CN100461516C - Natural gas melting carbonate fuel cell generation system - Google Patents
Natural gas melting carbonate fuel cell generation system Download PDFInfo
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- CN100461516C CN100461516C CNB2007100404664A CN200710040466A CN100461516C CN 100461516 C CN100461516 C CN 100461516C CN B2007100404664 A CNB2007100404664 A CN B2007100404664A CN 200710040466 A CN200710040466 A CN 200710040466A CN 100461516 C CN100461516 C CN 100461516C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The power generation system of fuel cell includes three subsystems: adsorption-enhanced subsystem for reforming vapor and methane; fuel cell subsystem of molten carbonate, and subsystem for cyclic utilizing carbon dioxide and tail gas. Through gas inlet pipe and gas outlet pipe, the three subsystems are connected. Combining with MCFC power generation system, the invention uses adsorption-enhanced subsystem for reforming vapor and methane instead of traditional reforming vapor and methane to constitute power generation system of fuel cell of natural gas and molten carbonate. Advantages are: simple system and low energy consumption.
Description
Technical field
What the present invention relates to is the electricity generation system in a kind of fuel cell technology field, and what be specifically related to is a kind of natural gas melting carbonate fuel cell generation system.
Background technology
Natural gas based on methane is that hydrogen/carbon ratio is the highest in the hydro carbons, is one of energy that calorific value is the highest in the fossil fuel.Natural gas is more much smaller than coal and oil to the pollution of environment, the SO that discharges after burning
2And NO
xSeldom, the greenhouse gas CO of generation
2Also less.Therefore, developed country is utilizing substitute gas coal and oil as slowing down CO
2One of important measures of discharge capacity.With natural gas as molten carbonate fuel cell (Molten Carbonate Fuel Cell, MCFC) fuel generates electricity, its major advantage is, be not heated machine Carnot cycle restriction of power generation process, energy conversion efficiency can reach 40%～60%, if realize cogeneration, fuel availability can reach more than 80%; Low pollution emission; Low noise; The reliability height; Modularization; Applied widely etc.
Find through literature search prior art, U.S. Patent number 5082752, name is called " fused carbonate electricity generation system " (" Power generation system using molten carbonate fuel cell ") and has introduced the fused carbonate electricity generation system that acts as a fuel with natural gas.In this patent natural gas is passed through the mode of traditional steam reforming, be transformed into the fuel of Fu Qing, be passed in the anode chamber of MCFC (fused carbonate electricity generation system), electrochemical reaction takes place and produces electric energy in simultaneously bubbling air and carbon dioxide in cathode chamber.Anode exhaust gas and cathode exhaust gas are passed into respectively in the combustion chamber of reformer, and the heat that burning produces is supplied to the reformer chamber of reformer, and the tail gas after the burning (carbon dioxide) flows to the cathode chamber of MCFC again, as one of raw material of cathode reaction.Because this system adopts the mode of traditional steam reforming that natural gas is reformed, the whole system structure is comparatively complicated, and the energy that is consumed is more relatively; Because reforming reaction temperature height, pressure is big, is generation and the inhibition side reaction that promotes hydrogen, " steam/hydrocarbons ratio " of having relatively high expectations when steam/hydrocarbons ratio is lower than 3, analysed the carbon side reaction easily on nickel reforming catalyst surface, cause catalyst activity reduction, but improve " steam/hydrocarbons ratio ", then energy consumption increases; Simultaneously, owing to be subjected to the restriction of chemical balance, the conversion ratio of natural gas can not be further enhanced, impurity content in the reformation gas (CO, CO
2, CH
4) more.In addition, the amount of anode exhaust gas and the cathode exhaust gas tail gas (carbon dioxide) after through the reformer burning very little, the proportion requirement that can't satisfy the MCFC cathode gas (is generally air/CO
2Be 7/3).
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of natural gas melting carbonate fuel cell generation system is provided.Adopt the method for adsorption forced steam methane reforming, replace traditional steam methane reforming, and combine with the MCFC electricity generation system, it is simple to have system, advantage of low energy consumption.
The present invention is achieved by the following technical solutions, the present invention includes: adsorption forced steam methane reforming subsystem, molten carbonate fuel cell subsystem, carbon dioxide and the recycling subsystem of tail gas, adsorption forced steam methane reforming subsystem is connected by the air inlet pipe of escape pipe with the molten carbonate fuel cell subsystem, the molten carbonate fuel cell subsystem is connected with adsorption forced steam methane reforming subsystem air inlet pipe by escape pipe, and this closed-loop path structure constitutes carbon dioxide and the recycling subsystem of tail gas.
Described adsorption forced steam methane reforming subsystem comprises: natural gas tube, preheater, desulfurizing tower, heat exchanger, natural gas tube, nitrogen tube, air hose, two or more reformer; Two reformers are that independent mutually that place or two above reformers are independent mutually placements; Described reformer comprises: combustion chamber and reative cell; After natural gas tube connects successively after natural gas tube, preheater, desulfurizing tower, the desulfurization, be connected to an air inlet of the reative cell of reformer; The reative cell of reformer has three air inlets, respectively with desulfurization after natural gas tube, nitrogen tube is connected with air hose; Reative cell has three gas outlets, respectively with the molten carbonate fuel cell subsystem in the anode air inlet pipe, the cathode inlet pipe, the nitrogen wash pipe connects; There are five air inlets the combustion chamber, respectively and natural gas tube, air hose, the anode escape pipe in the molten carbonate fuel cell subsystem, the negative electrode escape pipe, the nitrogen wash pipe connects; There is a gas outlet combustion chamber, is connected with the combustion chamber offgas duct.
Described reative cell is the gas piping shape, places the combustion chamber.
The reative cell of described reformer: be by CO
2The fixed bed reformer that adsorbent and Ni catalyst mix are filled.
Described molten carbonate fuel cell subsystem comprises: anode air inlet pipe, anode circulation air inlet pipe, cathode inlet pipe, molten carbonate fuel cell pile, anode escape pipe, anode recycle tracheae, negative electrode escape pipe, booster pump; The molten carbonate fuel cell pile has an anode chamber and a cathode chamber, respectively anodic gas and cathode gas is assigned in the anode and negative electrode of each monocell; There are two air inlets and two gas outlets in the anode chamber, and cathode chamber has an air inlet and a gas outlet; Two air inlets of anode chamber are connected with anode air inlet pipe, anode circulation air inlet pipe respectively, and two gas outlets of anode chamber recycle tracheae with anode escape pipe, anode respectively and are connected; The air inlet of cathode chamber is connected with the cathode inlet pipe, and the gas outlet of cathode chamber is connected with the negative electrode escape pipe; A gas outlet of anode chamber recycles tracheae with anode and is connected, and this anode recycles after tracheae and booster pump and anode circulation air inlet pipe be connected in turn, is connected with another air inlet of anode chamber again.
Described pile is to be in series by a plurality of monocell levels, and each monocell is formed by stacking from the bottom to top successively by negative electrode, electrolyte and anode.
In the described molten carbonate fuel cell subsystem, a gas outlet of the anode chamber of described pile recycles tracheae with anode and is connected, this anode recycles after tracheae and booster pump and anode circulation air inlet pipe be connected in turn, is connected with another air inlet of anode chamber again.Like this, just constituted anode exhaust gas self is recycling, anode is complete reaction fuel completely not, continues to get back in the anode chamber and react, and has improved the utilance of natural gas.
Described molten carbonate fuel cell subsystem, by the anode air inlet pipe, the outlet of the reative cell of the reformer when being in reaction-absorption phase in the adsorption forced steam methane reforming subsystem is connected, and is used for introducing the high-purity hydrogen that the reformer in hydrogen manufacturing stage produces.The molten carbonate fuel cell subsystem is connected with the outlet that is in the reative cell of the reformer of desorption during the stage in the adsorption forced steam methane reforming subsystem by the cathode inlet pipe, is used for introducing the CO that the reformer in desorption stage produces
2And air.Described molten carbonate fuel cell subsystem by the anode escape pipe, is connected with an air inlet of the combustion chamber of reformer in the adsorption forced steam methane reforming subsystem, and anode exhaust gas is transported to the combustion chamber; The molten carbonate fuel cell subsystem is connected with an air inlet of the combustion chamber of reformer in the adsorption forced steam methane reforming subsystem by the negative electrode escape pipe, and cathode exhaust gas is transported to the combustion chamber.
The recycling subsystem of described carbon dioxide and tail gas comprises: three separate mechanisms: self recycling mechanism of anode exhaust gas, carbon dioxide effectively utilize mechanism, the recycling mechanism of carbon dioxide, anode exhaust gas and cathode exhaust gas.
Self recycling mechanism of described anode exhaust gas is present in the molten carbonate fuel cell subsystem, and comprising: anode gas outlet, anode recycle tracheae, booster pump, anode circulation air inlet pipe, anode inlet, connects in turn.
The mechanism that effectively utilizes of described carbon dioxide comprises: the air hose in the adsorption forced steam methane reforming subsystem, be in CO
2Desorption stage (regeneration stage) reative cell, and cathode inlet pipe, cathode chamber in the molten carbonate fuel cell subsystem; Air hose, be in CO
2The connection in turn of desorption stage (regeneration stage) reative cell, cathode inlet pipe, cathode chamber.
The recycling mechanism of described carbon dioxide, anode exhaust gas and cathode exhaust gas, comprise: the nitrogen wash pipe in the adsorption forced steam methane reforming subsystem, the combustion chamber of reformer, the combustion chamber offgas duct, heat exchanger, booster pump, and the anode escape pipe in the molten carbonate fuel cell subsystem, negative electrode escape pipe; The nitrogen wash pipe, anode escape pipe, negative electrode escape pipe are connected with the air inlet of combustion chamber respectively, the gas outlet of combustion chamber is connected with the combustion chamber offgas duct, after combustion chamber offgas duct, heat exchanger, booster pump connect successively, be connected with air hose again, constituted the recycling part of carbon dioxide, anode exhaust gas and cathode exhaust gas.
Principle of the present invention is as follows:
(Sorption-Enhanced Reaction Process, notion SERP) is applied to steam methane reforming hydrogen production process, the high-purity H that obtains adsorption forced course of reaction in the present invention
2, as the anodic gas of molten carbonate fuel cell; The CO that desorption comes out
2And the CO of burning back generation
2After air mixed,,, chemical energy is converted into electric energy through after the electrochemical reaction as the cathode gas of molten carbonate fuel cell.According to Le Chatelier principle, for the chemical reaction that is subjected to chemical balance control, if remove the partial reaction product, then the conversion ratio of reactant and reaction rate will improve.According to this principle, the notion of SERP has been proposed, promptly utilize selective absorbent to adsorb to fall the partial reaction product, and (Pressure SwingAdsorption, PSA) method is regenerated to utilize pressure swing adsorption method to adsorbent.The advantage of SERP method is conspicuous: can improve the conversion ratio of reactant greatly, making to be reflected under the cryogenic conditions becomes possibility, reduces byproduct, directly obtains the major product of higher degree.
The present invention is applied to steam methane reforming hydrogen production process to the method for SERP, promptly utilizes reproducible CO
2Adsorbent constantly removes the CO that generates in the reformer reactor
2Gas makes that in temperature be not under the very high situation (400～650 ℃), CH
4Conversion ratio and H
2The purity of product is still very high, and this point is for the energy consumption that reduces reforming process, and can guarantee that impurity content low in the reformation gas is very meaningful.In addition, because water gas shift reaction is exothermic reaction, low temperature helps reducing CO content.Therefore,, can reduce reforming temperature (400～650 ℃), also just reduce energy consumption, also reduce the possibility of analysing the carbon side reaction simultaneously with the hydrogen manufacturing of SE-SMR method; Can directly obtain highly purified H
2, and CO, CO
2, CH
4Impurity content is lower; Under same temperature conditions, methane conversion improves; Meeting release portion heat promotes the conversion of methane in the adsorption process; Can suitably reduce steam/hydrocarbons ratio, to cut down the consumption of energy; Cancelled the CO conversion process, the process for making hydrogen flow process is simplified greatly, and equipment cost also reduces.
The present invention combines SE-SMR hydrogen producing technology and molten carbonate fuel cell technology again, constitutes the SE-SMR-MCFC electricity generation system, the highly purified H that makes from SE-SMR
2Do not need cooling, can directly enter the generating of MCFC subsystem, therefore shortcomings such as traditional reformation mode system complex, energy consumption height can have been avoided well, improved the purity of hydrogen in the transfer ratio of natural gas and the reformation gas, reduce the content of CO in the reformation gas, thereby the MCFC local temperature of avoiding water gas shift reaction to cause raises, and influences battery life.Simultaneously, also reduced under high-temperature and high-pressure conditions, CO takes place in the MCFC anode chamber analyses carbon side reaction possibility, and the carbon of separating out can stop up anode gas passages, causes generating efficiency to reduce.
Beneficial effect of the present invention:
The SE-SMR-MCFC electricity generation system that the present invention proposes is used and is strengthened adsorption reaction, has improved the conversion efficiency of natural gas, has reduced the content of impurity in the conversion gas, under the lower situation of energy consumption, obtains highly purified hydrogen; By the method for on-the-spot desorption, catalyst is regenerated, the CO that desorption comes out
2And the CO of anode reaction generation
2, the raw material as cathode reaction is used again, and by heat exchanger, the waste heat of tail gas obtains utilizing.Therefore, the SE-SMR-MCFC electricity generation system is a kind of very economical and generation mode efficiently.
Description of drawings
Fig. 1 is fuel cell generation schematic diagram in the embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment has provided detailed execution mode being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Three subsystems are: adsorption forced steam methane reforming subsystem, molten carbonate fuel cell subsystem, the recycling subsystem of carbon dioxide and tail gas; Adsorption forced steam methane reforming subsystem is connected by the air inlet pipe of escape pipe with the molten carbonate fuel cell subsystem, the molten carbonate fuel cell subsystem is connected with adsorption forced steam methane reforming subsystem air inlet pipe by escape pipe, and this closed-loop path structure constitutes carbon dioxide and the recycling subsystem of tail gas.
In adsorption forced steam methane reforming subsystem, generally comprise two stages: i.e. reaction-absorption phase (hydrogen manufacturing stage) and CO
2The desorption stage (regeneration stage).Therefore, in this subsystem, two or more two above reformers are set mainly, one or other several reformers are when the reforming reaction hydrogen manufacturing of carrying out natural gas, and another or other several reformers are then at the desorption and regeneration that carries out carbon dioxide.According to the difference of the stage of reaction, the reative cell air inlet of reformer is different with the switch situation of gas outlet.When reative cell is in reaction-absorption phase (hydrogen manufacturing stage), the reative cell air inlet of reformer only and the connection of the natural gas tube after the desulfurization, the inlet close of nitrogen tube, air hose and reative cell; The gas outlet of anode air inlet pipe and reative cell is communicated with, the cathode inlet pipe, and the gas outlet of nitrogen wash pipe and reative cell is closed.Like this, after the preheating of natural gas via over-heat-exchanger, at first by desulfurizing tower to remove the sulfur impurity that contains in the natural gas; Water has become water vapour through after the heat exchanger heats, is 2/1～3/1 ratio according to steam/hydrocarbons ratio, is injected into the reative cell of reformer, and the gas of coming out of reforming enters the anode of molten carbonate fuel cell subsystem.The temperature of this reformer is set in 400～650 ℃, and pressure imports the mixed airflow of natural gas and water vapour from air inlet under 4～10atm, through after the adsorption forced reforming reaction, make low impurity (CO, CH
4, CO
2) the high-purity H of content
2The gas that comes out from the reformer gas that acts as a fuel is supplied to the MCFC anode.CO/CO in exit gas
2, CH
4When reaching preset value (as 100ppm, 5%), close the gaseous mixture air intake valve of steam and methane and the reformation gas valve of giving vent to anger and cut off this reformer is switched to regenerative circuit, thereby enter CO
2The desorption stage.When reative cell is in CO
2In the desorption stage (regeneration stage), the reative cell air inlet of reformer and nitrogen tube, air hose are communicated with the natural gas tube after the desulfurization and the inlet close of reative cell; The cathode inlet pipe, the gas outlet of nitrogen wash pipe and reative cell is communicated with, and the gas outlet of anode air inlet pipe and reative cell is closed.Like this, at first purge out the imflammable gas that may contain in the reative cell with nitrogen, the gas that purges out, process nitrogen wash pipe enters the combustion chamber of reformer; Then, be adsorbed on CO in the catalyst with air purge
2, making catalyst regeneration, the gas that purges out through the cathode inlet pipe, enters the negative electrode of molten carbonate fuel cell subsystem, as the raw material of cathode reaction.Therefore, in adsorption forced steam methane reforming subsystem, need to be provided with two or more reformers, to guarantee the continuous operation of molten carbonate fuel cell subsystem.When one of them or several reformer are in reaction-absorption hydrogen manufacturing during the stage, another or several reformer are in CO
2The desorption stage, the reaction of each reformer-absorption hydrogen manufacturing stage and CO
2The desorption stage hockets.Like this, can guarantee all respond the at any time supply of gas of the anode of molten carbonate fuel cell subsystem and negative electrode.
Five air inlets of the combustion chamber of reformer, respectively and natural gas tube, air hose, the anode escape pipe, the negative electrode escape pipe, the nitrogen wash pipe connects, and a gas outlet of combustion chamber is connected with the combustion chamber offgas duct.This structure guarantees these five kinds of gas mixed combustions in the combustion chamber of flushing gas of natural gas, air, anode exhaust gas, cathode exhaust gas, nitrogen, for reative cell provides heat.The combustion chamber tail gas discharged mainly comprises CO
2And air, after passing through heat exchange and aqueous vapor being separated, major part enters air pipe line, the fraction emptying.
In the molten carbonate fuel cell subsystem, comprise that anode air inlet pipe, anode circulation air inlet pipe, cathode inlet pipe, molten carbonate fuel cell pile, anode escape pipe, anode recycle tracheae, negative electrode escape pipe, booster pump.The pile of molten carbonate fuel cell is to be in series by a plurality of monocell levels, each monocell is formed by stacking from the bottom to top successively by negative electrode, electrolyte and anode, there are two air inlets and two gas outlets in the anode chamber, and cathode chamber has an air inlet and a gas outlet.The anode air inlet pipe that the reative cell of the reformer of air inlet of the anode chamber of molten carbonate fuel cell when being in reaction-absorption phase from adsorption forced steam methane reforming subsystem comes out is connected, and is used for introducing the high-purity hydrogen that the reformer in hydrogen manufacturing stage produces.The air inlet of the cathode chamber of molten carbonate fuel cell is connected with the cathode inlet pipe that the reative cell that is in the reformer of desorption during the stage from adsorption forced steam methane reforming subsystem comes out, and is used for introducing the CO that the reformer in desorption stage produces
2And air.A gas outlet of the anode chamber of molten carbonate fuel cell is connected with the anode escape pipe, and the gas outlet of the cathode chamber of molten carbonate fuel cell is connected with the negative electrode escape pipe.Simultaneously, in this subsystem, another gas outlet and the anode of the anode chamber of molten carbonate fuel cell recycle tracheae and are connected, this anode recycles after tracheae and booster pump and anode circulation air inlet pipe be connected in turn, is connected with another air inlet of anode chamber, so again, just constituted anode exhaust gas self is recycling, anode is complete reaction fuel completely not, continues to get back in the anode chamber and react, and has improved the utilance of natural gas.
The low impurity content that the reative cell of the reformer when being in reaction-absorption phase comes out, highly purified hydrogen feeds anode; From being in CO
2CO that come out, that contain desorption in the reformer in desorption stage
2Air douche gas through the cathode inlet pipe, enters the MCFC negative electrode, by carbonate electrolyte, following electrochemical reaction takes place and generates electricity:
Anode: H
2+ CO
3 2-=H
2O+CO
2+ 2e
-(1)
Negative electrode: 1/2O
2+ CO
2+ 2e
-=CO
3 2-(2)
An anode exhaust gas part returns and continues reaction in the anode chamber, and another part anode exhaust gas and cathode exhaust gas then by anode escape pipe and negative electrode escape pipe, enter in the combustion chamber of reformer in the adsorption forced steam methane reforming subsystem.
The recycling subsystem of carbon dioxide and tail gas, comprise anode exhaust gas self is recycling, effective utilization of carbon dioxide, recycling three parts of carbon dioxide, anode exhaust gas and cathode exhaust gas.
(1) self recycling part of anode exhaust gas is present in the above-mentioned molten carbonate fuel cell subsystem.Comprise: anode gas outlet, anode recycle tracheae, booster pump, anode circulation air inlet pipe, anode inlet, connect in turn.
Effective utilization of carbon dioxide, carbon dioxide, anode exhaust gas and cathode exhaust gas recycling is to connect by the pipeline between adsorption forced steam methane reforming subsystem and the molten carbonate fuel cell subsystem to realize.On the structure, the closed-loop path that constitutes between adsorption forced exactly steam methane reforming subsystem and the molten carbonate fuel cell subsystem does not have self independently member.
(2) in the effective utilization part of carbon dioxide, air hose, be in CO
2The connection in turn of desorption stage (regeneration stage) reative cell, cathode inlet pipe, what constituted carbon dioxide effectively utilizes part.Be adsorbed on the CO of catalyst surface by the air handle
2Desorption gets off, and makes catalyst obtain regeneration on the one hand, on the other hand, and the CO that washes
2By the cathode inlet pipe, enter the negative electrode of molten carbonate fuel cell, participate in electrochemical reaction as reactant, the feasible CO that washes
2Not as toxic emission, but obtained effective utilization as reactant.
(3) in the recycling part of carbon dioxide, anode exhaust gas and cathode exhaust gas, described anode escape pipe, negative electrode escape pipe, nitrogen wash pipe are connected with the air inlet of combustion chamber respectively, the gas outlet of combustion chamber is connected with the combustion chamber offgas duct, after combustion chamber offgas duct, heat exchanger, booster pump connect successively, be connected with air hose again, air hose, be in CO
2The connection successively of desorption stage (regeneration stage) reative cell, cathode inlet pipe has constituted the recycling part of carbon dioxide, anode exhaust gas and cathode exhaust gas.After anode exhaust gas, cathode exhaust gas, nitrogen wash gas entered the combustion chamber, with air that replenishes in addition and the abundant mixed combustion of natural gas, the heat that burning obtains was supplied to reative cell, and gas fume after burning mainly contains air, CO
2And water, enter the combustion chamber offgas duct, by heat exchanger, aqueous vapor is injected air pipe line after separating also supercharging.Along with the reative cell in air douche regeneration stage, and be connected with the cathode inlet pipe, like this, the CO of anode reaction generation
2, the negative electrode CO that falls of complete reaction not
2CO with air, burning back generation in the combustion chamber
2All reenter the negative electrode of molten carbonate fuel cell, participate in electrode reaction.In carbon dioxide and the recycling subsystem of tail gas, embodied characteristics of the present invention, promptly, increased CO in the cathode gas by three approach
2Content, the gas that the gas that the desorption gas that just washes, anode produce, burning back produce wherein all contains CO
2, all entered the cathode chamber of molten carbonate fuel cell, participate in the electrochemical reaction of negative electrode, remedied the CO that exists in the contrast patent
2The shortcoming that content is not enough, simultaneously, the heat in anode exhaust gas, the cathode exhaust gas has obtained fully effectively utilizing, and the discharge capacity of whole system is but very low, has really realized purpose efficient, clean electric power generation.
As shown in Figure 1, after the preheating of the natural gas of present embodiment through natural gas tube 1 and heat exchanger I2, enter natural gas tube 3, by natural gas tube 4, natural gas tube 5 and natural gas tube 6, flow to three directions respectively:
First direction of natural gas, by natural gas tube 4, again behind over-heat-exchanger IV7, enter the natural gas tube 8 after the preheating, then by desulfurizing tower 9, to remove a spot of sulfur-containing impurities, subsequently, by the natural gas tube after the desulfurization 10, enter the reative cell 12 of the reformer I11 that is in reaction-absorption phase, through the gas after the adsorption forced reformation of high pressure, through anode air inlet pipe 14, enter the anode chamber 16 of molten carbonate fuel cell 15, reacted anode exhaust gas, a part recycles tracheae 22 by anode, after compressor I23 supercharging, by anode circulation air inlet pipe 24, carry out recycling again; The anode exhaust gas of another part by anode escape pipe 19, is divided into two-way, and one the tunnel through anode escape pipe 20, enters the combustion chamber 13 of reformer I11, and another road enters the combustion chamber 33 of reformer II31 through anode escape pipe 21.
Second direction of natural gas enters the combustion chamber 13 of reformer I11 by natural gas tube 5, and the 3rd direction of natural gas enters the combustion chamber 33 of reformer II31 by natural gas tube 6.
Air is through air hose 25, after heat exchanger III26 preheating, enter air hose 27 after, also be divided into three directions:
First direction of air by air hose 28, enters the reative cell 32 of reformer II31, and purge washes away and is adsorbed on CO
2CO on the adsorbent
2, the gas of producing by boasting enters the cathode chamber 18 of molten carbonate fuel cell 15 by cathode inlet pipe 34, and reacted cathode exhaust gas behind negative electrode escape pipe 35, is divided into two-way: lead up to negative electrode escape pipe 36, enter the combustion chamber 13 of reformer I11; Another road enters the combustion chamber 33 of reformer II31 through negative electrode escape pipe 37.
Second direction of air enters the combustion chamber 13 of reformer I11 by air hose 29, and the 3rd direction of air enters the combustion chamber 33 of reformer II31 by air hose 30.
Nitrogen is by nitrogen tube 38, behind over-heat-exchanger II39, enter nitrogen tube 40, subsequently, enter the reative cell 32 of reformer II31, irrigation as a part develops, and enters nitrogen wash pipe 41, again respectively by nitrogen wash pipe 42, enter the combustion chamber 13 of reformer I11, and nitrogen wash pipe 43, enter the combustion chamber 33 of reformer II31.
Like this, the air of coming in by air hose 29, the natural gas of coming in by natural gas tube 5, the cathode exhaust gas of coming in by negative electrode escape pipe 36, anode exhaust gas of coming in by anode outlet pipe 20 and the nitrogen wash gas of coming in by nitrogen wash pipe 42, fully burning in the combustion chamber 13 of reformer I11 provides energy for strengthening the absorption reformation, and the tail gas after the burning is discharged by combustion chamber offgas duct 44.
Equally, the air of coming in by air hose 30, the natural gas of coming in by natural gas tube 6, the cathode exhaust gas of coming in by negative electrode escape pipe 37, anode exhaust gas of coming in by anode outlet pipe 21 and the nitrogen wash gas of coming in by nitrogen wash pipe 43, fully burning is CO in the combustion chamber 33 of reformer II31
2Desorption energy is provided, the tail gas after the burning is discharged by combustion chamber offgas duct 45.
The tail gas of combustion chamber contains air, CO
2And water, after combustion chamber offgas duct 44 and combustion chamber offgas duct 45, merging enters combustion chamber offgas duct 46, behind over-heat-exchanger V47, after aqueous vapor was separated, a small amount of gas was by blast pipe 48 dischargings, most gases are integrated with air hose 25, CO wherein by after the compressor II50 supercharging
2The utilization that can obtain continuing.
Molten carbonate fuel cell 15 is by anode chamber 16, and electrolyte 17 and cathode chamber 18 constitute.The high-purity hydrogen that comes out from the reative cell 12 of reformer I11, and the air and the CO that come out from the reative cell 32 of reformer II31
2Electrochemical reaction takes place in mist in molten carbonate fuel cell 15, electric energy externally is provided.
The present embodiment natural gas is through after the adsorption forced reformation, the consisting of of the reformation gas that obtains: CH
4Between 2-4%, CO between 0.02-0.04%, CO
2Between 0.10-0.03%, H
2Between 96-98%, the conversion ratio of natural gas can reach between 85～95%, energy conversion efficiency can reach 75～85%, has reached the purpose that high-efficiency cleaning utilizes the energy.
Claims (9)
1. natural gas melting carbonate fuel cell generation system, comprise: adsorption forced steam methane reforming subsystem, molten carbonate fuel cell subsystem, carbon dioxide and the recycling subsystem of tail gas, it is characterized in that, adsorption forced steam methane reforming subsystem is connected by the air inlet pipe of escape pipe with the molten carbonate fuel cell subsystem, the molten carbonate fuel cell subsystem is connected with adsorption forced steam methane reforming subsystem air inlet pipe by escape pipe, and this closed-loop path structure constitutes carbon dioxide and the recycling subsystem of tail gas.
2. natural gas melting carbonate fuel cell generation system according to claim 1, it is characterized in that described adsorption forced steam methane reforming subsystem comprises: natural gas tube, nitrogen tube, air hose, two or more reformer after natural gas tube, preheater, desulfurizing tower, heat exchanger, the desulfurization; Two reformers are that independent mutually that place or two above reformers are independent mutually placements; Combustion chamber and reative cell are set in the described reformer; After natural gas tube connects successively after natural gas tube, preheater, desulfurizing tower, the desulfurization, be connected to an air inlet of the reative cell of adsorption forced stage reformer; The reative cell of reformer has three air inlets, and when reative cell is in reaction-absorption phase, the reative cell air inlet of reformer and the natural gas tube after the desulfurization are communicated with; When reative cell is in the carbon dioxide desorption stage, the reative cell air inlet of reformer is connected with air hose with nitrogen tube; Reative cell has three gas outlets, and when reative cell is in reaction-absorption phase, the gas outlet of reative cell is communicated with nitrogen wash pipe and anode air inlet pipe respectively; When reative cell is in the carbon dioxide desorption stage, the gas outlet of reative cell is connected with the cathode inlet pipe; There are five air inlets the combustion chamber, respectively and natural gas tube, air hose, the nitrogen wash pipe, the anode escape pipe in the molten carbonate fuel cell subsystem, the negative electrode escape pipe connects; There is a gas outlet combustion chamber, is connected with the combustion chamber offgas duct.
3. natural gas melting carbonate fuel cell generation system according to claim 2 is characterized in that: described reative cell is the gas piping shape, places the combustion chamber.
4. natural gas melting carbonate fuel cell generation system according to claim 1, it is characterized in that, described molten carbonate fuel cell subsystem comprises: the anode air inlet pipe, anode circulation air inlet pipe, the cathode inlet pipe, the molten carbonate fuel cell pile, the anode escape pipe, anode recycles tracheae, the negative electrode escape pipe, booster pump, the molten carbonate fuel cell pile has an anode chamber and a cathode chamber, there are two air inlets and two gas outlets in the anode chamber, cathode chamber has an air inlet and a gas outlet, two air inlets of anode chamber respectively with the anode air inlet pipe, anode circulation air inlet pipe connects, two gas outlets of anode chamber respectively with the anode escape pipe, anode recycles tracheae and connects, the air inlet of cathode chamber is connected with the cathode inlet pipe, the gas outlet of cathode chamber is connected with the negative electrode escape pipe, a gas outlet of anode chamber recycles tracheae with anode and is connected, this anode recycles after tracheae and booster pump and anode circulation air inlet pipe be connected in turn, is connected with another air inlet of anode chamber again.
5. natural gas melting carbonate fuel cell generation system according to claim 4 is characterized in that, described pile is to be in series by a plurality of monocell levels, and each monocell is formed by stacking from the bottom to top successively by negative electrode, electrolyte and anode.
6. natural gas melting carbonate fuel cell generation system according to claim 1, it is characterized in that, the recycling subsystem of described carbon dioxide and tail gas comprises three separate mechanisms: self recycling mechanism of anode exhaust gas, the recycling mechanism that effectively utilizes mechanism, carbon dioxide, anode exhaust gas and cathode exhaust gas of carbon dioxide.
7. natural gas melting carbonate fuel cell generation system according to claim 6, it is characterized in that, self recycling mechanism of described anode exhaust gas, be present in the molten carbonate fuel cell subsystem, comprise: anode gas outlet, anode recycle tracheae, booster pump, anode circulation air inlet pipe, anode inlet, connect in turn.
8. natural gas melting carbonate fuel cell generation system according to claim 6, it is characterized in that, the mechanism that effectively utilizes of described carbon dioxide comprises: the air hose in the adsorption forced steam methane reforming subsystem, be in the reative cell in carbon dioxide desorption stage, and the cathode inlet pipe in the molten carbonate fuel cell subsystem, connect in turn.
9. natural gas melting carbonate fuel cell generation system according to claim 6, it is characterized in that, described carbon dioxide, the recycling mechanism of anode exhaust gas and cathode exhaust gas comprises: the nitrogen wash pipe in the adsorption forced steam methane reforming subsystem, the combustion chamber of reformer, the combustion chamber offgas duct, heat exchanger, booster pump, and the anode escape pipe in the molten carbonate fuel cell subsystem, the negative electrode escape pipe, described nitrogen wash pipe, the anode escape pipe, the negative electrode escape pipe is connected with the air inlet of combustion chamber respectively, the gas outlet of combustion chamber is connected with the combustion chamber offgas duct, the combustion chamber offgas duct, heat exchanger, after booster pump connects successively, be connected with air hose again.
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| AU2008338509B2 (en) * | 2007-12-17 | 2011-08-18 | Shell Internationale Research Maatschappij B.V. | Fuel cell-based process for generating electrical power |
| US7910258B2 (en) * | 2008-04-09 | 2011-03-22 | Hce, Llc | Natural gas direct carbon fuel cell |
| CN101800326B (en) * | 2010-04-17 | 2012-09-05 | 上海交通大学 | Two-electrolyte direct carbon fuel cell and assembling method thereof |
| CN104377375B (en) * | 2014-11-03 | 2016-08-17 | 中国华能集团清洁能源技术研究院有限公司 | A kind of integral coal gasification melting carbonate fuel cell generation system |
| CN104538658B (en) * | 2014-12-26 | 2017-01-04 | 华北电力大学 | Scalable CO2the MCFC combined power system of the response rate and operation method |
| CN109181800B (en) * | 2018-10-22 | 2024-02-20 | 广东索特能源科技有限公司 | Coupling device for decarbonizing and reforming methane and decarbonizing and reforming system for methane |
| CN111193050B (en) * | 2018-11-14 | 2021-03-12 | 中国科学院大连化学物理研究所 | Reforming high-temperature fuel cell system and starting method thereof |
| KR20230011914A (en) * | 2020-03-11 | 2023-01-25 | 퓨얼셀 에너지, 인크 | Steam methane reforming unit for carbon capture |
| KR102600084B1 (en) * | 2021-09-14 | 2023-11-09 | 두산에너빌리티 주식회사 | System and process for reforming natural gas |
| CN114725432A (en) * | 2022-05-05 | 2022-07-08 | 成都岷山绿氢能源有限公司 | Zero-carbon power generation system and power generation process of solid oxide fuel cell |
| CN116544449B (en) * | 2023-07-03 | 2023-09-15 | 磐动(浙江)电气科技有限公司 | Low-carbon-emission fuel cell system and heat management method |
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