CN104538658A - MCFC hybrid power system capable of regulating CO2 recovery rate and operation method - Google Patents
MCFC hybrid power system capable of regulating CO2 recovery rate and operation method Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/14—Fuel cells with fused electrolytes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D15/00—Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
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- 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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- 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
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- H01M8/00—Fuel cells; Manufacture thereof
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- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
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Abstract
The invention belongs to the technical field of MCFC hybrid power systems, and in particular relates to an MCFC hybrid power system capable of regulating CO2 recovery rate and an operation method. A deep cooling air separation device is replaced by an integrated ITM to produce pure oxygen, and the pure oxygen is fed into a afterburner chamber together with battery anode exhaust gas to be completely combusted; the product only includes CO2 and H2O; then a part of exhaust gas is circulated to a battery cathode so as to supply CO2 required for cathodic reaction; the afterheat of the other part of exhaust gas is recovered by virtue of an afterheat boiler; tail gas and the air are subjected to heat exchange and condensation to separate out water; the surplus CO2 is compressed into a liquid state by using a three-level intercooling carbon dioxide compressor; one circulation is additionally arranged on a battery cathode, and the CO2 recovery rate of the MCFC hybrid power system can be adjusted by changing the proportion of the recycle gas. According to the system, the afterheat of the high-temperature exhaust gas of MCFC is fully utilized, along with the matching temperature, the energy consumption caused by separation and capture of CO2 is reduced while the system efficiency is improved, the power consumption is saved, and the CO2 recovery rate can be regulated by virtue of the new system through additionally-arranged cathodic circulation.
Description
Technical field
The invention belongs to molten carbonate fuel cell (MCFC) combined power system technical field, particularly the adjustable CO of one
2the MCFC combined power system of the rate of recovery and operation method.
Background technology
Greenhouse gas excessive emissions exacerbates greenhouse effect, as topmost greenhouse gas, and CO
2reduction of discharging caused the whole world extensive concern.Traditional generation mode is because be subject to the restriction of Carnot cycle, and generating efficiency is lower, and trapping CO
2efficiency can be made to decline further.And molten carbonate fuel cell (MCFC) electrogenesis is by electrochemical reaction process, breach the restriction of Carnot's cycle efficiency, and its exhaust temperature is high, is easy to and other system integration, improves system effectiveness further.Utilize the obtained pure oxygen of ITM low energy consumption that unreacted fuel gas can be made to burn completely simultaneously and generate CO
2and H
2o, is easy to be separated, can at utmost avoids N in air
2for CO in exhaust
2blending, make CO
2trapping energy consumption significantly reduces.
Summary of the invention
The invention provides a kind of adjustable CO
2the MCFC combined power system of the rate of recovery and operation method, by avoiding CO in exhaust by MCFC cathode and anode bypassing exhaust
2due to N
2the problem that blending causes separating energy consumption too high, and the advantage utilizing that ITM oxygen energy consumption is low, reduce combined power system total energy consumption further, reduces MCFC combined power system because reclaim CO
2the efficiency punishment brought, simultaneously by setting up MCFC cathode exhaust recycle, can realize combined power system CO
2the adjustment of the rate of recovery.
The technical scheme that combined power system of the present invention adopts is:
After first via air duct is connected with the 3rd heat exchanger, the 4th heat exchanger, the second blender, the second heat exchanger successively, the negative electrode of access MCFC battery pile; After second road air duct is connected with air compressor, First Heat Exchanger successively, the feed side of access ITM unit, First Heat Exchanger is arranged in afterburner; After fuel channel is connected with the first blender, pre-reformer successively, the anode of access MCFC battery pile;
The anode exhaust of MCFC battery pile is connected with the first separator, is then divided into two-way, is connected respectively with the first blender, afterburner; The cathode exhaust vent of MCFC battery pile is connected with the second separator, is then divided into two-way, and a road is connected with waste heat boiler and turbine system, and another road is connected with the second blender;
After the outlet of afterburner is connected with the second heat exchanger, access the 3rd separator, is then divided into two-way, is connected respectively with waste heat boiler and turbine system, the second blender;
After the feed side of ITM unit exports and is connected with air turbine, the 4th heat exchanger successively, waste gas enters air; The per-meate side outlet of ITM unit takes back afterburner;
The exhaust outlet of waste heat boiler and turbine system is connected with the 3rd heat exchanger, condenser, the cold carbon-dioxide gas compressor of three inter-stages successively;
The output of MCFC battery pile is connected with the first generator by AC/DC converter.
In described ITM unit, oxygen ion transport film uses atresia, hybrid conductive, has the ceramic membrane of electronics and ionic conductivity, and its operating temperature is 900 DEG C; The side air inlet of ITM unit raw material is HTHP air, exports as oxygen denuded air, and per-meate side outlet is pure oxygen; ITM unit raw material side and per-meate side oxygen partial pressure force rate are 6.3.
The cold carbon-dioxide gas compressor of described three inter-stage is composed in series by three-stage blower, cooler.
Described waste heat boiler and turbine system are connected with the second generator.
Described air turbine is connected with the 3rd generator.
The adjustable CO of the described integrated ITM of one provided by the invention
2the operation method of the MCFC combined power system of the rate of recovery, its process is:
The portion discharge mixing preheating that fuel under normal temperature loops back with MCFC cell stack anode in the first blender, and enter in pre-reformer occur pre-reforming reaction, the anode entering MCFC battery pile subsequently provides anode reaction gas; First via air under normal temperature is successively after the 3rd heat exchanger, the 4th heat exchanger heat exchange, the portion discharge looped back with MCFC stack cathode in the second blender and afterburner portion discharge mix further preheating, with after after the second heat exchanger be heated to 650 DEG C, enter MCFC stack cathode cathode reaction gas be provided;
The anode exhaust of MCFC battery pile is divided into two-way through the first separator: a road enters the first blender pre-heating fuel and prevents carbon distribution in reforming process, and another road enters afterburner and to burn remaining unreacting gas; The cathode exhaust gas of MCFC battery pile is divided into two-way through the second separator: a road loops back preheated air regulating system CO simultaneously in the second blender before battery pile
2the rate of recovery, another road enters air after entering waste heat boiler and turbine system recovery waste heat; The output of MCFC battery pile drives the first electrical power generators;
The heat exchanger that the second road air under normal temperature enters afterburner inside after air compressor compression is heated to 900 DEG C, pass into ITM unit raw material side entrance subsequently, the oxygen denuded air of ITM unit raw material side outlet carries out heat exchange with the 4th heat exchanger after air turbine expansion work, and the pure oxygen of ITM unit per-meate side outlet enters afterburner; Afterburner exiting exhaust gas and the second heat exchanger heat exchange are divided into two-way through the 3rd separator after lowering the temperature: a road enters the second blender and provides MCFC stack cathode reacting gas CO
2, another road enters waste heat boiler and turbine system recovery waste heat, and waste heat boiler and turbine system tail gas enter the cold carbon-dioxide gas compressor of three inter-stages through the 3rd heat exchanger heat exchange, condenser after separating out water respectively, prepare liquid CO
2.
Described air compressor outlet pressure is 30atm.
Beneficial effect of the present invention is:
Molten carbonate fuel cell (MCFC) electricity generation process is electrochemical reaction, and not by the restriction of Carnot's cycle efficiency, efficiency is high, utilizes its high-temperature exhaust air and vapor recycle is integrated can further improve generating efficiency; Adopt oxygen energy consumption low ITM generation pure oxygen that battery unreacting gas is burnt completely and generate CO
2and H
2o, wherein a part can be used for providing cell cathode to react desired gas, and another part can be passed through simple condensation moisture and obtains high-purity CO
2gas is used for compressing and liquefying storage; By setting up the CO of the adjustable whole combined power system of MCFC cathode circulation
2the rate of recovery.
Accompanying drawing explanation
Fig. 1 is not for reclaim CO
2mCFC composite power baseline system structural representation.
Fig. 2 is the adjustable CO of integrated ITM of the present invention
2the MCFC combined power system structural representation of the rate of recovery.
Number in the figure:
1-first blender; 2-pre-reformer; 3-first separator; 4-MCFC battery pile; 5-AC/DC converter; 6-first generator; 7-afterburner; 8-First Heat Exchanger; 9-second separator; 10-second heat exchanger; 11-the 3rd separator; 12-waste heat boiler and turbine system; 13-second generator; 14-the 3rd heat exchanger; 15-the 4th heat exchanger; 16-second blender; 17-condenser; The cold carbon-dioxide gas compressor of 18-tri-inter-stage; 19-air compressor; 20-ITM unit; 21-air turbine; 22-the 3rd generator.
Embodiment
The invention provides a kind of adjustable CO
2the MCFC combined power system of the rate of recovery and operation method, below by the drawings and specific embodiments, the present invention will be further described.
Baseline system is not for reclaim CO
2system, its structure chart as shown in Figure 1.Fuel and the segment anode looped back are vented and after the first blender 1 mixes, enter pre-reformer 2 reform, enter the anode of MCFC battery pile 4 subsequently, air and the part afterburner looped back are vented after the second blender 16 mixes through the second heat exchanger 10 preheating, enter the negative electrode of MCFC battery pile 4 subsequently, there is electrochemical reaction in battery pile inside, exports electric energy by AC/DC converter 5 and the first generator 6.After this anode exhaust is divided into two-way through the first separator 3: a road loops back the first blender 1 pre-heating fuel and prevents reformation carbon distribution, and another road is sent into afterburner 7 and burnt together with cathode exhaust gas.Burning and gas-exhausting through second heat exchanger 10 lower the temperature after be divided into two-way: a road loop back the second blender 16 preheated air provide simultaneously stack cathode react needed for CO
2, another road enters waste heat boiler and turbine system 12 recovery waste heat produces Steam Actuation steam turbine product merit, and export electric energy by the second generator 13, last cryopumping directly enters air.
The present invention is based on baseline system, propose the adjustable CO of integrated ITM
2the MCFC combined power system of the rate of recovery, structure chart as shown in Figure 2.Fuel and the segment anode looped back are vented and after the first blender 1 mixes, enter pre-reformer 2 reform, enter the anode of MCFC battery pile 4 subsequently, first via air is 1. successively after the 3rd heat exchanger 14, the 4th heat exchanger 15 preheating, enter the second blender 16 to be vented with part afterburner 7 and part cathode exhaust gas mixes, the negative electrode of MCFC battery pile 4 is entered subsequently after the second heat exchanger 10 heats, there is electrochemical reaction in battery pile inside, exports electric energy by AC/DC converter 5 and the first generator 6.The cathode exhaust gas of MCFC battery pile 4 is divided into two-way through the second separator 9: a road loops back the second blender 16 preheated air and regulating system CO
2the rate of recovery, another road enters waste heat boiler and turbine system 12 recovery waste heat.The anode exhaust of MCFC battery pile 4 is divided into two-way through the first separator 3: a road loops back the first blender 1 pre-heating fuel and prevents reformation carbon distribution, and another road enters afterburner 7 and burns.2. oxygen needed for afterburner 7 provided by the second road air, 2. second road air is compressed to through air compressor the First Heat Exchanger 8 entering afterburner 7 inside after 30atm and is heated to 900 DEG C, enter ITM unit 20 subsequently, two strands are become: one is the pure oxygen (pressure 1atm) of per-meate side outlet, sends into afterburner 7 combustion-supporting in this air separation; Another strand is the oxygen denuded air of feed side outlet HTHP, and generate electricity through air turbine 21 drive the 3rd generator 22 that expands, the gas after expansion enters air after the 4th heat exchanger 15 preheated air.Afterburner 7 is vented and is divided into two-way by the 3rd separator 11 after the second heat exchanger 10 is lowered the temperature: a road enters the second blender 16 preheated air and provides CO needed for MCFC battery pile 4 cathode reaction
2gas, another road enters waste heat boiler and turbine system 12 recovery waste heat, and its exhaust, after the 3rd heat exchanger 14 preheating Cryogenic air, separates out water by condenser 17, the high-purity CO obtained
2gas is sent into the cold carbon-dioxide gas compressor of three inter-stages 18 and is compressed and liquefied and obtain liquid CO
2.
Below in conjunction with example, effect of the present invention is described further.
Do not reclaim CO
2baseline system and the adjustable CO of integrated ITM
2the MCFC combined power system of the rate of recovery is based on identical hypothesis and identical parameter value.Table 1 lists system postulation condition and Selecting All Parameters.
Table 1 system postulation parameter
| Battery operating temperature | 650℃ | Operating pressure | 1atm |
| Propellant composition | CH 4 | Fuel flow rate | 0.226kmol/s |
| Steam/carbon ratio | 3.5 | Current density | 1500A/m 2 |
| MCFC thermal loss | 2％ | DC-AC changes efficiency | 0.92 |
| Fuel inlet temperature | 25℃ | Fuel availability | 85％ |
| Inlet air temp | 25℃ | Negative electrode CO 2Utilance | 85％ |
| Air compressor adiabatic efficiency | 85％ | Air compressor mechanical efficiency | 98％ |
| Air turbine expansion efficiency | 88％ | Air turbine mechanical efficiency | 98％ |
| Steam turbine high-pressure cylinder efficiency | 90％ | Steam Turbine Through IP Admission efficiency | 92％ |
| Turbine low pressure cylinder efficiency | 92％ | Waste heat boiler exhaust gas temperature | 107℃ |
The present invention carries the adjustable CO of integrated ITM
2the MCFC combined power system of the rate of recovery is by changing the CO of the recycle ratio regulating system of MCFC cathode exhaust gas
2the rate of recovery.Table 2 lists CO corresponding to system under different recycle ratio
2the rate of recovery and net efficiency.
The CO of system under the different recycle ratio of table 2MCFC cathode exhaust gas
2the rate of recovery and net efficiency
| Cathode circulation ratio | CO 2The rate of recovery, % | System net efficiency, % |
| 0.15 | 49.1 | 66.23 |
| 0.25 | 54.9 | 65.83 |
| 0.35 | 61.1 | 65.39 |
| 0.45 | 66.8 | 64.89 |
| 0.55 | 73 | 64.31 |
| 0.65 | 79.2 | 63.6 |
| 0.75 | 85 | 62.68 |
| 0.85 | 91.2 | 61.35 |
The adjustable CO of integrated ITM is carried in the present invention
2the CO of the MCFC combined power system of the rate of recovery
2the rate of recovery is under the prerequisite of 85%, and its analog result and baseline system are contrasted, result is as shown in table 3.
Table 3 system results compares
As can be seen from Table 3, CO is not reclaimed
2baseline system net efficiency is 63.36%, works as CO
2when the rate of recovery is 85%, the adjustable CO of integrated ITM
2the MCFC combined power system net efficiency of the rate of recovery is 62.68%, and its net efficiency is compared with not reclaiming CO under the same terms
2baseline system reduced by only 0.68 percentage point, demonstrates the beneficial effect that invention achieves expection.
Claims (7)
1. adjustable CO
2the MCFC combined power system of the rate of recovery, its feature is as follows: after first via air duct is connected with the 3rd heat exchanger (14), the 4th heat exchanger (15), the second blender (16), the second heat exchanger (10) successively, the negative electrode of access MCFC battery pile (4); After second road air duct is connected with air compressor (19), First Heat Exchanger (8) successively, the feed side of access ITM unit (20), First Heat Exchanger (8) is arranged in afterburner (7); After fuel channel is connected with the first blender (1), pre-reformer (2) successively, the anode of access MCFC battery pile (4);
The anode exhaust of MCFC battery pile (4) is connected with the first separator (3), is then divided into two-way, is connected respectively with the first blender (1), afterburner (7); The cathode exhaust vent of MCFC battery pile (4) is connected with the second separator (9), is then divided into two-way, and a road is connected with waste heat boiler and turbine system (12), and another road is connected with the second blender (16);
After the outlet of afterburner (7) is connected with the second heat exchanger (10), access the 3rd separator (11), then be divided into two-way, be connected with waste heat boiler and turbine system (12), the second blender (16) respectively;
After the feed side of ITM unit (20) exports and is connected with air turbine (21), the 4th heat exchanger (15) successively, waste gas enters air; The per-meate side outlet of ITM unit (20) takes back afterburner (7);
The exhaust outlet of waste heat boiler and turbine system (12) is connected with the 3rd heat exchanger (14), condenser (17), the cold carbon-dioxide gas compressor of three inter-stage (18) successively;
The output of MCFC battery pile (4) is connected with the first generator (6) by AC/DC converter (5).
2. adjustable CO according to claim 1
2the MCFC combined power system of the rate of recovery, is characterized in that: in described ITM unit (20), oxygen ion transport film uses atresia, hybrid conductive, has the ceramic membrane of electronics and ionic conductivity, and its operating temperature is 900 DEG C; ITM unit (20) feed side air inlet is HTHP air, exports as oxygen denuded air, and per-meate side outlet is pure oxygen; ITM unit (20) feed side and per-meate side oxygen partial pressure force rate are 6.3.
3. adjustable CO according to claim 1
2the MCFC combined power system of the rate of recovery, is characterized in that: the cold carbon-dioxide gas compressor of described three inter-stage (18) is composed in series by three-stage blower, cooler.
4. adjustable CO according to claim 1
2the MCFC combined power system of the rate of recovery, is characterized in that: described waste heat boiler and turbine system (12) are connected with the second generator (13).
5. adjustable CO according to claim 1
2the MCFC combined power system of the rate of recovery, is characterized in that: described air turbine (21) is connected with the 3rd generator (22).
6. one kind based on the arbitrary adjustable CO of claim 1-5
2the operation method of the MCFC combined power system of the rate of recovery, is characterized in that,
The portion discharge mixing preheating that fuel under normal temperature is returned with MCFC battery pile (4) anode circulation in the first blender (1), and in entering pre-reformer (2), there is pre-reforming reaction, the anode entering MCFC battery pile (4) subsequently provides anode reaction gas; First via air under normal temperature is successively after the 3rd heat exchanger (14), the 4th heat exchanger (15) heat exchange, the portion discharge of returning with MCFC battery pile (4) cathode circulation in the second blender (16) and afterburner (7) portion discharge mix further preheating, with after after the second heat exchanger (10) be heated to 650 DEG C, enter MCFC battery pile (4) negative electrode cathode reaction gas be provided;
The anode exhaust of MCFC battery pile (4) is divided into two-way through the first separator (3): a road enters the first blender (1) pre-heating fuel and prevents carbon distribution in reforming process, and another road enters afterburner (7) and to burn remaining unreacting gas; The cathode exhaust gas of MCFC battery pile (4) is divided into two-way through the second separator (9): a road loops back preheated air regulating system CO simultaneously in the second blender (16) before battery pile
2the rate of recovery, another road enters air after entering waste heat boiler and turbine system (12) recovery waste heat; The output of MCFC battery pile (4) drives the first generator (6) to generate electricity;
The heat exchanger (8) that the second road air under normal temperature enters afterburner (7) inner after air compressor (19) compression is heated to 900 DEG C, pass into ITM unit (20) feed side inlet subsequently, the oxygen denuded air of ITM unit (20) feed side outlet carries out heat exchange with the 4th heat exchanger (15) after air turbine (21) expansion work, and the pure oxygen of ITM unit (20) per-meate side outlet enters afterburner (7); Afterburner (7) exiting exhaust gas and the second heat exchanger (10) heat exchange are divided into two-way through the 3rd separator (11) after lowering the temperature: a road enters the second blender (16) and provides MCFC battery pile (4) cathode reaction gas CO
2another road enters waste heat boiler and turbine system (12) recovery waste heat, waste heat boiler and turbine system (12) tail gas enter the cold carbon-dioxide gas compressor of three inter-stage (18) through the 3rd heat exchanger (14) heat exchange, condenser (17) after separating out water respectively, prepare liquid CO
2.
7. operation method according to claim 6, is characterized in that, described air compressor (19) outlet pressure is 30atm.
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| CN106025313A (en) * | 2016-07-15 | 2016-10-12 | 中国华能集团清洁能源技术研究院有限公司 | Integrated gasification fuel cell power generation system capable of realizing CO2 trapping before combustion |
| CN106122977A (en) * | 2016-09-05 | 2016-11-16 | 重庆科技学院 | CO2 recovery system based on refuse gasification combustion gas and steam turbine cogeneration |
| CN108428919A (en) * | 2018-04-13 | 2018-08-21 | 中国华能集团清洁能源技术研究院有限公司 | A kind of hybrid power system and method based on Direct Carbon Fuel Cells |
| CN109004244A (en) * | 2018-07-09 | 2018-12-14 | 中国石油大学(北京) | Solid oxide fuel cell association system based on solar energy preparing hydrogen by reforming methanol |
| CN109326805A (en) * | 2018-09-04 | 2019-02-12 | 新地能源工程技术有限公司 | A kind of solid oxide fuel cell power generating system and technique |
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| CN112290055A (en) * | 2020-10-28 | 2021-01-29 | 中国科学技术大学 | Self-humidifying anode fuel circulation system and method of fuel cell system |
| DE102020122082A1 (en) | 2020-08-24 | 2022-02-24 | Audi Aktiengesellschaft | Solid oxide fuel cell device and fuel cell vehicle |
| CN115763883A (en) * | 2022-11-17 | 2023-03-07 | 华北电力大学 | Zero-carbon-emission solid oxide fuel cell power generation system integrated with oxygen permeable membrane |
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| CN106025313B (en) * | 2016-07-15 | 2018-07-10 | 中国华能集团清洁能源技术研究院有限公司 | CO before burning can be achieved2The integral coal gasification fuel cell generation of trapping |
| CN106025313A (en) * | 2016-07-15 | 2016-10-12 | 中国华能集团清洁能源技术研究院有限公司 | Integrated gasification fuel cell power generation system capable of realizing CO2 trapping before combustion |
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| CN108428919A (en) * | 2018-04-13 | 2018-08-21 | 中国华能集团清洁能源技术研究院有限公司 | A kind of hybrid power system and method based on Direct Carbon Fuel Cells |
| CN108428919B (en) * | 2018-04-13 | 2023-07-07 | 中国华能集团清洁能源技术研究院有限公司 | Hybrid power generation system and method based on direct carbon fuel cell |
| CN109004244A (en) * | 2018-07-09 | 2018-12-14 | 中国石油大学(北京) | Solid oxide fuel cell association system based on solar energy preparing hydrogen by reforming methanol |
| CN109326805A (en) * | 2018-09-04 | 2019-02-12 | 新地能源工程技术有限公司 | A kind of solid oxide fuel cell power generating system and technique |
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| WO2022043154A1 (en) | 2020-08-24 | 2022-03-03 | Audi Ag | Solid oxide fuel cell device including an arrangement for co2 separation, and fuel cell vehicle |
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| CN112290055B (en) * | 2020-10-28 | 2021-12-10 | 中国科学技术大学 | Self-humidifying anode fuel circulation system and method of fuel cell system |
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| CN115763883A (en) * | 2022-11-17 | 2023-03-07 | 华北电力大学 | Zero-carbon-emission solid oxide fuel cell power generation system integrated with oxygen permeable membrane |
| CN115763883B (en) * | 2022-11-17 | 2024-03-08 | 华北电力大学 | Zero-carbon-emission solid oxide fuel cell power generation system integrated with oxygen permeable membrane |
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