fuel battery cathode side.Gas with high concentration carbon dioxide helps the activating fuel battery reaction.Based on this reason, content is no more than common can the use of carbon dioxide of 0.03% volume in the air after improving gas concentration lwevel.For example, produce carbon dioxide by electrochemical reaction in anode-side the in service of fuel cell, the method that the waste gas that contains this carbon dioxide is reclaimed is applied to concentrating the carbon dioxide in the gas (cathode gas) that supplies to cathode side.Yet,, therefore too little so that be not enough to improve and supply to concentration of carbon dioxide in the cathode side gas by the recovery anode waste gas in the amount of carbon dioxide that anode-side produces because fuel cell reaction is gentle starting after just having begun.A kind of compressed-air actuated energy of method needs that before supplying to cathode side, concentrates carbon dioxide by transformation absorption (PSA) system, thus the high-energy cost caused.Do not use in the molten carbonate fuel cell of PSA system at other, when starting, a part of battery fuel that burns produces heat and carbon dioxide.The heat that is produced is used for the heating fuel battery unit reaching operating temperature, and carbon dioxide then is used for supplying to cathode side.This method is also owing to the fuel gas that burnt has been wasted energy (for example, Japanese Patent Application Publication No.1993-89899).
Various industrial circles have all used various industrial furnaces to heat multiple material.The high-temp waste gas (furnace exhaust) that the burning fossil energy comes the industrial furnace of heating material to produce to contain carbon dioxide in a large number, the burning by fuel simultaneously produces heat.The angle of environment side effect is considered that it is very gainful thing that the entrained heat of furnace exhaust is for recycling and reuse from present high-temp waste gas.And, contain problem special and global warming recent years and the similar problem significant correlation of CO 2 waste gas.Need collect effectively strongly to reduce the amount of its carbonated simultaneously from the heat of industrial furnace waste gas.
On the other hand, too much heat that is used for ceramic or similar sintering furnace and the amount that reduces the waste gas carbon dioxide that it produced are not reclaimed in research, and these stoves are relatively little industrial furnaces.The carbonated combustion gas cognition that is used for the heat-agglomerating material in the sintering furnace is discharged into air by former state.On the contrary, for example, designed a kind of method (for example Japanese patent application No.2002-340482) that reclaims heat energy from waste gas in the sintering furnace that turns back to by the waste gas that will discharge in the sintering furnace.This method can reclaim the partial heat energy in the waste gas, and reduces total amount of fuel, therefore can reduce the amount of the titanium dioxide carbon that produces.Yet, be limited to the reduction of amount of carbon dioxide.
Summary of the invention
The problem in the prior art molten carbonate fuel cell of The present invention be directed to is finished, and these problems comprise that the extra energy of needs supplies to cathode side with the gas that contains high carbon dioxide concentration and furnace exhaust heat can only be by insufficient recovery.Especially, an object of the present invention is to provide the method for operation of a kind of molten carbonate fuel cell and this fuel cell, it comprises a kind of cathode gas of use, promptly, the furnace exhaust that from the industrial furnace of heating material, discharges as carbon dioxide source, furnace exhaust and negative electrode be with gas or the negative electrode mixture (mist) with preheating gas, perhaps negative electrode preheating gas, and this negative electrode is to use the negative electrode gas of furnace exhaust as the thermal source preheating with preheating gas.When using furnace exhaust or mist as cathode gas, the gas that contains high concentration carbon dioxide can be fed into cathode side and not utilize extra energy, because the furnace exhaust that contains carbon dioxide that discharges from sintering furnace can use without any need for the processing that improves gas concentration lwevel.When preheating gas was used for negative electrode, the heat of furnace exhaust can be reclaimed effectively, also can reduce the consumption of fuel.Another object of the present invention provides a kind of sintering furnace and generator, it comprises the cathode side that carbonated furnace exhaust that sintering furnace is discharged or mist supply to fuel cell, and without any need for the processing that improves gas concentration lwevel, therefore guaranteed that high concentration carbon dioxide gas supplies to cathode side and do not use extra energy, perhaps will be used for negative electrode and supply to the cathode side of fuel cell, guarantee effective utilization like this furnace exhaust with preheating gas.
Top purpose can reach by following fuel cell, its method of operation, sintering furnace and generator in the present invention.
(1) a kind of fuel cell, it comprises negative electrode, anode and the dielectric substrate that between negative electrode and anode, contains fused carbonate, supply to the gas that contains oxygen and carbon dioxide (cathode gas) of cathode side and supply to anode-side to produce the gas that contains hydrogen (anodic gas) of electric energy, wherein cathode gas is a kind of gas, it comprises the furnace exhaust that the industrial furnace of heating material discharges, furnace exhaust and negative electrode are used the mist of preheating gas with gas or negative electrode, perhaps negative electrode preheating gas, this negative electrode is to use the negative electrode gas of furnace exhaust as the thermal source preheating with preheating gas, and concentration of carbon dioxide is 0.1～50% volume in the cathode gas.
(2) according to the fuel cell of front (1), when wherein cathode gas contains furnace exhaust or mist, it is the waste gas (burnt gas) of burning gases and/or the decomposition gas that decomposition produced (waste gas decomposition) by contained organic material in material-to-be-heated that described industrial furnace is to use burning gases that combustion fuel produces to come the sintering furnace of heating material, described furnace exhaust.
(3) according to the fuel cell of front (2), wherein fuel is the fuel of hydrocarbonaceous.
(4) according to the fuel cell of front (3), wherein the fuel of hydrocarbonaceous is selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil.
(5), wherein use catalyst combustion chamber target gas to carry out preheating according to any one fuel cell in front (1)～(4).
(6) according to the fuel cell of front (5), wherein the thermal source of catalyst combustion chamber is the anode waste gas that discharges from anode.
(7) according to any one fuel cell in front (1)～(6), when wherein cathode gas contained negative electrode and uses preheating gas, then the negative electrode preheating gas was by being to carry out preheating with described furnace exhaust as the heat exchanger of thermal source.
(8) according to any one fuel cell in front (1)～(7), wherein anodic gas uses contained hydrogen in the reformation gas, and this reformation gas is to reform in the steam reformer on being installed on industrial furnace.
(9) a kind of method of operation of fuel cell, this fuel cell is equipped with negative electrode, anode and the dielectric substrate that between negative electrode and anode, contains fused carbonate, this method comprises: the gas (cathode gas) that will contain oxygen and carbon dioxide supplies to cathode side, the gas that will contain hydrogen (anodic gas) supplies to anode-side to produce electric energy, wherein cathode gas comprises the furnace exhaust that industrial furnace discharged of heating material, furnace exhaust and negative electrode are used the mist of preheating gas with gas or negative electrode, perhaps negative electrode preheating gas, this negative electrode is to use the negative electrode gas of furnace exhaust as the thermal source preheating with preheating gas, and concentration of carbon dioxide is 0.1～50% volume in the cathode gas.
(10) according to the method for front (9), wherein, when cathode gas contains furnace exhaust or mist, the burning gases that described industrial furnace is to use combustion fuel to produce come the sintering furnace of heating material, and described furnace exhaust is the waste gas (burnt gas) of burning gases and/or the decomposition gas that decomposition produced (waste gas decomposition) by contained organic material in material-to-be-heated.
(11) according to the method for front (10), wherein fuel is the fuel of hydrocarbonaceous.
(12) according to the method for front (11), wherein the fuel of hydrocarbonaceous is selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil.
(13), wherein use catalyst combustion chamber target gas to carry out preheating according to any one method in front (9)～(12).
(14) according to the method for front (13), wherein the thermal source of catalyst combustion chamber is the anode waste gas that discharges from anode.
(15) according to any one method in front (9)～(14), wherein, cathode gas contains negative electrode when using preheating gas, and the negative electrode preheating gas is by using described furnace exhaust to carry out preheating as the heat exchanger of thermal source.
(16) according to any one method in front (9)～(15), wherein anodic gas uses contained hydrogen in the reformation gas, and this reformation gas is to reform in the steam reformer on being installed on industrial furnace.
(17) a kind of sintering furnace, it comprises that the hydrocarbon containing fuels that is used for burning is with the combustion chamber that produces burning gases, sintering furnace main body and according to the fuel cell of front (1)～(8), wherein the sintering furnace main body be used for by burning gases heating and sintering wherein material and discharge as the burning gases of furnace exhaust and/or the decomposition gas that decomposition produced by material-to-be-heated contained organic material, described fuel cell is installed so that be used as cathode gas and is supplied to cathode side from the furnace exhaust of sintering furnace main body release.
(18) according to the sintering furnace of front (17), further comprise steam reformer, producing the reforming reaction of reformed gas, this reformed gas contains hydrocarbon is fed hydrogen and the carbon dioxide that is obtained in stove and the steam.
(19) according to the sintering furnace of front (18), wherein steam reformer comprises low temperature reformation part and high temperature reformation part, the low temperature part of reforming has and is used to cause metal reaction pipe or the ceramic reaction tube that steam reforming reaction takes place therein and be packaged in the reforming catalyst that reaction tube is used to quicken steam reforming reaction, and the high temperature part of reforming has and is used to the ceramic reaction tube that causes that steam reaction reacts therein.
(20) according to the sintering furnace of front (18) or (19), wherein steam reformer is installed in sintering furnace main body and/or furnace exhaust circulation road, and low temperature reforming section branch is arranged on and is heated to 600～1,000 ℃ position, high temperature reforming section branch is arranged on and is heated to 1,000～1,800 ℃ position.
(21) according to the sintering furnace of front (18)～(20), the some or all of hydrogen that wherein is included in the reformed gas is used as anodic gas.
(22) according to any one sintering furnace in front (18)～(21), further comprise hydrogen gas segregator, optionally Hydrogen Separation is entered the hydrogen fuel from reformed gas that steam reformer is formed being used for, by introducing reformed gas to it, this hydrogen fuel comprises the hydrogen and the residual gas that contains carbon dioxide as key component.
(23) according to the sintering furnace of front (22), further comprise the carbon dioxide fixation device with the carbon dioxide in the fixing isolated residual gas of hydrogen gas segregator, and/or fixed packet is contained in the carbon dioxide from the anodic gas (anode waste gas) that molten carbonate fuel cell discharges.
(24) according to any one sintering furnace in front (17)～(22), wherein the sintering furnace main body is introduced material with heating continuously, and continuously heated material is transported.
(25) according to any one sintering furnace in front (17)～(24), wherein heated material is a pottery.
(26) according to any one sintering furnace in front (17)～(25), wherein heated material is a honeycomb.
(27) a kind of generator, it comprises a kind of fuel cell, this fuel cell comprises negative electrode, anode, the dielectric substrate that contains fused carbonate between negative electrode and anode, generator comprises that also the gas (cathode gas) that will contain oxygen and carbon dioxide supplies to the cathode gas supply arrangement of negative electrode, and the gas (anodic gas) that will contain hydrogen supplies to anode to produce the anodic gas supply arrangement of electric energy, wherein the cathode gas supply arrangement has the furnace exhaust supply arrangement, the furnace exhaust that its industrial furnace that can supply with heating material discharges, and/or negative electrode gas feeding apparatus, it can supply to negative electrode with gas with negative electrode, the cathode gas that supplies to negative electrode by the cathode gas supply arrangement comprises the furnace exhaust that transports by the furnace exhaust supply arrangement, furnace exhaust and the negative electrode that transports with gas feeding apparatus by negative electrode are with gas or the negative electrode mist with preheating gas, perhaps negative electrode preheating gas, the negative electrode gas (negative electrode preheating gas) that this negative electrode is to use furnace exhaust to be preheated as thermal source with preheating gas, concentration of carbon dioxide is 0.1～50% volume in the cathode gas.
(28) according to the generator of front (27), wherein, when cathode gas contains furnace exhaust or mist, the burning gases that described industrial furnace is to use combustion fuel to produce come the sintering furnace of heating material, and described furnace exhaust is the waste gas (burnt gas) of burning gases and/or the decomposition gas that decomposition produced (waste gas decomposition) by contained organic material in material-to-be-heated.
(29) according to the generator of front (28), wherein fuel is the fuel of hydrocarbonaceous.
(30) according to the generator of front (29), wherein the fuel of hydrocarbonaceous is selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil.
(31), wherein use catalyst combustion chamber target gas to carry out preheating according to any one generator in front (27)～(30).
(32) according to the generator of front (31), wherein the thermal source of catalyst combustion chamber is the anode waste gas that discharges from anode.
(33) according to any one generator in front (27)～(32), wherein, engine also comprises heat exchanger, and the preheating gas that is used for negative electrode is by being to carry out preheating with described furnace exhaust as the heat exchanger of thermal source.。
(34) according to any one generator in front (27)～(33), wherein engine also comprises steam reformer, and anodic gas uses contained hydrogen in the reformation gas, and this reformation gas is reformed in steam reformer.
Description of drawings
Fig. 1 is the generalized section of an execution mode of fuel cell of the present invention.
Fig. 2 is the schematic block follow diagram of an execution mode of sintering furnace of the present invention.
Fig. 3 is the schematic block follow diagram of an execution mode of generator of the present invention.
Embodiment
According to fuel cell of the present invention, when using furnace exhaust or furnace exhaust and negative electrode with the mist of gas or negative electrode usefulness preheating gas during as cathode gas, the furnace exhaust that contains carbon dioxide that discharges from sintering furnace can be as the cathode gas of molten carbonate fuel cell, and without any need for the process that improves gas concentration lwevel.Therefore, can not need extra energy to produce electric energy by the gas of supplying with high concentration carbon dioxide.When using negative electrode to use preheating gas, the heat of recovery furnace waste gas effectively, and can reduce the consumption of fuel.The method of operation of fuel cell according to the present invention, using under furnace exhaust or the situation of mist as cathode gas, discharge the cathode gas that the furnace exhaust that contains carbon dioxide can be used as molten carbonate fuel cell from sintering furnace, and without any need for the process that improves gas concentration lwevel.Therefore, can not need extra energy to produce electric energy by the gas of supplying with high concentration carbon dioxide.When using negative electrode to use preheating gas, the heat of recovery furnace waste gas effectively, and can reduce the consumption of fuel.According to sintering furnace of the present invention and generator, when using furnace exhaust or mist as cathode gas, discharge the cathode side that the furnace exhaust that contains carbon dioxide can offer fuel cell from the sintering furnace main body, and without any need for the process that improves gas concentration lwevel.Therefore, can have the gas of high concentration carbon dioxide and not need extra energy to produce electric energy by supplying with cathode side.When using negative electrode to use preheating gas, the heat of recovery furnace waste gas effectively, and can reduce the consumption of fuel.
Following quoted figures is described embodiments of the present invention.Yet the present invention is not limited in the following execution mode.Can carry out various changes and raising to the present invention based on those skilled in the art's knowledge and do not exceed scope of the present invention.
Fig. 1 is the generalized section of an embodiment of fuel cell of the present invention.As shown in Figure 1, the fuel cell 1 of this execution mode comprises negative electrode 2, anode 3 and the dielectric substrate that contains fused carbonate 4 between negative electrode 2 and anode 3.The gas (cathode gas) 21 that contains oxygen and carbon dioxide is fed into negative electrode 2 sides, and the gas (anodic gas) 23 that contains hydrogen is fed into anode 3 sides to produce electric energy.Cathode gas 21 is a kind of gas, it contains the furnace exhaust that industrial furnace discharged, furnace exhaust and the negative electrode of heating material mist or the negative electrode preheating gas with gas or negative electrode usefulness preheating gas, and this negative electrode is to use furnace exhaust to carry out the negative electrode gas of preheating as thermal source with preheating gas.Concentration of carbon dioxide is 0.1～50% volume in the cathode gas 21.Gas concentration lwevel is preferably 10～45% volumes in the cathode gas 21, more preferably is 20～40% volumes.If concentration of carbon dioxide is lower than 0.1% volume, electrochemical reaction can take place to such an extent that relax very much, if surpass 50% volume, the amount of oxygen molecule can be not enough to produce enough carbonic acid ions.When cathode gas 21 contains furnace exhaust or mist, the burning gases that industrial furnace preferably uses combustion fuel and produced come the sintering furnace of heating material, and furnace exhaust is waste gas of burning gases (burnt gas) and/or the decomposition gas that decomposition produced (waste gas decomposition) by contained organic material in material-to-be-heated preferably.The gas that use contains waste gas decomposition can be eliminated as cathode gas 21 use is arranged on the afterburner of stove outside or the needs (detoxification treatment) that similar devices burns into waste gas decomposition non-toxic gas.In cell of fuel cell, carry out the needed fuel of operation that detoxification treatment can be saved afterburner or similar devices.It also contains the furnace exhaust that contains the height gas concentration lwevel that cathode gas 21 also can be discharged by sintering furnace oxygen (burnt gas and/or waste gas decomposition) simultaneously and forms, perhaps can be furnace exhaust (burnt gas and/or waste gas decomposition) and the negative electrode mixture with gas or negative electrode usefulness preheating gas.Furnace exhaust (burnt gas and/or waste gas decomposition) and negative electrode be with gas or negative electrode during with preheating gas mixed (if using mist), furnace exhaust (burnt gas and/or waste gas decomposition) and negative electrode with gas or negative electrode with the ratio of preheating gas be preferably 100: 0～1: 4.Can not need to use any for example PSA method for concentration to obtain although contain the cathode gas 21 of suitable gas concentration lwevel, can optimize gas concentration lwevel by the method that adopts any such raising gas concentration lwevel with the process that improves gas concentration lwevel.In this case, the cost that is used to improve the process of gas concentration lwevel is low-down, because used the furnace exhaust (burnt gas and/or waste gas decomposition) that contains high concentration carbon dioxide as cathode gas 21.Above-mentioned discussion is based on the supposition of furnace exhaust as cathode gas 21 carbon dioxide sources.When reducing fuel consumption by the heat of recovery furnace waste gas effectively is under the prior situation, and cathode gas 21 can not contain furnace exhaust, can be only by the preheating cathode gas composition of using furnace exhaust as the thermal source heating.
In this method, when using furnace exhaust or mist as cathode gas 21 in the fuel cell 1 in present embodiment, the furnace exhaust that contains carbon dioxide (burnt gas and/or waste gas decomposition) that discharges from industrial furnace (for example sintering furnace) can be used as the cathode gas 21 of fuel cell 1, and without any need for the process that improves gas concentration lwevel.Therefore, can not need extra energy to produce electric energy by supplying with the gas that contains high concentration carbon dioxide for negative electrode 2 sides.
In this embodiment, industrial furnace is the equipment that is used for heating material.For example, sintering furnace is that the burning gases that utilize combustion fuel to produce heat with agglomerated material.The preferred hydrocarbon containing fuels of employed fuel in sintering furnace, special, at least a fuel is selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil.Term " domestic gas " representative contains 70～90% volume methane as main component and for example gas of other hydrocarbon of ethane, propane and butane.
In the fuel cell 1 of this execution mode, cathode gas 21 enters cathode gas passage 5 and is fed into negative electrode 2 from cathode gas inlet 6, and wherein cathode gas 21 is supplied with carbon dioxide and oxygen, and is released as cathode exhaust by cathode exhaust outlet 7.Anodic gas 23 enters anode gas passages 8 and is fed into anode 3 from anodic gas inlet 9, anodic gas 23 hydrogen supplies wherein, and be excluded as anode waste gas by anode waste gas outlet 10.The electronics that reaction produced at negative electrode 2 and anode 3 propagates into negative electrode 2 according to route 25 from anode 3, and at load (load) 31 places as electric energy.When cathode gas 21 or anodic gas 23 contain allogenic material such as dust, preferably before being admitted to cathode gas passage 5 or anode gas passages 8, use these gases filter to remove these allogenic materials.
The typical reaction that takes place in fuel cell of the present invention (molten carbonate fuel cell) is as follows:
(1) at cathode side: CO 2+ (1/2) O 2+ 2e -=CO 3 2-
(2) carbanion (CO 3 2-) be transported to anode-side by dielectric substrate.
(3) in anode-side: H 2+ CO 3 2-=H 2O+CO 2+ 2e -
(4) contain CO when anodic gas, will be in the reaction below anode-side takes place.
CO+H 2O＝CO+H 2
The hydrogen that is produced in this reaction is as the H in the anode reaction (3) 2
Fig. 2 is the schematic block follow diagram of an execution mode of sintering furnace of the present invention, and this sintering furnace is equipped with fuel cell.Can make an explanation with reference to the execution mode of 2 pairs of fuel cells of the present invention of figure.When cathode gas 51 (in Fig. 1, be labeled as numeral 21) when containing furnace exhaust or mist, then contained furnace exhaust 72 or mist 72a preferably carries out preheating in the cathode gas 51 in the 42a of catalyst combustion chamber, particularly contains under the situation of waste gas decomposition of relative low temperature as furnace exhaust 72 or mist 72a.In this method, particularly contain under the situation of waste gas decomposition at furnace exhaust 72, cathode gas can be changed into non-toxic gas fully by carry out preheating in the 42a of catalyst combustion chamber.Because negative electrode 42 is heated to 600～650 ℃ usually, even so waste gas decomposition directly supplied to negative electrode 42, it also keeps nontoxic fully.In this case, although consider from the angle of the heat efficiency, the thermal source (fuel) that is used for catalyst combustion chamber 42a also can be from other fueling of originating preferably from the anode waste gas 54 of anode 43 releases.
Except furnace exhaust and as the component of mist 72a, the application that negative electrode is mentioned above also being used for preheating gas 73b with gas 73 or negative electrode.Because air is usually as negative electrode gas 73 under the room temperature, more preferably use negative electrode to reduce the amount of the anode waste gas 54 that is used for heatable catalyst combustion chamber 42a and improve generating efficiency with preheating gas 73b, for example, negative electrode is preheated in using the heat exchanger 73a of furnace exhaust as thermal source with preheating gas 73b.Not containing furnace exhaust 72 but only containing negative electrode uses the gas of preheating gas 73b can be used as cathode gas 51.Here, anode waste gas 54 is not to be consumed the gas that fuel meat discharges.Therefore, the reduction of anode waste gas amount can cause the reduction of fuel quantity.The energy productive rate here is can be divided by the numerical value of input fuel the subject of knowledge and the object of knowledge acquisition by institute's electrogenesis.The energy that uses low amount fuel to produce can improve the energy productive rate.Residue anode waste gas 54 contains hydrogen and similar gas, therefore, and the outside that it can be used as the fuel of fuel cell as required or be discharged into cell of fuel cell.In this case,, be used for the preferred furnace exhaust 72 of thermal source (fuel) of heat exchanger 73a although consider from the angle of the heat efficiency, also can be from other fueling of originating.The combustible component (hydrogen and carbon monoxide) that preferably in the anode waste gas 54 of catalyst combustion chamber 42a, burns, and to wherein injecting air, thereby heated air and produce the required carbon dioxide of negative electrode 42.Yet owing to only use under anode waste gas 54 situations, gas concentration lwevel may be insufficient, so preferred cycle part cathode exhaust 52 is as cathode gas 51.When the carbon dioxide that supplies to negative electrode 42 was inadequate, the circulation ratio that needs to improve cathode exhaust was kept stable gas concentration lwevel.
Anodic gas 53 (being labeled as numeral 23 among Fig. 1) contains hydrogen, and its concentration is preferably 100～50% volumes, more preferably 90～70% volumes.As anodic gas 53, can use the reformed gas that contains hydrogen and carbon dioxide, it is installed on 63 pairs of hydrocarbon of steam reformer on the industrial furnace and water by use and reforms and obtain.Reformed gas can directly use or use hydrogen gas segregator 64 to use after improving density of hydrogen with selectivity separating hydrogen gas from reformed gas.
In the fuel cell of present embodiment, can use the nickel oxide that contains lithium and similarly come to be used as cathode material.As the material of anode, can provide the nickel that contains aluminium, the nickel that contains chromium and similar.As the material of dielectric substrate, the lithium aluminate (LiAlO that can use fused carbonate to soak into 2).Although the form of fuel cell, negative electrode, anode and dielectric substrate does not have particular determination, in cylindrical fuel battery container, can put into plate-like cathodes, plate-shaped anode and therebetween tabular dielectric substrate and the layered product that forms.
As fused carbonate, sodium carbonate, lithium carbonate, potash and similar can being used alone, but also also mix together.
The reaction temperature of fuel cell is preferably 500～700 ℃ in the present embodiment fuel cell 1.If be lower than 500 ℃, carbonate enters inadequate molten state, consequently the reduction of conductivity.If be higher than 700 ℃, not only can increase the volatile quantity of fused carbonate, consequently reduced electrolytical amount, and the stainless intensity of the battery structure cellular construction material that acts as a fuel can reduce also, it causes the distortion of fuel cell.
An embodiment of fuel cell operating method of the present invention is described below.As shown in fig. 1, the method of operation of present embodiment comprises to negative electrode 2 sides supplies with the cathode gas 21 that contains carbon dioxide and oxygen, and anode 3 is supplied with the anodic gas 23 that contains hydrogen, to produce electric energy, wherein cathode gas is a kind of gas, the furnace exhaust (burnt gas and/or waste gas decomposition) that its industrial furnace that contains heating material discharges, furnace exhaust and negative electrode are used the mist of preheating gas with gas or negative electrode, perhaps negative electrode preheating gas, the negative electrode gas that this negative electrode is to use furnace exhaust to be preheated as thermal source with preheating gas, and concentration of carbon dioxide is 0.1～50% volume in the cathode gas.
In the method for operation of present embodiment, concentration of carbon dioxide is preferably 10～45% volumes in the cathode gas 21, more preferably 20～40% volumes.If concentration of carbon dioxide is less than 0.1% volume, the reaction of fuel cell can take place to such an extent that relax very much, if surpass 50% volume, the amount of oxygen molecule can be not enough to produce enough carbonic acid ions.Cathode gas 21 can only contain from sintering furnace and to discharge the furnace exhaust that the carbon dioxide that contains high concentration also contains oxygen (burnt gas and/or waste gas decomposition), perhaps can be furnace exhaust (burnt gas and/or waste gas decomposition) with negative electrode with gas or negative electrode mixture with preheating gas.When furnace exhaust (burnt gas and/or waste gas decomposition) and negative electrode with gas or negative electrode during with preheating gas mixed (using the situation of mist), furnace exhaust (burnt gas and/or waste gas decomposition) and negative electrode with gas or negative electrode with the ratio of preheating gas be preferably 100: 0～1: 4.Can not need to use any for example PSA method for concentration to improve the process of gas concentration lwevel and obtain although contain the cathode gas 21 of suitable gas concentration lwevel, can optimize gas concentration lwevel by the method that adopts any such raising gas concentration lwevel.In this case, the cost that is used to improve the gas concentration lwevel process is low-down, because used the furnace exhaust (burnt gas and/or waste gas decomposition) that contains high concentration carbon dioxide as cathode gas 21.Above-mentioned discussion is based on the supposition of furnace exhaust as the carbon dioxide source of cathode gas 21.When reducing under the even more important situation of fuel consumption by the heat of recovery furnace waste gas effectively, cathode gas 21 can not contain furnace exhaust, but can be only by the preheating cathode gas composition of using furnace exhaust as the thermal source heating.
In this method, when using furnace exhaust or mist as cathode gas 21 in the method for operation in present embodiment, the furnace exhaust that contains carbon dioxide (burnt gas and/or waste gas decomposition) that discharges from industrial furnace (for example sintering furnace) can be used as the cathode gas of fuel cell, and without any need for the process that improves gas concentration lwevel.Therefore, can not need extra energy to produce electric energy by supplying with the gas that contains high concentration carbon dioxide for cathode side.
Other composition of the method for operation of present embodiment fuel cell, service condition with similar be identical with fuel cell of the present invention that discussed.In this embodiment can be by adopting such composition, service condition and similar reaching identical effect.
Then, the sintering furnace of the present invention be equipped with above-mentioned fuel cell (below abbreviate " sintering furnace " as) is described.As described in Figure 2, the sintering furnace 100 of this execution mode comprises that the hydrocarbon containing fuels 71 that is used to burn is to produce combustion furnace 62, sintering furnace main body 61 and the above-mentioned fuel cell 41 of burning gases, wherein sintering furnace main body 61 is used to heat with sintering and is brought into material wherein and discharged burning gases as furnace exhaust 72 (burnt gas and/or decomposition gas) behind sintering by burning gases, and fuel cell 41 is set to make to supply to negative electrode 42 sides as cathode gas 51 from the furnace exhaust 72 (burnt gas and/or decomposition gas) that sintering furnace main body 61 discharges.The content of carbon dioxide is 0.1～50% volume in the cathode gas 51, is preferably 10～45% volumes, more preferably is 20～40% volumes.If concentration of carbon dioxide is lower than 0.1% volume, the very mitigation that fuel cell reaction can take place; If surpass 50% volume, the amount of oxygen molecule can be not enough to produce enough carbonic acid ions.Cathode gas 51 can be to contain the furnace exhaust 72 (burnt gas and/or decomposition gas) that contains oxygen from the high concentration carbon dioxide of sintering furnace main body 61 releases simultaneously, perhaps can be furnace exhaust 72 (burnt gas and/or decomposition gas) and the negative electrode air 73 of gas or the mixture that negative electrode is used the preheated air 73b of preheating gas.When furnace exhaust (burnt gas and/or waste gas decomposition) 72 and negative electrode mix (situation of using mist) with gas 73 or negative electrode with preheating gas 73b, furnace exhaust (burnt gas and/or waste gas decomposition) 72 and negative electrode with gas 73 or negative electrode with the ratio of preheating gas 73b be preferably 100: 0～1: 4.Although the process that containing the cathode gas 51 of suitable gas concentration lwevel can not need to use any for example PSA method for concentration to improve gas concentration lwevel obtains, can adopt the method for any such raising gas concentration lwevel to optimize concentration of carbon dioxide.In this case, the cost that is used to improve the process of gas concentration lwevel is low-down, because used furnace exhaust (burnt gas and/or the waste gas decomposition) 72 that contains high concentration carbon dioxide as cathode gas 51.Above-mentioned discussion is based on the supposition of furnace exhaust as the carbon dioxide source of cathode gas 51.When reducing fuel consumption by the heat of recovery furnace waste gas effectively is under the prior situation, and cathode gas 21 can not contain furnace exhaust, but can be only by using furnace exhaust to form with preheating gas as the negative electrode of thermal source heating.
In this manner, when using sintering furnace of the present invention, wherein the sintering furnace main body is equipped with fuel cell, the furnace exhaust (burnt gas and/or waste gas decomposition) that then contains the carbon dioxide that discharges from the sintering furnace main body is fed into the cathode side of fuel cell, and without any need for the process that improves gas concentration lwevel.Therefore, can in addition, can effectively utilize the furnace exhaust (burnt gas and/or waste gas decomposition) that in the sintering furnace main body, produces by supplying with the gas of high concentration carbon dioxide and do not need extra energy to produce electric energy to cathode side.And, can the carbon dioxide that be contained in anode of fuel cell waste gas be fixed by using carbon dioxide fixation device or similar, reduce the amount that is discharged into carbon dioxide in air.
In the sintering furnace of this execution mode, the dielectric substrate 44 that fuel cell is equipped with negative electrode 42, anode 43 and contains fused carbonate between negative electrode 42 and anode 43.The gas (cathode gas 51) that contains oxygen and carbon dioxide is fed into negative electrode 42 sides, and the gas (anodic gas 53) that contains hydrogen is fed into anode 43 sides, to produce electric energy.With previously described fuel cell identical similar of the composition of fuel cell, service condition with other, and can by adopt such composition, service condition and other similar obtain identical effect.
As shown in Figure 2, in the sintering furnace 100 of present embodiment, sintering furnace main body 61 there is not special restriction.Can use usual means, wherein, be sintered material, for example pottery and similar is transmitted the sintering by burning gases then, and burning gases are by using available burner 61 hydrocarbon containing fuels 71 of burning to produce.Material preferably is fired into ceramic honeycomb.The ceramic honeycomb of this execution mode is the structure that ceramic masses forms, and it has the many cells that separator separated as the fluid passage.Sintering furnace main body 61 can be the batch processing type, its off and on sintering Unit one for the material of sintering.Yet, more preferably continuous type sintering furnace main body 61, be sintered into ceramic honeycomb for example material can by continuously to wherein send into, heating and sintering therein, and behind sintering, send.
As described in Figure 2, the sintering furnace 100 of this execution mode does not have special restriction to combustion furnace 62, the hydrocarbon containing fuels 71 of can burning effectively in stove.Combustion furnace 62 can be installed in the outside of sintering furnace main body, and is designed to import burning gases by pipe to sintering furnace main body 61, and perhaps combustion furnace 62 also can be installed in the inside of sintering furnace main body 61.According to the capacity of combustion furnace 62, the size and the similar condition of sintering furnace main body 61, sintering furnace main body 61 can be installed one, two or more combustion furnace 62.As combustion furnace 62, can use any type of combustion furnace with burner, burner is equipped with the circuit of input air and fuel.The preferred regeneration type burner that uses, the air that wherein is used to burn is preheated.Can supply with hydrocarbon containing fuels 85 by hydrocarbon containing fuels supply arrangement (not shown) and obtain hydrocarbon containing fuels 71.The hydrogen partial fuel of supplying with from hydrogen gas segregator 64 83 can mix.The hydrogen fuel 83 that interpolation is supplied with from hydrogen gas segregator 64 can reduce the consumption of fuel.Hydrocarbon containing fuels 85 preferred at least a fuel are selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil.
As described in Figure 2, sintering furnace 100 preferred disposition of this execution mode have steam reformer 63, hydrogen gas segregator 64 and carbon dioxide fixation device, in steam reformer 63, the hydrocarbon material that will be reformed 81 and feed wherein steam and heat and be reacted into the reformed gas 82 that contains hydrogen and carbon dioxide, in hydrogen gas segregator 64, institute's hydrogen is separated selectively in the reformed gas 82 that forms in the steam reformer 63, to obtain to comprise hydrogen and the hydrogen fuel that contains the residual gas 84 of carbon dioxide as key component, carbon dioxide fixation device 65 is used for fixing the carbon dioxide in the residual gas 84, so that carbon dioxide can not be discharged into the outside with gaseous state.Among Fig. 2, each equipment all flows by fuel and is connected with miscellaneous equipment with the pipe of transmission.
In this method, the partial combustion heat that produces in sintering furnace main body 61 reclaims in steam reformer 63 producing the reformed gas 82 of hydrogen, and it is as anodic gas 53, perhaps is used as anodic gas 53 by hydrogen gas segregator 64 from separating hydrogen gas wherein.Be released as anode waste gas 54 as the residual gas component behind the anodic gas 53.Because anode waste gas 54 contains carbon dioxide, this gas can mix with cathode gas 51, perhaps supplies to carbon dioxide fixation device 65 so that carbon dioxide is absorbed.The furnace exhaust (burnt gas and/or decomposition gas) 72 that discharges from sintering furnace main body 61 is preferably steam reformer 63 heat supplies, and then this gas is preferably used as cathode gas 51.When as cathode gas 51, residual gas is released as cathode exhaust 52.
Carbon dioxide fixation device 65 is designed to be used in NaOH as the fixing fixative 88 that feeds the carbon dioxide in it, fixative 88 is contacted with residual gas 84 and then make fixative 88 absorb contained carbon dioxide generating sodium carbonate in the residual gass 84, and discharge the waste liquid that contains sodium carbonate.Any can be as fixative 88 with the material of carbon dioxide reaction or absorbing carbon dioxide, and, for example can use NaOH, Mg (OH) without any particular restriction 2And it is similar.
The sintering furnace 100 of this execution mode is preferably designed in steam reformer 63 steam reforming reaction takes place, this steam reformer is installed in the passage of sintering furnace main body 61 and furnace exhaust (burnt gas and/or waste gas decomposition) 72, utilize burning gases (furnace exhaust) and/or by burning gases from the radiant heat that is sintered material, sintering equipment and furnace wall (conduit wall of furnace exhaust (burnt gas and/or waste gas decomposition)), the material 81 that will be reformed that heating is flowed in steam reformer 63.Resulting reformed gas 82 is supplied to hydrogen gas segregator 64 and is separated into hydrogen fuel 83 and residual gas 84.Hydrogen fuel 83 (hydrogen fuel that is used for anode 86) is preferably used as anodic gas 53.In this mode, highly purified hydrogen can be used for fuel cell.Reformed gas 82 also can be used as anode and is directly supplied to anode 43 sides with reformed gas 82a.Can use the anode of supplying with by hydrogen supply arrangement (not shown) to supply to the anodic gas 53 of fuel cell 41 with gas containing hydrocarbon 87 conducts.Can use steam reformation hydrogen gas generation, hydrogen fixture, hydrogen bucket and similar as the hydrogen supply arrangement.
The heat of burning gases can be used for the raw-material heat absorption reforming reaction of steam reformer.In this method, the part heat that can effectively utilize in the burning gases to be contained, otherwise will be bled off.
The steam reformer 63 that is used for the sintering furnace 100 of this execution mode has no particular limits.Can use any equipment that can be installed in the passage of sintering furnace main body 61 and furnace exhaust (burning gases and/or waste gas decomposition) 72 and can use the heat permission generation steam reforming reaction of being supplied with.For example, when temperature was lower than 1000 ℃, such device can be to be equipped with the metal of reforming catalyst or the reaction tube that pottery is made.Temperature is higher than or when equaling 1000 ℃, can uses ceramic reaction tube.As the steam reformer 63 that comprises combinations thereof, can use a unit, this unit comprises low temperature reformation part, it has and is used to the metal reaction pipe or the ceramic reaction tube that cause that steam reforming reaction takes place therein, and be packaged in the reforming catalyst that is used to quicken steam reforming reaction in the reaction tube, also comprise high temperature reformation part, it has and is used to the ceramic reaction tube that causes that steam reforming reaction takes place therein.In said units, steam reformer 63 preferably is installed on sintering furnace main body 61 and/or furnace exhaust (burnt gas and/or decomposition gas) 72 circulation roads, low temperature is reformed partly to be placed in and is heated to 600～1,000 ℃ position, high temperature is reformed partly to be placed in and is heated to 1,000～1,800 ℃ position.The metal reaction pipe is suitable for use in and is lower than 1,000 ℃ temperature, because the thermal resistance temperature is not high enough.Yet,, therefore in this pipe, can react fully because the catalyst that improves steam reforming reaction is housed in pipe.The pottery reaction tube can make to be reflected under the situation that does not have reforming catalyst to exist steam reforming reaction takes place fully, because ceramic reaction tube can be used for 1,000 ℃ or above high temperature.Also can use ceramic reaction tube by the reforming catalyst of packing in the temperature below 1,000 ℃.
In Fig. 2, steam reformer 63 is installed in the passage of sintering furnace main body 61 and furnace exhaust (burning gases and/or waste gas decomposition) 72.Steam reformer 63 can be installed on sintering furnace main body 61 or exhaust steam passage.
Supply to preferably a kind of mixture of the hydrocarbon material 81 that to be reformed in the steam reformer 63, by obtaining from the hydrocarbon and the steam of hydrocarbon supply arrangement (not shown) and vapor supplying apparatus (not shown) respectively to the supply of blender (not shown).Any hydrocarbon supply arrangement commonly used can be used, and without any particular restriction.For example, when using domestic gas, can from existing tracheae, supply with hydrocarbon.If there is not pipeline to use, gas tank can be installed comes from jar, to supply with hydrocarbon by pipeline.Other hydrocarbon such as liquefied petroleum gas and kerosene also can be supplied with by pipe laying in an identical manner, perhaps by pipeline from storage equipment such as jar, bucket or similar supplying with.In this case, liquified hydrocarbonaceous materials gasifies by heating before supplying to reformer.If necessary, can use force (forcing) pump to improve air pressure.This is the effective ways that react, because reacting dose can improve along with raw-material pressure.Can use vapor supplying apparatus commonly used, and not have particular restriction.For example, can use boiler commonly used, be used to from the heat recovery boiler of the used heat of stove or other thermal source and similar device.
As the material of ceramic reaction tube in the steam reformer 63, preferably use at least a silicon nitride, carborundum, aluminium nitride, aluminium oxide and the zirconic pottery of being selected from.Use this pottery can guarantee that steam reforming reaction at high temperature carries out with high thermal resistance.As the embodiment of metal reaction tube material, can use SUS309, SUS310, SCH22CF (HK40), SCH24CF (H.P.), HA230 and similar.
When reaction tube was sintered air in the stove 100 and corrodes, reaction tube can be inserted in the hole of boring on the thermal resistance brick, imports in the reaction tube by brick so that heat energy is enough.Because the thermal resistance brick has blocked corrosive gas in this structure, reaction tube is also protected to avoid corrosion.
Reforming catalyst as using in the steam reformer 63 preferably uses Raney nickel, for example the Synetix catalyst of Johnson Matthey Co. manufacturing.As other effective catalyst, also can provide Raney nickel, copper catalyst, transition-metal catalyst, platinum catalyst and similar.Steam reforming reaction preferred embodiment as using nickel-containing catalyst can provide the ICI method, wherein passes through the temperature and 1.01 * 10 at 700～950 ℃ 5～40.52 * 10 5(N/m 2) pressure and exist under the situation of nickel-containing catalyst, by the mixture that produces hydrogen (4 moles) and carbon dioxide (1 mole) in methane (1 mole) and the water (2 moles) through the endothermic reaction.
The reactive ratio of hydrocarbon and water in steam reformer 63 (actual amounts of hydrogen and the ratio that produces amounts of hydrogen in theory of producing) is preferably 50mol% or more.If less than 50mol%, can increase the consumption of fuel.The reactive ratio of hydrocarbon and water is preferably high as much as possible.
The content of hydrogen in the reformed gas that institute's steam reformer 63 produces is preferably 10～80mol%, and the content of carbon dioxide is preferably 1～20mol%.
As the hydrocarbon that is used for the raw material of steam reforming reaction in the steam reformer 63, can use methane, ethane, propane, butane and similar.Wherein, optimization methane.
When using ceramic reaction tube 24 to be used for steam reforming reaction, hydrocarbon and water are preferably 1,000～1, and 800 ℃ are reacted down to produce hydrogen and carbon dioxide.
As described in Figure 2, in the sintering furnace 100 of this execution mode, hydrogen gas segregator 64 Selective Separation become the hydrogen and the hydrogen fuel 83 that contains the residual gas 84 of carbon dioxide that comprise as main component at the reformed gas that contains hydrogen and carbon dioxide 82 that steam reformer 63 produces.Hydrogen gas segregator 64 is not had special restriction, if this equipment can be from the mist that contains hydrogen separating hydrogen gas optionally.For example, can use a kind of system, it comprise by palladium or contain cylindrical hydrogen separator that the film of palldium alloy makes with by stainless steel or the similar hydrostatic column of making, the hydrogen gas segregator setting wherein makes the air of hydrogen gas segregator cylinder interior to cut off with the air of cylinder outside.Inject the mist that contains hydrogen to hydrostatic column, then be incorporated into the inboard of Hydrogen Separation film cylinder so that hydrogen selective ground is penetrated into the outside from Hydrogen Separation film inboard.The hydrogen that flows to the Hydrogen Separation film outside is sent to the outside of cylindrical chamber as hydrogen fuel 83.Also can make the inboard of other gas by the Hydrogen Separation film as residual gas 84 and be sent to the outside of cylindrical chamber.The mist that contains hydrogen can be guided to the outside of Hydrogen Separation film cylinder and make hydrogen flow to the inboard of Hydrogen Separation film cylinder.Use the hydrogen that is separated as containing the hydrogen fuel 83 of hydrogen as key component, the residual gas 84 that contains other gas that comprises carbon dioxide is input to carbon dioxide fixation device 65.The residual gas 84 that contains carbon dioxide can mix with cathode gas 51 to use carbon dioxide to produce electric energy in fuel cell.Hydrogen fuel 83 employed terms " contain hydrogen as key component " and are meant that hydrogen content is 50% volume or more in the fuel.Hydrostatic column must not be columniform, and it can make any shape with inner space, and is for example box-like.In order to improve mechanical strength, the Hydrogen Separation film can be installed in for example ceramic surface of penetration material or inboard.The Hydrogen Separation film must not be columniform, its can be the plane or other Any shape.
Hydrogen gas segregator 64 can be integrally formed with steam reformer 63, and the hydrogen that generates in steam reformer 63 hydrogen gas segregator 64 that can be installed in steam reformer 63 optionally separates like this, discharges the back from steam reformer 63 and is used as hydrogen fuel 83.As the method for hydrogen gas segregator 64 being installed at steam reformer 63, a kind of method is provided with the cylindrical hydrogen diffusion barrier and the reforming catalyst of packing at hydrogen gas segregator 64 in cylinder.In this case, because the Hydrogen Separation film is as hydrogen gas segregator 64, the hydrogen gas segregator 64 of playing effectiveness is arranged on steam reformer 63.Use this system, the hydrocarbon-containing feedstock of being reformed 81 injects Hydrogen Separation film cylinder and its reaction by the reforming catalyst institute catalysis of the Hydrogen Separation film bucket of packing into changes into hydrogen, and the hydrogen that is produced can be transported to the cylinder outside by the Hydrogen Separation film.
Use the Hydrogen Separation efficient of hydrogen gas segregator 64 separating hydrogen gas from reformed gas 82, according to the residual volume of hydrogen in the reformed gas 82: the amount of the hydrogen that is separated is preferably 50: 50～1: 99 (volume ratio).If less than 50: 50 (volume ratio), fuel may not make full use of.Although expect high separative efficiency, act as a fuel with the organic efficiency of hydrogen, 1: 99 (volume ratio) also is enough.Higher separative efficiency may need higher cost.
As described in Figure 2, in the sintering furnace 100 of this execution mode, carbon dioxide fixation device 65 is fixed the carbon dioxide in the isolated residual gas 84 from hydrogen gas segregator 64, so that carbon dioxide can not be discharged into the outside with gaseous state.Carbon dioxide fixation device 65 there is not special restriction, so long as fixedly the carbon dioxide in the residual gas 84 makes carbon dioxide can not be discharged into the equipment of outside with gaseous state.Can be rightly as an embodiment of stabilizing carbon dioxide method, be included in the aqueous solution that NaOH is provided in the container fixative 88 as carbon dioxide, residual gas 84 is passed in the sodium hydrate aqueous solution so that solution and gas bubble, and then carbon dioxide and NaOH in the residual gas 84 are reacted, generate sodium carbonate.Because the anode waste gas 54 that fuel cell 41 is discharged contains carbon dioxide, and this gas is passed into absorbing carbon dioxide in the carbon dioxide fixation device 65.Here, the meaning of " stabilizing carbon dioxide " is meant the process that carbon dioxide is operated, and for example, by making the reaction of carbon dioxide and other compound or absorbed by other compound, thereby carbon dioxide can not be released with gaseous state.
When use contains for example above-mentioned sodium hydrate aqueous solution of NaOH material (solution) as fixative 88, in carbon dioxide fixation device 65, obtain sodium carbonate.From the waste liquid 89 that carbon dioxide fixation device 65 discharges, can be used as and contain sodium carbonate liquor and be removed.Like this, carbon dioxide fixation device 65 can be used as the sodium carbonate production equipment.With regard to the situation of carbon dioxide fixation device 65, carbon dioxide fixation device 65 is explained in more detail below as the sodium carbonate production equipment.
Structure as the container of carbon dioxide fixation device 65 there is not special restriction, as long as the sodium hydrate aqueous solution that this container can hold therein with carbon dioxide reaction generates sodium carbonate then.For example, can use a kind of cylindrical chamber, it has at least one and is used to import the input pipe of residual gas and NaOH and is used for the effluent discharge outlet of (hereinafter referred to as " containing sodium carbonate liquor ").Shape to container does not have special restriction.Can use cylinder, polygonal tube for example have the square bottom surface tube (comprising box-like), have the tube (comprising box-like) of any other shape bottom surface and similar.If desired, carbon dioxide fixation device 65 can assemble blender and overcoat or helix tube in order to heat or to cool off.Can use batch processing or half batch carbon dioxide fixation device 65.Batch carbon dioxide fixation device 65 uses a container of the above-mentioned type, makes carbon dioxide and NaOH reaction by supplying with residual gas.When nearly all NaOH reacts, stop residual gas stream and remove the whole solution that contains sodium carbonate, then inject NaOH and supply with residual gas to container again.In half batch carbon dioxide fixation device, use the container of two or more the above-mentioned types.Nearly all NaOH reacts in one of them container, and residual gas fails to be convened for lack of a quorum and switches in another container, wherein begins to generate sodium carbonate, and discharges the solution that contains sodium carbonate in the container that nearly all NaOH has reacted.
Method as producing sodium carbonate by stabilizing carbon dioxide provides a kind of method, and it recycles the sodium hydrate aqueous solution as fixative 88, supplies with residual gas 84 so that NaOH and carbon dioxide reaction to the sodium hydrate aqueous solution of circulation.As the method (it also can contain the sodium carbonate that generates in reaction) of recycle hydrogen aqueous solution of sodium oxide, can use a kind of method, it is carried the sodium hydrate aqueous solution of release from container by pipeline and the solution that discharges is turned back in the container.In this case, carbon dioxide fixation device 65 can carry out continued operation, continuous in circulatory system input NaOH, and continuous contain aqueous sodium carbonate (waste liquid) 89 from the aqueous sodium carbonate conduct that contains of removing the part circulation the system that aqueous sodium carbonate forms that contains that generates by NaOH and reaction.
When using carbon dioxide fixation device 65 as the sodium carbonate production equipment, using hydrogen gas segregator 64 carbon dioxide content in the residual gas behind the separating hydrogen gas 84 from reformed gas 82 to be preferably 15～99.9% weight, more preferably 60% weight or more.If less than 15% weight, impurity can increase in residual gas 84, makes to obtain the high-purity carbonic acid sodium difficulty that becomes by purifying from the carbonic acid waste liquor of sodium 89 that contains that carbon dioxide fixation device 65 discharges.
When residual gas 84 contain in a large amount of steam reformers 63 produce as the carbon monoxide of byproduct the time, also the carbon monoxide transducer can be installed, supply with residual gas 84 to it.A kind of carbon monoxide transducer of preferred use, the residual gas 84 that wherein is controlled in 350～360 ℃ contacts to transform carbon monoxide with Fe-Cr is catalyst based.In this carbon monoxide transducer, carbon monoxide and water reaction generate hydrogen and carbon dioxide.The carbon monoxide transducer can reduce the concentration of carbon monoxide in residual gas 84, and it will be by being converted into carbon dioxide at the carbon monoxide in the residual gas 84.Owing to also produce hydrogen at the carbon monoxide transducer except carbon dioxide, so can process hydrogen gas segregator to collect hydrogen from the residual gas 84 of carbon monoxide transducer removal, it can use by mixing with anodic gas 53.In this case, hydrogen gas segregator can be installed and, perhaps also can use hydrogen gas segregator 64, wherein can isolate a part of residual gas 84 to its input residual gas 84, import hydrogen gas segregator 64 with reformed gas 82 then, thereby circulate a part of residual gas 84.As the result that carbon monoxide transforms, the residual gas 84 that gas concentration lwevel improves (perhaps when using hydrogen gas segregator to handle, from the residual gas 84 of hydrogen gas segregator discharge) is imported into carbon dioxide fixation device 65.
The sodium carbonate that is generated in carbon dioxide fixation device 65 is discharged as waste liquid (containing sodium carbonate liquor) 89 from carbon dioxide fixation device 65, and it preferably carries out purifying and is removed as high-purity carbonic acid sodium in sodium carbonate purification step (not shown).For this purpose, in containing in the sodium carbonate liquor 89 in the component except that anhydrating that carbon dioxide fixation device 65 is produced, carbonate content is preferably 80～99.9% weight, more preferably 95% weight or higher.If less than 80% weight, can be difficult to improve the purity of the sodium carbonate that in sodium carbonate purification step (not shown), is obtained.
In order to improve the purity of sodium carbonate that purifying obtains by this method, be desirably in when using carbon dioxide fixation device 65, utilize highly purified NaOH and carbon dioxide reaction.Especially, join in the outer component (when fixative 88 does not contain water, the total amount of fixative 88) that dewaters in the fixative 88 of carbon dioxide fixation device 65, the content of NaOH is preferably 80～99.9% weight, more preferably 95% weight or higher.If less than 80% weight, can be difficult to improve purity by the sodium carbonate that is obtained in the purifying.As fixative 88, can use above-mentioned sodium hydrate aqueous solution, perhaps also can use molten sodium hydroxide.When using sodium hydrate aqueous solution as fixative 88, the content of NaOH in sodium hydrate aqueous solution is preferably 30～95% weight.If less than 30%, because the NaOH of low concentration, carbon dioxide may be not enough to abundant reaction, contains high carbon dioxide concentration in the gas that causes discharging from the carbon dioxide fixation device.If be higher than 95% weight, the flowability of NaOH can since the high viscosity of solution and destroyed, it can cause being difficult to effectively react with carbon dioxide.
Use the purification step (not shown) that the sodium carbonate liquor 68 that contains that discharges from carbon dioxide fixation device 65 is carried out purifying, resulting sodium carbonate purity is preferably 98～99.9% weight, more preferably 99.0% weight or more than.The sodium carbonate of 98% weight or above purity needing can be used for the field of high-purity carbonic acid sodium, for example optical glass, medical supply and similar.The purity of sodium carbonate is preferably high as much as possible.The content of sodium carbonate in whole aqueous sodium carbonate 89 is preferably 60～95% weight.If be lower than 60% weight, can be difficult to obtain crystals of sodium carbonate because the concentration of sodium carbonate is low.If be higher than 95% weight, owing to the resulting crystals of sodium carbonate slurry of crystallize sodium carbonate excessive concentration causes mobile destruction.
As the purification process that contains sodium carbonate liquor 89 that carbon dioxide fixation device 65 discharges, cause the crystals of sodium carbonate precipitation and from mother liquor the method for the sodium carbonate of precipitation separation be preferred.Sodium carbonate preferably carries out purifying by the purification step (not shown), comprise and use the crystallizer (not shown) from contain sodium carbonate liquor 89, precipitating crystals of sodium carbonate, and the crystals of sodium carbonate that generated from mother liquor, to be separated in the crystallizer of filter (not shown).
Then, the generator of the present invention that is equipped with above-mentioned fuel cell is described.Fig. 3 is the schematic block follow diagram of an execution mode of generator of the present invention.As shown in Figure 3, a kind of generator 200 of the present invention comprises fuel cell 141, it has negative electrode 142, anode 143 and the dielectric substrate that contains fused carbonate 144 between negative electrode 142 and anode 143, comprise that also the cathode gas 151 that will contain oxygen and carbon dioxide supplies to the cathode gas supply arrangement 190 of negative electrode 142, and the anodic gas 153 that will contain hydrogen supplies to the anodic gas supply arrangement 195 of anode 143, by cathode gas 151 being supplied to negative electrode 142 and anodic gas 153 being supplied to anode 143 to produce electric energy, wherein cathode gas supply arrangement 190 has furnace exhaust supply arrangement 191, it can supply with the furnace exhaust 172 of industrial furnace (sintering furnace) the 100a release of heating material for negative electrode 142, and/or the negative electrode supply arrangement 192 of gas, it can supply to negative electrode 142 with gas 173 with negative electrode, the cathode gas 151 that supplies to negative electrode 142 by cathode gas supply arrangement 190 comprises the furnace exhaust 172 that loads and transports by furnace exhaust supply arrangement 191, perhaps furnace exhaust 172 and cathode gas 173 that transports with gas feeding apparatus 192 by negative electrode or the mist 172a of negative electrode usefulness preheating gas 173b, perhaps negative electrode preheating gas 173b, this negative electrode preheating gas is a kind of negative electrode gas that uses furnace exhaust 172 as the thermal source preheating, and concentration of carbon dioxide is 0.1～50% volume in the cathode gas.
In execution mode, when cathode gas 151 is furnace exhaust 172 or mist 172a, industrial furnace is sintering furnace 100a preferably, it comes heating material by the burning gases that combustion fuel 171 is produced, and furnace exhaust 172 is the waste gas (burnt gas) of burning gases and/or the decomposition gas that decomposition produced (waste gas decomposition) by contained organic material in material-to-be-heated.
Fuel 171 is the fuel of hydrocarbonaceous preferably.
The fuel 171 preferred at least a fuel that are selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil of hydrocarbonaceous.
Generator preferably also is furnished with catalyst combustion chamber 142a, and the cathode gas 151 preferred catalyst combustion chamber 142a that use heat.
The anode waste gas 154 that the thermal source of catalyst combustion chamber 142a preferably discharges from anode 143.
Generator preferably also disposes heat exchanger 173a, and preferably uses furnace exhaust 172 to carry out preheating as the thermal source target with preheating gas 173 by heat exchanger 173a.
Preferably, generator further disposes steam reformer 163, and cathode gas 153 uses contained hydrogen in the reformation gas of reforming 182 in steam reformer 163.
Other composition of generator, service condition and similar method of operation with fuel cell that discussed and fuel cell are identical.For example, although do not show that in Fig. 3 generator can further be equipped with hydrogen gas segregator shown in Figure 2 64, carbon dioxide fixation device 65 and similar.Can adopt these equipment, service condition and similar reach identical effect.
Fuel cell of the present invention, the method of operation of fuel cell, sintering furnace and generator, supply with the gas of following high carbon dioxide concentration for negative electrode, and do not need the process of concentration of carbon dioxide in the condensed air, and the heat of recovery furnace waste gas effectively, therefore reduced fuel consumption, wherein, a kind of gas comprises: be used for ceramic industry sintered ceramic and the similar furnace exhaust that sintering furnace discharged (burnt gas and/or waste gas decomposition), furnace exhaust and negative electrode are used the mist of preheating gas with gas or negative electrode, perhaps negative electrode preheating gas, this negative electrode preheating gas is a kind of negative electrode gas that uses furnace exhaust as the thermal source preheating.So the method for operation of fuel cell of the present invention, fuel cell, sintering furnace and generator are effectively applied in the manufacturing of molten carbonate fuel cell and generator, and use in each industrial circle of molten carbonate fuel cell and generator.

Claims (18)

1. sintering furnace, it comprises that the hydrocarbon containing fuels that is used to burn is to produce combustion chamber, sintering furnace main body and the fuel cell of burning gases, wherein the sintering furnace main body is used for by wherein material of burning gases heating and sintering, and discharges as the burnt gas of furnace exhaust and/or the waste gas decomposition that decomposition produced of material-to-be-heated contained organic material, and described fuel cell is arranged so that the furnace exhaust of sintering furnace main body release is used as cathode gas and supplies to cathode side;
This fuel cell comprises negative electrode, anode and the dielectric substrate that between negative electrode and anode, contains fused carbonate, the cathode gas that supplies to cathode side contains oxygen and carbon dioxide, supplying to anode-side is anodic gas with the gas that contains hydrogen that produces electric energy, wherein cathode gas is a kind of gas, contain above-mentioned furnace exhaust, perhaps furnace exhaust and negative electrode are with the mist of gas, perhaps furnace exhaust and negative electrode are with the mist of preheating gas, the negative electrode gas that this negative electrode is to use furnace exhaust to be preheated as thermal source with preheating gas, and concentration of carbon dioxide is 0.1～50% volume in the cathode gas.
2. according to the sintering furnace of claim 1, wherein use catalyst combustion chamber target gas to carry out preheating.
3. according to the sintering furnace of claim 2, wherein the thermal source of catalyst combustion chamber is the anode waste gas that discharges from anode.
4. according to the sintering furnace of claim 1, further comprise steam reformer, to produce the steam reforming reaction of reformed gas, this reformed gas contains and comes from hydrogen and the carbon dioxide that enters into stove and steam hydrocarbon.
5. according to the sintering furnace of claim 4, wherein steam reformer comprises low temperature reformation part, it has and is used to the metal reaction pipe or the ceramic reaction tube that cause that steam reforming reaction takes place therein, with be packaged in the reforming catalyst that is used to quicken steam reforming reaction in the reaction tube, steam reformer also comprises high temperature reformation part, and it has and is used to the ceramic reaction tube that causes that steam reaction reacts therein.
6. according to the sintering furnace of claim 4, wherein steam reformer is installed in sintering furnace main body and/or the furnace exhaust circulation road, and low temperature reforming section branch is arranged on and is heated to 600～1,000 ℃ position, high temperature reforming section branch is arranged on and is heated to 1,000～1,800 ℃ position.
7. according to the sintering furnace of claim 4, the some or all of hydrogen that wherein is included in the reformation gas is to use as anodic gas.
8. according to the sintering furnace of claim 4, further comprise hydrogen gas segregator, be used for optionally Hydrogen Separation being entered the hydrogen fuel from reformed gas that steam reformer forms, by introducing reformed gas to it, this hydrogen fuel comprises the hydrogen and the residual gas that contains carbon dioxide as key component.
9. sintering furnace according to Claim 8 further comprises the carbon dioxide fixation device with the carbon dioxide in the fixing isolated residual gas of hydrogen gas segregator, and/or fixed packet is contained in the carbon dioxide in the anode waste gas that molten carbonate fuel cell discharges.
10. according to the sintering furnace of claim 1, wherein the sintering furnace main body is introduced material continuously and is heated, and continuously with heated material output.
11. according to the sintering furnace of claim 1, wherein, described cathode gas is described furnace exhaust.
12. the dielectric substrate that the method for operation of a fuel cell, this fuel cell are equipped with negative electrode, anode and contain fused carbonate between negative electrode and anode,
This method comprises:
The cathode gas that will contain oxygen and carbon dioxide supplies to cathode side,
The anodic gas that will contain hydrogen supplies to anode-side with the generation electric energy,
Wherein cathode gas is a kind of gas, it contains the furnace exhaust that industrial furnace discharged or the mist of this furnace exhaust and negative electrode usefulness gas or the mist of this furnace exhaust and negative electrode usefulness preheating gas of heating material, the negative electrode gas that this negative electrode is to use furnace exhaust to be preheated as thermal source with preheating gas, and concentration of carbon dioxide is 0.1～50% volume in the cathode gas;
The burning gases that described industrial furnace is to use combustion fuel to produce come the sintering furnace of heating material, described furnace exhaust be burning gases burnt gas and/or material-to-be-heated in the decomposition gas that decomposition produced of contained organic material.
13. according to the method for claim 12, wherein fuel is the fuel of hydrocarbonaceous.
14. according to the method for claim 13, wherein the fuel of hydrocarbonaceous is selected from domestic gas, liquefied natural gas, liquefied petroleum gas, diesel oil and heavy oil.
15., wherein use catalyst combustion chamber target gas to carry out preheating according to the method for claim 12.
16. according to the method for claim 15, wherein the thermal source of catalyst combustion chamber is the anode waste gas that discharges from anode.
17. according to the method for claim 12, wherein, cathode gas contains negative electrode when using preheating gas, the negative electrode preheating gas is by using described furnace exhaust to carry out preheating as the heat exchanger of thermal source.
18. according to the method for claim 12, wherein anodic gas uses contained hydrogen in the reformation gas, this reformation gas is to reform in the steam reformer on being installed on industrial furnace.
CNB2005101302531A 2004-12-13 2005-12-12 Fuel cell, operating method thereof, sintering furnace, and power generator Expired - Fee Related CN100440596C (en)

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JPH0589899A (en) * 1991-09-27 1993-04-09 Hitachi Ltd Internal reforming type fused carbonate fuel cell and operation thereof
JPH0963608A (en) * 1995-08-18 1997-03-07 Ishikawajima Harima Heavy Ind Co Ltd Fuel cell power generating system
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CN1039002A (en) * 1988-07-01 1990-01-24 赫多特普索化工设备公司 Make the method for ammonia
CN1050338A (en) * 1989-09-19 1991-04-03 石川岛播磨重工业株式会社 Utilize and reclaim the method and apparatus of carbonic acid gas in the combustion exhaust
JPH0589899A (en) * 1991-09-27 1993-04-09 Hitachi Ltd Internal reforming type fused carbonate fuel cell and operation thereof
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