CN101436672A - Fuel battery generating system and method - Google Patents
Fuel battery generating system and method Download PDFInfo
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- CN101436672A CN101436672A CNA2007101703837A CN200710170383A CN101436672A CN 101436672 A CN101436672 A CN 101436672A CN A2007101703837 A CNA2007101703837 A CN A2007101703837A CN 200710170383 A CN200710170383 A CN 200710170383A CN 101436672 A CN101436672 A CN 101436672A
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/755—Nickel
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a system and a method for generating electricity for a fuel cell. The system for generating electricity for the fuel cell uses hydrocarbons as raw materials to generate electricity and comprises a raw material feeder, a reforming hydrogen production device, the fuel cell, and a positive pole outlet gas circulation device for circulating the positive pole outlet gas of the fuel cell to an inlet of the reforming hydrogen production device. Through circulating CH4 and CO2 in the positive pole outlet gas, the system for generating electricity reduces the reforming reaction temperature required by the hydrocarbons to reach certain conversion rate and inhibits the sintering and the carbon deposition of a reforming catalyst to reach the effects of prolonging the service life of the reforming catalyst, in particular of a low-cost Ni series reforming catalyst.
Description
Technical field
The present invention relates to fuel cell generation and method, particularly relating to a kind of is the Proton Exchange Membrane Fuel Cells electricity generation system and the method for raw material with the hydrocarbon.
Background technology
The fuel cell generation that with hydrogen is fuel has the feature of clean and effective, thereby has been one of the research focus in distributed energy field from last century since the nineties always.Hydrogen is a kind of secondary energy sources, is converted by various primary energy.Therefore, for being the fuel cell plant of raw material with the fossil fuel, the hydrogen source systems technology that fossil fuel is converted into the hydrogen that satisfies the fuel cell power generation requirement is very important.Among many hydrogen manufacturing approach, because hydrocarbon prices such as natural gas are lower, the industrial technology of gas renormalizing hydrogen manufacturing is very ripe, and gas renormalizing hydrogen manufacturing is considered to the most economically viable selection in the quite a while from now on.; middle-size and small-size fuel cell plant below the 100kW level is the hydrogen source system in Proton Exchange Membrane Fuel Cells (PEFC) cogeneration of heat and power power station especially; since in hydrogen production efficiency, reformer hydrogen CO content, reliability and stability, startup stops and the aspects such as following characteristic, compactedness and useful life of loading all must satisfy new more harsh requirement, is a frontier different with traditional industrial reforming hydrogen producing technology.
In gas water vapour reforming hydrogen producing process, catalyst is one of key factor that influences system cost and life-span.Because have active high, advantage such as easy-sintering carbon distribution not under required working temperature, the hydrogen source system in PEFC cogeneration of heat and power power station adopts the Ru series catalysts as reforming catalyst usually., because the resource scarcity of metal Ru, the market price is expensive and fluctuation is very big, the problem that caused reformation hydrogen production cost height, has a big risk.
The Ni series catalysts is industrial the most frequently used steam reforming catalyst, compare with the Ru series catalysts have aboundresources, cheap advantage, but the shortcoming of active lower, easy-sintering carbon distribution is arranged also.To replace the Ru series catalysts as the steam reforming catalyst with the Ni series catalysts, normally attempt waiting the approach that improves its anti-sintering anti-carbon performance by the chemical composition or the preparation method that improve the Ni series catalysts, as (Matsumura Yasuyuki such as Matsumura Yasuyuki, Nakamori Toshie.Steamreforming of methane over nickel catalyst at low reaction temperature.AppliedCatalysis A:General, 2004,258:107-114), by adopting different carriers to improve the performance of Ni series catalysts.
To have cheap, ripe industrial Ni series catalysts now in order making full use of, and further to improve the efficient of hydrocarbon vapor reforming hydrogen production, the present invention proposes a kind of is the fuel cell generation and the method for raw material with the hydrocarbon.
Summary of the invention
In order to solve the problem that existing fuel cell generation and method are brought owing to required reformation working temperature height, and problem such as reformation hydrogen production efficient is low, the inventor has carried out intensive theoretical modeling and experimental study, and obtained by CH4, CO2, H2 and water steam during anode of fuel cell is worked off one's feeling vent one's spleen to of the gas composition of reforming hydrogen production device inlet with change reforming hydrogen production device inlet, can reach and reduce required reformation working temperature, improve the Research on effect result of reformation hydrogen production efficient simultaneously.The purpose of this invention is to provide a kind of new fuel cell generation and method, specifically, when an object of the present invention is to reduce the material carbon hydrogen compound and carrying out steam reforming in order to reach certain required reforming reaction temperature of conversion ratio, thereby can adopt the catalyst of cheap Ni series catalysts as reforming reaction, and reduce requirement, thereby be suitable for practicality more to structure of reactor material corrosion-and high-temp-resistant.Another object of the present invention is to save to be specifically designed to reformation water feeder and the heat of evaporation thereof that imports the required water of reforming reaction to reforming reactor, thereby reaches the purpose of simplified system and raising reformation hydrogen production efficient.
Purpose of the present invention and solve its technical task and realize by the following technical solutions.According to a kind of of the present invention's proposition is the fuel cell generation that raw material generates electricity with the hydrocarbon, it comprises raw material feed device, reforming hydrogen production device and fuel cell, it also comprises anode export gas circulating device, is used for the anode export gas of fuel cell is circulated to the reforming hydrogen production device inlet.Described reforming hydrogen production device according to connection fuel cell to the requirement of reformer hydrogen, can only contain reforming reactor and burner, also can comprise reforming reactor and burner and CO shift-converter and then also can comprise reforming reactor and burner, CO shift-converter and CO and remove reactor.
Purpose of the present invention and solve its technology and ask that problem also can be applied to the following technical measures to achieve further.
Preferably, aforesaid fuel cell generation, wherein said anode export gas circulating device comprises anode export gas storage tank, gas pressurized device and flowmeter.
Preferably, aforesaid fuel cell generation, it is reforming catalyst that the reforming reactor of wherein said reforming hydrogen production device adopts Ni.
Preferably, aforesaid fuel cell generation, it also comprises desulfurizer, is arranged at before the reforming hydrogen production device, is used for removing the sulphur of raw material.
Preferably, aforesaid fuel cell generation, it also comprises the reformation water feeder that is used for importing to reforming hydrogen production device the required water of reforming reaction.
Purpose of the present invention and solve its technical task and also adopt following technical scheme to realize.Is the fuel cell power generation method that raw material generates electricity according to a kind of of the present invention's proposition with the hydrocarbon, it is characterized in that it comprises following steps:
The material carbon hydrogen compound with after anode export gas mixes, is imported reforming hydrogen production device and carries out the reaction of hydrocarbon reformation hydrogen production with the preparation reformer hydrogen;
Above-mentioned reformer hydrogen is imported fuel cell to generate electricity; And
The anode export gas of fuel cell is circulated to the inlet of reforming hydrogen production device.
Preferably, aforesaid fuel cell power generation method, wherein with described anode export gas shunting, the anode export gas of being shunted enters burner and burns, and is used for providing the hydrocarbon reforming reaction required heat to reforming hydrogen production device.
Preferably, the ratio of the molar flow of carbon is 4.0 to 10.0 in the aforesaid fuel cell power generation method, the molar flow of the wherein said anode export gas that is circulated to reforming hydrogen production device inlet and material carbon hydrogen compound, the CH of anode export gas
4, H
2And CO
2Mole percent level be respectively 10～35%, 10～35% and 10～30%, make CH in the anode export gas
4Molar flow and material carbon hydrogen compound in the ratio of molar flow of carbon be 0.5～3.5, in the anode export gas in molar flow and the material carbon hydrogen compound of hydrogen the ratio of the molar flow of carbon be 0.5～3.5, in the anode export gas in molar flow and the material carbon hydrogen compound of steam the ratio of the molar flow of carbon be 1.5～4.0.
Preferably, aforesaid fuel cell power generation method, it is included in before the reformation hydrogen production reactions steps, and material carbon hydrogen compound and anode export gas are mixed the step that back importing desulfurizer carries out desulfurization.
Preferably, aforesaid fuel cell power generation method, it is reforming catalyst that wherein said reforming reaction adopts Ni.
Preferably, aforesaid fuel cell power generation method, the reaction temperature of wherein said reforming reaction is 560～660 ℃.
Purpose of the present invention and solve its technical task and also adopt following technical scheme to realize.Is the fuel cell power generation method that raw material generates electricity according to a kind of of the present invention's proposition with the hydrocarbon, and it comprises following steps:
After reformation water, material carbon hydrogen compound and the mixing of anode export gas, import reforming hydrogen production device and carry out the reformation hydrogen production reaction of hydrocarbon with the preparation reformer hydrogen;
Above-mentioned reformer hydrogen is imported fuel cell to generate electricity; And
The anode export gas of fuel cell is circulated to the inlet of reforming hydrogen production device.
The reaction of described reformation hydrogen production according to connection fuel cell to the requirement of reformer hydrogen, can only contain the reforming reaction step, also can comprise reforming reaction step and CO shift-reaction step and then also can comprise reforming reaction step, CO shift-reaction step and CO removal reactions steps.
Purpose of the present invention and solve its technical task and also can be applied to the following technical measures to achieve further.
Preferably, aforesaid fuel cell power generation method, wherein with described anode export gas shunting, the anode export conductance of being shunted is gone into burner and is burnt, and is used for providing the hydrocarbon reforming reaction required heat to reforming hydrogen production device.
Preferably, aforesaid fuel cell power generation method, the ratio of the molar flow of carbon is 1.5～8.0 in the molar flow of the wherein said anode export gas that is circulated to reforming hydrogen production device inlet and the material carbon hydrogen compound, and it is 10～35% CH that the anode export gas bag contains molar percentage
4, 10～35% H
2With 15～30% CO
2
Preferably, aforementioned fuel cells electricity-generating method, CH in the wherein said anode export gas that is circulated to reforming hydrogen production device inlet
4Molar flow and material carbon hydrogen compound in the ratio of molar flow of carbon be 0.2～3.0, in the anode export gas in molar flow and the material carbon hydrogen compound of hydrogen the ratio of the molar flow of carbon be 0.2～3.0.
Preferably, aforesaid fuel cell power generation method, it also comprises: before the reforming reaction step, with the step of carrying out desulfurization after material carbon hydrogen compound and the mixing of anode export gas.
Preferably, aforesaid fuel cell power generation method, it is reforming catalyst that wherein said reforming reaction adopts Ni.
Preferably, aforesaid fuel cell power generation method, the reaction temperature of described reforming reaction is 560～660 ℃.
The material carbon hydrogen compound is selected from following material described in above-mentioned each technical scheme of the present invention: fossil fuels such as methane, natural gas, liquefied petroleum gas, kerosene, diesel oil, methyl alcohol, GTL and DME also are selected from biomass energies such as biogas, refuse gasification gas and ethanol etc.Described fuel cell comprises Proton Exchange Membrane Fuel Cells (PEFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC) and Solid Oxide Fuel Cell (SOFC) etc.
Ni of the present invention is that reforming catalyst is the reforming catalyst that its active component comprises metal Ni, and there is no particular restriction for its auxiliary agent, carrier and form, and auxiliary agent can comprise CeO
2, La
2O3, K
2O etc., its carrier comprises Al
2O3, ZrO
2, SiO
2And TiO
2Comprise graininess such as spherical, cylindric and cellular etc. Deng, its form.
By technique scheme, fuel cell generation of the present invention and method have following advantage at least:
1, one aspect of the present invention, the CH in working off one's feeling vent one's spleen by circulating anode
4And CO
2Reduce the material carbon hydrogen compound and reach the set required reforming reaction temperature of conversion ratio, thereby the sintering and the carbon distribution that suppress reforming catalyst, and then reach prolong reforming catalyst, especially cheap Ni is the useful life of reforming catalyst, and prolongs the reforming reactor structural material effect in useful life;
2, another aspect of the present invention, the H in working off one's feeling vent one's spleen by circulating anode
2, suppress the carbon distribution of reforming catalyst, be the reforming catalyst effect in useful life thereby reach prolongation reforming catalyst, the especially Ni of cheapness;
3, another aspect of the present invention, steam in working off one's feeling vent one's spleen by circulating anode, the steam that fuel cell reaction generated effectively is used in the reforming reaction of material carbon hydrogen compound, thereby reduce and even save the required reformation evaporation of water of reforming reaction heat fully, and then reach the effect that improves reformation hydrogen production efficient.
In sum, the fuel cell generation of special construction of the present invention and method, it has above-mentioned many advantages and practical value, thereby is suitable for practicality more.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Description of drawings
Fig. 1 and Fig. 2 are the flow charts of Proton Exchange Membrane Fuel Cells electricity generation system of the present invention;
Fig. 3 and Fig. 4 are the flow charts that contains the Proton Exchange Membrane Fuel Cells electricity generation system of desulfurizer of the present invention;
Fig. 5 is the flow chart of existing Proton Exchange Membrane Fuel Cells electricity generation system.
1: reforming hydrogen production device
1a reforming reactor 2:CO shift-converter
3:CO removes reactor 4: Proton Exchange Membrane Fuel Cells
4a: anode of fuel cell 4b: fuel battery negative pole
5: circulating air basin 6: supercharging device
7: adjuster valve 8a, 8b: flowmeter
9: anode export gas circulating device
10: burner 11: raw material
12: reformation water basin 13: water pump
14: reformation water gasifier 15: reformation water feeder
16: desulfurizer
Embodiment
Reach technological means and the effect that goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, to fuel cell generation and method embodiment, structure, feature and the effect thereof that foundation the present invention proposes, describe in detail as after.
Fig. 1 is the flow chart of Proton Exchange Membrane Fuel Cells electricity generation system one embodiment of the present invention.It is that raw material generates electricity that this Proton Exchange Membrane Fuel Cells electricity generation system adopts natural gas, comprise by reforming reactor 1a and burner 10, CO shift-converter 2, CO removes reforming hydrogen production device 1 and the Proton Exchange Membrane Fuel Cells 4 that reactor 3 constitutes, compare with existing Proton Exchange Membrane Fuel Cells electricity generation system shown in Figure 5, fuel cell generation of the present invention also comprises by circulating air basin 5, the anode export gas circulating device 9 that supercharging device 6 and flowmeter 8a form is used for the anode export gas of Proton Exchange Membrane Fuel Cells is circulated to reforming hydrogen production device 1 inlet.Wherein, filling Ni among the reforming reactor 1a is reforming catalyst, and this catalyst is the catalyst described in the background technology, and it belongs to prior art, so repeat no more; The reaction mass of reforming reactor outlet enters CO shift-converter 2, and the CO content in transformationreation shift-converter 2 outlet reaction masses significantly reduces; Then CO shift-converter 2 outlet reaction masses enter CO and remove reactor 3, and removing reaction CO through CO, to remove reactor 3 outlet reaction masses be that CO content in the reformer hydrogen is reduced to and satisfies the degree that 4 pairs of fuel gas of Proton Exchange Membrane Fuel Cells require; Then reformer hydrogen enters the anode 4a of Proton Exchange Membrane Fuel Cells 4, thereby generates electricity with the air generation cell reaction that enters negative electrode 4b.Anode 4a discharges and contains H
2, CH
4, CO
2Anode export gas with steam etc.The part of anode export gas is shunted and is imported burner 10 and burnt, the reforming reaction heat of supplying raw materials for reforming hydrogen production device 1.Enter reforming reactor 1a after raw material mixes with the anode export gas that is circulated to the reforming hydrogen production device inlet and carry out reforming reaction.Because utilized steam in the anode gas, present embodiment need not to be provided with the reformation water feeder, thereby simplified system constitutes and saves the required heat of evaporation of reformation water.
Fig. 2 is the flow chart of another preferred embodiment of Proton Exchange Membrane Fuel Cells electricity generation system of the present invention.Proton Exchange Membrane Fuel Cells electricity generation system in the present embodiment, it comprises also that reformation water feeder 15 is used for providing to reforming hydrogen production device 1 and carries out the needed water of reforming reaction, this feedway 15 comprises reformation water basin 12, water pump 13 and reformation water gasifier 14.Like this, help in the anode gas of circulation water vapour content to take place to guarantee that reforming hydrogen production device 1 can have stable water source supply when fluctuation or water vapour content are low.
Fig. 3 and Fig. 4 are the flow chart of the present invention corresponding to the Proton Exchange Membrane Fuel Cells electricity generation system that contains desulfurizer of Fig. 1 and Fig. 2.Need the raw material of desulfurization for some, the present invention can set up desulfurizer 16 before reforming hydrogen production device 1.
The above-mentioned fuel cell generation that each embodiment proposed of the present invention, owing to be provided with anode export gas circulating device, can use cheap Ni series catalysts and improve hydrogen production efficiency, thereby can reduce the cost of Proton Exchange Membrane Fuel Cells electricity generation system and improve its energy efficiency.
Experimental technique
The present invention proposes a kind of fuel cell power generation method, it adopts above-mentioned fuel cell generation to be realized, this method may further comprise the steps: the material carbon hydrogen compound with after anode export gas mixes, is imported reforming hydrogen production device and carries out the reformation hydrogen production reaction of hydrocarbon with the preparation reformer hydrogen; Above-mentioned reformer hydrogen is imported fuel cell generate electricity, this step can adopt existing fuel cell power generation method; And the anode export gas of fuel cell is circulated to the reforming hydrogen production device inlet.This method is circulated to the reforming hydrogen production device inlet by the anode export gas with fuel cell, with carry out reforming reaction after raw material mixes, because the anode export gas of fuel cell contains steam, so reforming reaction process does not in the present embodiment need the supplying step of specialized designs reformation water.The response data of present embodiment all is that benchmark calculates with the raw material as the conversion ratio of air speed, steam/hydrocarbons ratio, reforming reaction.Present embodiment is raw material with the natural gas, and it is reforming catalyst (Ni-TiO that the reforming reaction of reforming hydrogen production device adopts spherical commercial Ni
2/ Al
2O
3, NiO 18%), fuel cell adopts Proton Exchange Membrane Fuel Cells.The ratio that is circulated to the molar flow of carbon in molar flow and the raw material of anode export gas of reforming hydrogen production device inlet is defined as the circular flow ratio.The Control Circulation flow-rate ratio is 4.0～10.0, and a part of anode export gas is branched to burner and burns, for the reforming reaction of raw material provides heat.The anode export gas bag contains the CH of molar content 10～35%
4, 10～35% H
2, 10～30% CO
2And steam, make CH in the anode export gas be circulated to the reforming hydrogen production device inlet
4Molar flow and raw material in the ratio of molar flow of carbon be that the cyclic carbon carbon ratio is 0.5～3.5, the ratio of the molar flow of carbon is that the recycle hydrogen carbon ratio is 0.5～3.5 in molar flow and the raw material of hydrogen in the anode export gas, the ratio of the molar flow of carbon is that the recirculated water carbon ratio is 1.5～4.0 in the molar flow that is circulated to steam in the anode export gas of reforming hydrogen production device inlet and the raw material.The CH of this anode export gas
4, H
2And CO
2Content can be regulated by the hydrogen utilization ratio of control reforming reaction temperature and anode of fuel cell reaction, and water vapour content can be regulated by the working temperature of fuel cell.The temperature of reforming reaction is advisable with 560～660 ℃ scope, and the raw material air speed is advisable with the scope of 200～800/h.
The invention allows for a kind of is the fuel cell power generation method of raw material with the hydrocarbon, and it adopts the electricity generation system of the above embodiment of the present invention to be realized.Present embodiment may further comprise the steps: a mixes back importing reforming hydrogen production device with reformation water, natural gas and anode export gas and carries out the reformation hydrogen production reaction with the preparation reformer hydrogen; B imports fuel cell with reformer hydrogen and generates electricity; And c is circulated to the reforming hydrogen production device inlet with the anode export gas of fuel cell.Above-mentioned steps b and existing fuel cell power generation method are basic identical, so repeat no more.This method is circulated to the reforming hydrogen production device inlet through circulating device with anode export gas, mixes with raw material, and desulfurization was carried out before this gaseous mixture enters reforming hydrogen production device.The Control Circulation flow-rate ratio is 1.5～8.0, and a part of anode export gas is branched to burner and burns, for the reforming reaction of raw material provides heat.The anode export gas bag contains the CH of molar content 10～35%
4, 10～35% H
2, 10～30% CO
2And steam, make that the cyclic carbon carbon ratio is 0.2～3.0, the recycle hydrogen carbon ratio is 0.2～3.0.The CH of this anode export gas
4, H
2And CO
2Content can be regulated by the hydrogen utilization ratio of control reforming reaction temperature and anode of fuel cell reaction, and water vapour content can be regulated by the working temperature of fuel cell.The temperature of reforming reaction is advisable with 560～660 ℃ scope, and the raw material air speed is advisable with the scope of 200～800/h.
Preferable, can also comprise in the above-described embodiment: before the reformation hydrogen production reactions steps, raw material is mixed the back import the step that desulfurizer carries out desulfurization with anode export gas.Concrete sulfur removal technology parameter can adopt prior art to finish.
The present invention is to the principal component CH of natural gas
4The steam reforming process comprise the CH of reaction equation (1)
4The CO transformationreation of steam reforming reaction and reaction equation (2):
CH
4+H
2O→CO+3H
2ΔH
298 0＝206kJmol
-1 (1)
CO+H
2O→CO
2+H
2ΔH
298 0＝-41kJmol～
1 (2)
Raw material CH
4The calculating formula of conversion ratio is as follows:
Raw material CH
4Conversion ratio=1-(CH in the product
4Flow-circulating air in CH
4Flow)/raw material CH
4Flow (3)
CH
4Steam reforming reaction is a strong endothermic reaction, and the reforming reaction working temperature is higher, CH
4Conversion ratio is just higher.As the formula (1), CH in product
4Flow is greater than the circulating anode middle CH that works off one's feeling vent one's spleen
4Raw material CH during flow
4Conversion ratio is less than 1, CH in product
4Flow equals the circulating anode middle CH that works off one's feeling vent one's spleen
4Raw material CH during flow
4Conversion ratio equals 1, i.e. raw material CH
4Obtained 100% conversion.And in the product CH
4Flow is less than the circulating anode middle CH that works off one's feeling vent one's spleen
4Raw material CH during flow
4Conversion ratio that is to say greater than 1, except raw material CH
4Outside, the portion C H during circulating anode is worked off one's feeling vent one's spleen
4Conversion has also taken place, and the present invention makes it conversion ratio not take place greater than 1 situation by the condition of control reforming reaction.
Before fuel cell generation of the present invention brings into operation, fill with definite composition (CH in anode export gas circulating device and reforming hydrogen production device and connecting line thereof in advance
4: 10～35%, H
2: 10～35%, CO
2: gas 10～30%) reaches the required time of stable state with the work of shortening this system.
Present embodiment is set reformation discharge and is 0, does not promptly have special reformation water supplying step, raw material CH
4Air speed is that 400/h, Proton Exchange Membrane Fuel Cells working temperature are 75 ℃.Raw material CH
4Conversion ratio is that 90% o'clock experimental result sees Table 1.
Table 1
The circular flow ratio of experiment sequence number 1 is 0 in the table 1, and promptly this is tested and is comparative test of the present invention.As seen result by comparative experiments sequence number 2～9 and comparative test adopts fuel cell generation of the present invention and method, can significantly reduce material carbon hydrogen compound (CH
4) reach certain required reforming reaction temperature of conversion ratio (90%), and can save special reformation water feeder, reformation water and heat of evaporation thereof.
Present embodiment experimentizes according to above-mentioned experimental technique.Table 2 is raw material CH
4Air speed is that 400/h, Proton Exchange Membrane Fuel Cells working temperature are that 75 ℃, steam/hydrocarbons ratio are 3.0, raw material CH
4Conversion ratio is 90% o'clock a experimental result.
The molar flow sum of steam is divided by the molar flow of carbon in the raw material in the molar flow of the reformation water that the steam/hydrocarbons ratio in the table 2 is supplied with for the reformation water feeder and the circulating air.
Table 2
The circular flow ratio of experiment sequence number 1 is 0 in the table 2, and promptly this is tested and is comparative test of the present invention.As seen result by comparative experiments sequence number 2～7 and comparative test adopts fuel cell generation of the present invention and method, can significantly reduce material carbon hydrogen compound (CH
4) reach certain required reforming reaction temperature of conversion ratio (90%).
The fuel cell generation of the present invention that above-mentioned structure like this constitutes and the technological innovation of method have many saving graces for technical staff of the same trade now, and possess skills really novelty, progressive and practicality.The other technologies details of not described in detail among the embodiment of the present invention, those skilled in the art all can adopt corresponding scheme of the prior art to realize.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention,, all still belong within the scope of technical solution of the present invention any simple modification, equivalent variations that above embodiment did according to technical spirit of the present invention.
Claims (17)
1, a kind of is the fuel cell generation that raw material generates electricity with the hydrocarbon, it is characterized in that it comprises: raw material feed device, reforming hydrogen production device, fuel cell and anode export gas circulating device are used for the anode export gas of fuel cell is circulated to the inlet of reforming hydrogen production device.
2,, it is characterized in that wherein said anode export gas circulating device comprises anode export gas storage tank, gas pressurized device and flowmeter according to the described fuel cell generation of claim 1.
3,, it is characterized in that the reforming reactor employing Ni of described reforming hydrogen production device is a reforming catalyst according to the described fuel cell generation of claim 1.
4, according to the described fuel cell generation of claim 1, it is characterized in that it also comprises desulfurizer, be arranged at before the reforming hydrogen production device, be used for removing the sulphur of raw material.
5,, it is characterized in that it also comprises the reformation water feeder that is used for importing to reforming hydrogen production device the required water of reforming reaction according to each described fuel cell generation of claim 1～4.
6, a kind of is the fuel cell power generation method that raw material generates electricity with the hydrocarbon, it is characterized in that it comprises following steps:
The material carbon hydrogen compound with after anode export gas mixes, is imported reforming hydrogen production device and carries out the reformation hydrogen production reaction of hydrocarbon with the preparation reformer hydrogen;
Above-mentioned reformer hydrogen is imported fuel cell to generate electricity; And
The anode export gas of fuel cell is circulated to the reforming hydrogen production device inlet.
7,, it is characterized in that the anode export conductance of being shunted is gone into burner and burnt, and is used for providing the hydrocarbon reforming reaction required heat to reforming hydrogen production device with the shunting of anode export gas according to the described fuel cell power generation method of claim 6.
8, according to the described fuel cell power generation method of claim 6, the ratio that it is characterized in that being circulated to the molar flow of carbon in molar flow and the material carbon hydrogen compound of anode export gas of reforming hydrogen production device inlet is 4.0～10.0, the CH of anode export gas
4, H
2And CO
2Mole percent level be respectively 10～35%, 10～35% and 10～30%, make CH in the anode export gas be circulated to the reforming hydrogen production device inlet
4Molar flow and material carbon hydrogen compound in the ratio of molar flow of carbon be 0.5～3.5, in the anode export gas in molar flow and the material carbon hydrogen compound of hydrogen the ratio of the molar flow of carbon be 0.5～3.5, in the anode export gas in molar flow and the material carbon hydrogen compound of steam the ratio of the molar flow of carbon be 1.5～4.0.
9, according to the described fuel cell power generation method of claim 6, it is characterized in that being included in before the reformation hydrogen production reactions steps, material carbon hydrogen compound and anode export gas are mixed the step that back importing desulfurizer carries out desulfurization.
10,, it is characterized in that the reforming reaction employing Ni of described reforming hydrogen production device is a reforming catalyst according to each described fuel cell power generation method of claim 6～9.
11, according to the described fuel cell power generation method of claim 10, the reaction temperature that it is characterized in that reforming reaction is 560～660 ℃.
12, a kind of is the fuel cell power generation method that raw material generates electricity with the hydrocarbon, it is characterized in that it comprises following steps:
After reformation water, material carbon hydrogen compound and the mixing of anode export gas, import reforming hydrogen production device and carry out the reformation hydrogen production reaction of hydrocarbon with the preparation reformer hydrogen;
Above-mentioned reformer hydrogen is imported fuel cell to generate electricity; And
The anode export gas of fuel cell is circulated to the inlet of reforming hydrogen production device.
13, according to the described fuel cell power generation method of claim 12, it is characterized in that described anode export gas shunting, the anode export conductance of being shunted is gone into burner and is burnt, and is used for providing the hydrocarbon reforming reaction required heat to reforming hydrogen production device.
14, according to the described fuel cell power generation method of claim 12, the ratio that it is characterized in that being circulated to the molar flow of carbon in molar flow and the material carbon hydrogen compound of anode export gas of reforming hydrogen production device inlet is 1.5 to 8.0, the CH of anode export gas
4, H
2And CO
2Mole percent level be respectively 10～35%, 10～35% and 10～30%, make CH in the anode export gas be circulated to the reforming hydrogen production device inlet
4Molar flow and material carbon hydrogen compound in the ratio of molar flow of carbon be 0.2～3.0, in the anode export gas in molar flow and the material carbon hydrogen compound of hydrogen the ratio of the molar flow of carbon be 0.2～3.0.
15, according to the described fuel cell power generation method of claim 12, it is characterized in that comprising: before the reformation hydrogen production reactions steps, with the step of carrying out desulfurization after material carbon hydrogen compound and the mixing of anode export gas.
16,, it is characterized in that the reforming reaction employing Ni of described reforming hydrogen production device is a reforming catalyst according to each described fuel cell power generation method of claim 12～15.
17, according to the described fuel cell power generation method of claim 16, the reaction temperature that it is characterized in that reforming reaction is 560～660 ℃.
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| CNA2007101703837A CN101436672A (en) | 2007-11-15 | 2007-11-15 | Fuel battery generating system and method |
| PCT/CN2008/001877 WO2009070976A1 (en) | 2007-11-15 | 2008-11-14 | Fuel cell power generation system and power generating method thereof |
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| CN109546189A (en) * | 2018-10-29 | 2019-03-29 | 南京航空航天大学 | It is a kind of to reform electricity generation system by the multistage of fuel cell hydrogen source of liquid fuel |
| CN110301059A (en) * | 2017-02-23 | 2019-10-01 | 罗伯特·博世有限公司 | Fuel-cell device |
| CN111336510A (en) * | 2020-02-28 | 2020-06-26 | 武汉理工大学 | Porous medium combustion and fuel cell multistage coupling energy system |
| CN113224360A (en) * | 2021-05-14 | 2021-08-06 | 华能（天津）煤气化发电有限公司 | Method and system for producing hydrogen and generating power by co-gasification of coal and biomass |
| CN113581015A (en) * | 2021-06-08 | 2021-11-02 | 北京科技大学 | Safety early warning method and device for fuel cell system |
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| CN111320135A (en) * | 2020-03-31 | 2020-06-23 | 张家港氢云新能源研究院有限公司 | Small-size distributed combined heat and power generation system |
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| JPS59116017A (en) * | 1982-12-22 | 1984-07-04 | Mitsubishi Electric Corp | Device for measuring flow rate of hydrogen in fuel cell power generating system |
| JPH11238520A (en) * | 1998-02-24 | 1999-08-31 | Ishikawajima Harima Heavy Ind Co Ltd | Fuel cell power generating apparatus |
| JP2000331698A (en) * | 1999-05-19 | 2000-11-30 | Ishikawajima Harima Heavy Ind Co Ltd | Fuel cell generating device using gas turbine exhaust gas |
| JP4696513B2 (en) * | 2004-09-27 | 2011-06-08 | トヨタ自動車株式会社 | Fuel cell system |
| JP4593311B2 (en) * | 2005-02-24 | 2010-12-08 | 三菱電機株式会社 | Fuel cell power generation system and method for stopping the same |
| JP2007128680A (en) * | 2005-11-01 | 2007-05-24 | Toyota Central Res & Dev Lab Inc | Fuel cell system |
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| CN110301059A (en) * | 2017-02-23 | 2019-10-01 | 罗伯特·博世有限公司 | Fuel-cell device |
| CN110301059B (en) * | 2017-02-23 | 2022-11-18 | 罗伯特·博世有限公司 | Fuel cell device |
| CN109546189A (en) * | 2018-10-29 | 2019-03-29 | 南京航空航天大学 | It is a kind of to reform electricity generation system by the multistage of fuel cell hydrogen source of liquid fuel |
| CN109546189B (en) * | 2018-10-29 | 2021-10-22 | 南京航空航天大学 | Multi-stage reforming power generation system using liquid fuel oil as hydrogen source of fuel cell |
| CN111336510A (en) * | 2020-02-28 | 2020-06-26 | 武汉理工大学 | Porous medium combustion and fuel cell multistage coupling energy system |
| CN111336510B (en) * | 2020-02-28 | 2021-04-02 | 武汉理工大学 | Porous medium combustion and fuel cell multistage coupling energy system |
| CN113224360A (en) * | 2021-05-14 | 2021-08-06 | 华能（天津）煤气化发电有限公司 | Method and system for producing hydrogen and generating power by co-gasification of coal and biomass |
| CN113581015A (en) * | 2021-06-08 | 2021-11-02 | 北京科技大学 | Safety early warning method and device for fuel cell system |
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