CN106086924B - One kind coupling CO2The hydrogen manufacturing energy storage method of recycling - Google Patents
One kind coupling CO2The hydrogen manufacturing energy storage method of recycling Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 160
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 160
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- 238000004064 recycling Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004146 energy storage Methods 0.000 title claims abstract description 27
- 238000010168 coupling process Methods 0.000 title claims description 25
- 238000005859 coupling reaction Methods 0.000 title claims description 25
- 230000008878 coupling Effects 0.000 title claims description 24
- 230000002441 reversible effect Effects 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 53
- 238000010248 power generation Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 54
- 230000005611 electricity Effects 0.000 claims description 25
- 239000000446 fuel Substances 0.000 claims description 15
- 239000007772 electrode material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000001218 confocal laser scanning microscopy Methods 0.000 claims description 3
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 claims description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract description 12
- 230000001172 regenerating effect Effects 0.000 abstract description 5
- 206010068052 Mosaicism Diseases 0.000 abstract description 3
- 210000003765 sex chromosome Anatomy 0.000 abstract description 3
- 238000009165 androgen replacement therapy Methods 0.000 description 38
- 238000005516 engineering process Methods 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 230000007812 deficiency Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Materials Engineering (AREA)
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- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides one kind to couple CO2The hydrogen manufacturing energy storage method of recycling, for controlling TRT, device for producing hydrogen and reversible SOFC devices using wind energy and solar power generation, and obtain the generated energy Q1 of TRT, the power consumption Q2 needed for device for producing hydrogen electrolysis water, reversible SOFC devices electrolysis water and CO altogether2Required power consumption Q3；Work as Q1>During Q2+Q3, TRT is powered to device for producing hydrogen and reversible SOFC devices respectively；Work as Q2+Q3>Q1>During Q2, TRT is only powered to device for producing hydrogen；Work as Q2>During Q1, reversible SOFC devices enter SOFC mode of operations, and caused electric energy is powered for device for producing hydrogen.The method of the present invention has not only laid in regenerative resource, also achieves CO2Recycling, efficiently solve the intermittence and fluctuation sex chromosome mosaicism because causing electrolytic hydrogen production using wind energy, solar power generation, and also it is avoided that the conventional electric energy of consumption, electrolytic hydrogen production cost is greatly reduced, improves electrolytic efficiency, extends the service life of device for producing hydrogen, improve the stability and capacity usage ratio of device for producing hydrogen.
Description
Technical field
The invention belongs to technical field of energy utilization, more particularly to the SPE that a kind of wind energy-solar energy-SOEC energy is complementary
Couple CO2The hydrogen manufacturing energy storage method of recycling.
Background technology
In the development course of the mankind, the fossil energy such as coal, oil, natural gas is made that Zhuo for the progress of human civilization
Contribution more, in following decades development of the fossil energy to human society still play very important effect.However, with
The fast development of economy and population, the factors such as the excessive exploitation of fossil energy and utilization rate are low have resulted in worldwide energy
Source crisis, and seriously destroy the ecological balance, especially in technology relatively backward undeveloped country or developing country,
Environmental pollution becomes increasingly conspicuous to the harm that people's life is brought, and therefore, develops novel energy, develops the energy conversion of clean and effective
Strategy has turned into the inevitable choice of survival and development of mankind.
As a kind of regenerative resource of cleaning, hydrogen is acknowledged as the final choice of energy supply, soild oxide
Electrolyte (SPE) water electrolysis hydrogen production technology can prepare High Purity Hydrogen, thus be highly suitable for developing hydrogen fuel cell.SPE at present
The electrolytic efficiency of hydrogen manufacturing reaches as high as 75%, but total hydrogen production efficiency only has 35%, because hydrogen producing technology mainly consumes
Be electric energy, it is 4.5~5.5kWh averagely to produce the electric energy needed for every cubic metre of hydrogen, and electricity charge consumption accounts for whole hydrogen manufacturing cost
80%, therefore, how effectively to reduce hydrogen manufacturing cost, improve hydrogen production efficiency be this area research important topic.
In recent years, hair at full speed has been obtained in the world using the generation technology of the regenerative resources such as wind energy, solar energy
The production scale of exhibition, wind energy and solar power generation and the marketization are also further expanded.But due to wind energy and solar power generation
There is deficiency that is unstable, being difficult to intelligent grid connection, so can by wind energy and solar energy by SPE water electrolysis hydrogen productions and
Ground connection is stored in H2In, this mode is more beneficial for the storage and transport of the energy, and complicated power network is not needed in transportation
Transportation system, energy loss are few.For example, Chinese patent literature CN105631230A disclose a kind of solar photovoltaic assembly with
The direct-coupling optimization method of SPE electrolytic cells, this method pass through to the tandem photovoltaic cells plate number in photovoltaic generation hydrogen generating system
Amount is accurately calculated so that photovoltaic module directly can be connected with SPE electrolytic cells, so as to optimize resource distribution, be improved
The whole work efficiency of hydrogen generating system.However, wind energy and solar power generation are larger by inside even from weather, night is without daylight, the moon
Wind energy and solar energy can be all caused individually to generate electricity in the presence of intermittent and fluctuation, so as to influence when it rains or wind-force deficiency
The efficiency of SPE electrolytic hydrogen productions, above-mentioned technology obviously do not account for this reality, thus can not overcome because using wind energy and
Solar power generation and cause the intermittence of SPE electrolytic hydrogen productions and the defects of fluctuation.
It is well known that consumption and the CO of fossil energy2Discharge it is closely related, CO2It is global caused by isothermal chamber gas
Climate warming problem has turned into the important issue of current international community discussion.Electrolytic tank of solid oxide (SOEC) technology can be total to
It is electrolysed CO2With aquatic production of synthetic gas, make CO2Turn waste into wealth, realize CO2Recycling.In addition, SOEC inverse operation is
As SOFC (SOFC), chemical energy can be converted into electric energy by it, have wide (such as the institute of fuel tolerance
Can be H with fuel2, CO or hydrocarbon), it is compact-sized, safeguard the advantages that simple, part load efficiency is high.It is above-mentioned this
Kind both may be at SOFC mode of operations, may be at the SOFC of SOEC mode of operations again, referred to as may be used
Inverse solid oxidized fuel cell, referred to as reversible SOFC.
In summary, reversible SOFC and SPE electrolytic hydrogen production technologies coupling how to be realized so that both using SOFC
Electricity generation system is that SPE is powered to solve the intermittence because being caused SPE electrolytic hydrogen productions using wind energy and solar power generation and fluctuation
Sex chromosome mosaicism, CO can be reached by SOEC electrolysis systems again2The purpose of recycling, this is still the technology of this area research
Blank spot.
The content of the invention
The technical problems to be solved by the invention are to overcome prior art can not realize reversible because conversion efficiency is low
The defects of SOFC couples with electrolytic hydrogen production, and then offer one kind can couple CO2The hydrogen manufacturing energy storage method of recycling, with solution
Certainly because causing electrolytic hydrogen production the problem of intermittent and fluctuation to be present using wind energy and solar power generation, while realize CO2's
Recycling.
Therefore, the present invention realizes that the technical scheme of above-mentioned purpose is：
One kind coupling CO2The hydrogen manufacturing energy storage method of recycling, for controlling the hair using wind energy and solar power generation
Electric installation, device for producing hydrogen and reversible SOFC devices, obtain the generated energy Q1 of the TRT, the device for producing hydrogen electrolysis water institute
The common electrolysis water of power consumption Q2, the reversible SOFC devices and CO needed2Required power consumption Q3；
Work as Q1>During Q2+Q3, the TRT is powered to the device for producing hydrogen and the reversible SOFC devices respectively, with
Make the device for producing hydrogen production hydrogen and oxygen, while the reversible SOFC devices are made into SOEC mode of operations and contain H2、
CO、CH4And C2H4Mixed gas；
Work as Q2+Q3>Q1>During Q2, the TRT is only powered to the device for producing hydrogen；
Work as Q2>During Q1, the reversible SOFC devices enter SOFC mode of operations, are generated electricity using fuel and air, caused
Electric energy is powered for the device for producing hydrogen.
Preferably, Q1 is worked as>During Q2+Q3, in addition to electric energy caused by the TRT is incorporated into the power networks.
Preferably, Q2 is worked as>During Q1, in addition to electric energy caused by the reversible SOFC devices is incorporated into the power networks.
Preferably, the fuel is hydrogen or reversible SOFC devices obtained gaseous mixture under SOEC mode of operations
Body.
Preferably, the hydrogen is obtained by the device for producing hydrogen electrolysis water.
Further, the required water of mixed gas heating electrolysis is utilized.
Further, the caused cathode exhaust gas heating electrolysis under SOFC mode of operations using the reversible SOFC devices
Required water.
Preferably, in the reversible SOFC devices, hydrogen electrode material be Ni-YSZ, Ni-SDC, Ni-GDC, LSCM or
SFM, Oxygen Electrode Material BSCF, LSCF or SSC, the one or more in electrolyte YSZ, SDC, GDC or LSGM.
Preferably, under the conditions of existing for catalyst, the common electrolysis water of the reversible SOFC devices and CO2The mixing is made
Gas, the catalyst are nanometer Cu-series catalyst.
The above-mentioned technical proposal of the present invention has the following advantages that：
1st, coupling CO of the present invention2The hydrogen manufacturing energy storage method of recycling, wind energy and the sun are utilized for controlling
TRT, device for producing hydrogen and the reversible SOFC devices that can be generated electricity, and obtain the generated energy Q1 of TRT, device for producing hydrogen electrolysis
The common electrolysis water of power consumption Q2, reversible SOFC devices and CO needed for water2Required power consumption Q3；Work as Q1>During Q2+Q3, generate electricity dress
Put and powered respectively to device for producing hydrogen and reversible SOFC devices, so that device for producing hydrogen production hydrogen and oxygen, while reversible SOFC is filled
Put to be made into SOEC mode of operations and contain H2、CO、CH4And C2H4Mixed gas；Work as Q2+Q3>Q1>During Q2, TRT
Only powered to device for producing hydrogen；Work as Q2>During Q1, reversible SOFC devices enter SOFC mode of operations, are generated electricity using fuel and air,
Caused electric energy is powered for device for producing hydrogen.The method of the present invention is electrolysed institute by the generated energy according to TRT, device for producing hydrogen
Need power consumption and reversible SOFC devices electrolysis needed for power consumption to control the electric energy of TRT to export, the electricity of device for producing hydrogen
Can input and reversible SOFC devices electric energy output or input, efficiently solve prior art because conversion efficiency is low can not be real
The defects of existing reversible SOFC couples with electrolytic hydrogen production so that wind energy, solar energy can be converted into chemical energy and stored up respectively by the present invention
It is stored in hydrogen and above-mentioned mixed gas, has not only laid in regenerative resource, the fuel gas of cleaning has been made, has also achieved simultaneously
CO2Recycling, and the combination of wind energy and solar energy cause the present invention cope with substantially various weather conditions to hair
Negatively affected caused by electric installation, even in the case of wind energy, solar energy deficiency, the present invention can also be filled by reversible SOFC
The generating put continues as device for producing hydrogen and provides electric energy, on the one hand can ensure that the continued electrolysis hydrogen manufacturing of device for producing hydrogen, so as to effectively solve
Determine because causing electrolytic hydrogen production the problem of intermittent and fluctuation to be present using wind energy, solar power generation, on the other hand also may be used
The conventional electric energy of device for producing hydrogen consumption is avoided, the cost of electrolytic hydrogen production is significantly reduced, improves electrolytic efficiency so that the present invention
Hydrogen production efficiency may be up to 70%, the third aspect, which additionally aids, to extend the service life of device for producing hydrogen, improves the steady of device for producing hydrogen
Qualitative and capacity usage ratio.
2nd, coupling CO of the present invention2The hydrogen manufacturing energy storage method of recycling, works as Q1>During Q2+Q3, TRT
Electric energy caused by the TRT can also be incorporated into the power networks in addition to being powered to device for producing hydrogen and reversible SOFC devices；Work as Q2
>During Q1, reversible SOFC devices can also be grid-connected by electric energy caused by the reversible SOFC devices in addition to being powered to device for producing hydrogen
Operation；So that the method for the present invention can not only hydrogen storage, moreover it is possible to which realization is incorporated into the power networks, and in peak times of power consumption, generate electricity dress
Unnecessary electric energy can be supplied in power network by putting, while reversible SOFC devices can also utilize the change stored by its own common-battery solution
For huge numbers of families can be transmitted electric power, and reach the purpose of peak load shifting.
3rd, coupling CO of the present invention2The hydrogen manufacturing energy storage method of recycling, because reversible SOFC devices are in SOEC
Operating temperature under mode of operation is 800 DEG C or so, at such high temperatures electrolysis water and CO altogether2Caused mixed gas itself
Substantial amounts of heat is carry, in addition, reversible SOFC devices caused cathode exhaust gas under SOFC mode of operations also has necessarily
Heat, thus water of the present invention needed for by using the mixed gas or cathode exhaust gas heating electrolysis, so as to be advantageous to further
Reduce hydrogen manufacturing cost, improve system effectiveness, realize cogeneration.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in the specific embodiment of the invention, embodiment will be retouched below
The required accompanying drawing used is briefly described in stating, it should be apparent that, drawings in the following description are some realities of the present invention
Mode is applied, for those of ordinary skill in the art, on the premise of not paying creative work, can also be attached according to these
Figure obtains other accompanying drawings.
Fig. 1 is coupling CO of the present invention2The flow chart of the hydrogen manufacturing energy storage method of recycling；
Fig. 2 is the coupling CO described in the embodiment of the present invention 62The schematic diagram of the hydrogen manufacturing energy storage device of recycling；
Wherein, reference is as follows：
1- solar cells；2- wind-driven generators；3- electrolysis units；4- hydrogen containers；The electricity output end of 5- TRTs；6-
The electricity output end of reversible SOFC devices；The electrical input of the reversible SOFC devices of 7-, the reversible SOFC devices of 8-；9- control units；
10- negative electrode apparatus for recovering；11-CO2Gas tank；12- mixing gas tanks；13- water tanks；14- tank bodies；The heat exchanger tubes of 15- first
Road；The heat exchange pipelines of 16- second；17- condensate recycling devices；The magnetic valves of 18- first；19- second solenoid valves；The electromagnetism of 20- the 3rd
Valve；The magnetic valves of 21- the 4th；The magnetic valves of 22- the 5th；The magnetic valves of 23- the 6th；24- water vaporizers；25- gas mixers；26- oxygen
Gas tank.
Embodiment
Technical scheme is clearly and completely described below in conjunction with accompanying drawing, it is clear that described implementation
Example is part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill
The every other embodiment that personnel are obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
In addition, as long as technical characteristic involved in invention described below different embodiments does not form conflict just each other
It can be combined with each other.
Embodiment 1
As shown in figure 1, the coupling CO described in the present embodiment2The hydrogen manufacturing energy storage method of recycling can be used for control to utilize
The TRT of wind energy and solar power generation, SPE device for producing hydrogen and reversible SOFC devices, the generated energy Q1 of the TRT
Power consumption Q2=58 kilowatt hours, the reversible SOFC devices needed for=1200 kilowatt hours, the SPE device for producing hydrogen electrolysis water are total to
Electrolysis water and CO2Required power consumption Q3=95 kilowatt hours；
On this condition, an electric energy part caused by the TRT is powered to the SPE device for producing hydrogen so that described
SPE device for producing hydrogen electrolysis water produces hydrogen and oxygen, and another part is powered to the reversible SOFC devices, at this moment described reversible
SOFC devices enter SOEC mode of operations, common electrolysis water and CO in the presence of nanometer Cu-series catalyst2It is made and contains H2、CO、
CH4And C2H4Mixed gas, and remainder electric energy is incorporated into the power networks.
In the present embodiment, the hydrogen electrode material of the reversible SOFC devices is Ni-YSZ, Oxygen Electrode Material LSCF, electricity
Solution matter is LSGM.
Embodiment 2
As shown in figure 1, the coupling CO described in the present embodiment2The hydrogen manufacturing energy storage method of recycling, which is used to control, utilizes wind
Can be with TRT, SPE device for producing hydrogen and the reversible SOFC devices of solar power generation, the generated energy Q1=of the TRT
Power consumption Q2=58 kilowatt hours, the reversible SOFC devices common-battery needed for 135 kilowatt hours, the SPE device for producing hydrogen electrolysis water
Xie Shui and CO2Required power consumption Q3=95 kilowatt hours；
On this condition, the TRT is only powered to the SPE device for producing hydrogen, and reversible SOFC devices are then cut
Power-off can supply.
In the present embodiment, the hydrogen electrode material of the reversible SOFC devices is LSCM, Oxygen Electrode Material BSCF, is electrolysed
Matter is SDC.
Embodiment 3
As shown in figure 1, the coupling CO described in the present embodiment2The hydrogen manufacturing energy storage method of recycling, which is used to control, utilizes wind
Can be with TRT, SPE device for producing hydrogen and the reversible SOFC devices of solar power generation, the generated energy Q1=10 of the TRT
The common electrolysis water of power consumption Q2=58 kilowatt hours, the reversible SOFC devices needed for kilowatt hour, the SPE device for producing hydrogen electrolysis water
And CO2Required power consumption Q3=95 kilowatt hours；
On this condition, the reversible SOFC devices enter SOFC mode of operations, are mixed using made from its own common-battery solution
Close gas to generate electricity as fuel and air, caused electric energy fills up to 86 kilowatt hours, a portion electric energy for the SPE hydrogen manufacturing
Power supply is put, remainder electric energy is then incorporated into the power networks.
In the present embodiment, the hydrogen electrode material of the reversible SOFC devices is SFM, Oxygen Electrode Material SSC, electrolyte
For GDC.
Embodiment 4
As shown in figure 1, the coupling CO described in the present embodiment2The hydrogen manufacturing energy storage method of recycling, which is used to control, utilizes wind
Can be with TRT, SPE device for producing hydrogen and the reversible SOFC devices of solar power generation, the generated energy Q1=of the TRT
Power consumption Q2=58 kilowatt hours, the reversible SOFC devices common-battery needed for 1142 kilowatt hours, the SPE device for producing hydrogen electrolysis water
Xie Shui and CO2Required power consumption Q3=95 kilowatt hours；
On this condition, an electric energy part caused by the TRT is powered to the SPE device for producing hydrogen so that described
SPE device for producing hydrogen electrolysis water produces hydrogen and oxygen, and another part is powered to the reversible SOFC devices, at this moment described reversible
SOFC devices enter SOEC mode of operations, common electrolysis water and CO in the presence of nanometer Cu-series catalyst2It is made and contains H2、CO、
CH4And C2H4Mixed gas, and remainder electric energy is incorporated into the power networks；
At the same time, exchanged heat using the mixed gas and water, to heat water, then heated water is used as the SPE
Water source needed for device for producing hydrogen and the reversible SOFC devices electrolysis.
In the present embodiment, the hydrogen electrode material of the reversible SOFC devices is Ni-SDC, Oxygen Electrode Material SSC, electricity
Solution matter is YSZ.
Embodiment 5
As shown in figure 1, the coupling CO described in the present embodiment2The hydrogen manufacturing energy storage method of recycling, which is used to control, utilizes wind
Can be with TRT, SPE device for producing hydrogen and the reversible SOFC devices of solar power generation, the generated energy Q1=10 of the TRT
The common electrolysis water of power consumption Q2=58 kilowatt hours, the reversible SOFC devices needed for kilowatt hour, the SPE device for producing hydrogen electrolysis water
And CO2Required power consumption Q3=95 kilowatt hours；
On this condition, the reversible SOFC devices enter SOFC mode of operations, are mixed using made from its own common-battery solution
Close gas to generate electricity as fuel and air, caused electric energy fills up to 86 kilowatt hours, a portion electric energy for the SPE hydrogen manufacturing
Power supply is put, remainder electric energy is then incorporated into the power networks；
At the same time, exchanged heat using the cathode exhaust gas of the reversible SOFC devices discharge with water, to heat water, then will be through adding
The water of heat is used as the water source needed for SPE device for producing hydrogen electrolysis.
In the present embodiment, the hydrogen electrode material of the reversible SOFC devices is Ni-GDC, Oxygen Electrode Material LSCF, electricity
Solution matter is GDC.
Embodiment 6
Method described in above-described embodiment 1-5 is based on coupling CO as shown in Figure 22The hydrogen manufacturing energy storage of recycling
Device and realize, the device includes TRT, device for producing hydrogen, reversible SOFC devices and control unit, wherein：The hair
Electric installation includes solar cell 1 and wind-driven generator 2；The device for producing hydrogen include electrolysis unit 3 and with the electrolysis unit 3
Connected hydrogen container 4 and oxygen tank 26, the electrolysis unit 3 are connected with the electricity output end 5 of the TRT；It is described reversible
The electrical input 7 of SOFC devices 8 is connected with the electricity output end 5 of the TRT, the electricity output of the reversible SOFC devices 8
End 6 is connected with the electrolysis unit 3, and the reversible SOFC devices 8 are additionally provided with CO2Import and fuel inlet；The control is single
Power consumption and the reversible SOFC needed for member 9 is used for the generated energy according to the TRT, the device for producing hydrogen is electrolysed fill
Put power consumption needed for 8 electrolysis control the electric energy output of the TRT, control the electric energy of the device for producing hydrogen input and
The electric energy of the reversible SOFC devices 8 is controlled to export or input.
Device described in the present embodiment is by setting control unit so that control unit can be according to the generating of TRT
Measure Q1, the required power consumption Q2 of device for producing hydrogen electrolysis and reversible SOFC devices and be electrolysed the required triangular sizes of power consumption Q3
Relation determines the electric energy output of TRT, the electric energy input of device for producing hydrogen and the electric energy output or input of reversible SOFC devices,
Specifically, Q1 is worked as>During Q2+Q3, TRT is powered to device for producing hydrogen and reversible SOFC devices respectively so that device for producing hydrogen
Hydrogen is made in generation electrolysis, while reversible SOFC devices also enter SOEC mode of operations electrolysis water and CO altogether2It is made and contains H2、CO、
CH4And C2H4Mixed gas, be stored into hydrogen and above-mentioned mixed gas respectively so that wind energy, solar energy are converted into chemical energy
In, regenerative resource is not only laid in, while also achieve CO2Recycling；Work as Q2+Q3>Q1>During Q2, TRT
Only powered to device for producing hydrogen, to ensure to continue hydrogen manufacturing；And work as Q2>During Q1, i.e., electric energy caused by TRT can not meet hydrogen manufacturing
Device is electrolysed required electric energy, then reversible SOFC devices enter SOFC mode of operations, is generated electricity using fuel and air, and then is system
Hydrogen production device provides electric energy, therefore ensures that the continued electrolysis hydrogen manufacturing of device for producing hydrogen, so as to effectively solve because being sent out using wind energy, solar energy
Intermittence that is electric and causing electrolytic hydrogen production and fluctuation sex chromosome mosaicism.Also, the device of the present embodiment is by using wind energy and solar energy
For device for producing hydrogen and the work of reversible SOFC devices provides electric energy Deng renewable energy power generation, the combination of wind energy and solar energy causes
The device of embodiment copes with various weather conditions to negative effect caused by TRT substantially；Even if in wind energy, the sun
The present embodiment can also be generated electricity by reversible SOFC devices and continue as device for producing hydrogen offer electric energy in the case of energy deficiency, on the one hand be kept away
Exempt from the conventional electric energy of device for producing hydrogen consumption, significantly reduce the cost of electrolytic hydrogen production, improve electrolytic efficiency so that the present embodiment
Hydrogen production efficiency may be up to 70%, on the other hand additionally aid extend electrolysis unit service life, improve electrolysis unit it is steady
Qualitative and capacity usage ratio.
In the present embodiment, described control unit 9 includes A/D converter, transformer and the controller being sequentially connected with；It is described
Controller be used for by electric energy caused by the TRT be transferred to the electrolysis unit 3, the reversible SOFC devices 8 and/or
Power network and electric energy caused by the reversible SOFC devices 8 is transferred to the electrolysis unit 3 and/or power network, so that this
The device of embodiment can not only hydrogen storage, moreover it is possible to which realization is incorporated into the power networks, and in peak times of power consumption, TRT can will be unnecessary
Electric energy is supplied to power network, while it is huge numbers of families that reversible SOFC devices, which can also utilize the chemical energy stored by its own common-battery solution,
Transmit electric power, reach the purpose of peak load shifting.
As preferred embodiment, the fuel inlet is connected with the hydrogen container 4, to be electrolysed using device for producing hydrogen
Caused hydrogen is generated electricity as SOFC fuel.Further, the reversible SOFC devices 8 are additionally provided with cathode exhaust gas and gone out
Mouthful, the cathode exhaust gas outlet is connected with negative electrode apparatus for recovering 10.
As selectable embodiment, the device in the present embodiment also includes the CO with the reversible SOFC devices 82
The CO that import is connected2Gas tank 11, respectively with the water inlet of the reversible SOFC devices 8 and the water inlet of the electrolysis unit 3
The water tank 13 that is connected, water vaporizer 24, gas mixer 25 and it is connected with the gas outlet of the reversible SOFC devices 8
The mixing gas tank 12 connect；In the present embodiment, the water in water tank 13 after the vaporization of water vaporizer 24 and comes from CO2Gas tank 11
In CO2Gas is sufficiently mixed in gas mixer 25, then enters and common-battery solution occurs in reversible SOFC devices 8, generation contains
H2、CO、CH4And C2H4Mixed gas and be stored in mixing gas tank 12 in, the mixed gas can both make as SOFC fuel
With can also respectively obtain pure H after separation2、CO、CH4And C2H4Gas.
Because operating temperature of the reversible SOFC devices 8 under SOEC mode of operations is 800 DEG C or so, at such high temperatures altogether
Electrolysis water and CO2Caused mixed gas it is self-contained substantial amounts of heat, also, reversible SOFC devices 8 SOFC work
Caused cathode exhaust gas also has certain heat under pattern, thus is used as preferred embodiment, the dress described in the present embodiment
Put and be additionally provided with heat-exchanging water tank, the heat-exchanging water tank includes tank body 14 and set along the outer wall spiral of the tank body 14
The first heat exchange pipeline 15 and the second heat exchange pipeline 16, wherein, the tank body 14 is provided with water inlet and delivery port, described
Water inlet is connected with the water tank 13, the delivery port water inlet with the reversible SOFC devices 8 and the electricity respectively
The water inlet of solution device 3 is connected, the both ends of first heat exchange pipeline 15 gas outlet with the reversible SOFC devices 8 respectively
It is connected with the mixing gas tank 12, the both ends of second heat exchange pipeline 16 export and negative electrode water with the cathode exhaust gas respectively
Retracting device 10 is connected；So as to preheat the water source needed for electrolytic process respectively using mixed gas and cathode exhaust gas,
So as to be advantageous to further reduce hydrogen manufacturing cost, improve system effectiveness, cogeneration is realized.
To obtain pure fuel gas as much as possible, the device described in the present embodiment also includes condensate recycling device 17,
It is arranged at the tank body 14 with first heat exchange pipeline 15 mixed between gas tank 12, and with the reversible SOFC
The gas outlet of device 8 is connected with the mixing gas tank 12, can so remove and be adulterated in mixed gas caused by common-battery solution
Water vapour.
It is more pure in view of the water in condensate recycling device and negative electrode apparatus for recovering and there is certain temperature, because
And the device described in the present embodiment is also further provided with the first magnetic valve 18 and second solenoid valve 19, with respectively by the condensation
Retracting device 17, the negative electrode apparatus for recovering 10 are connected with the tank body 14.In addition, the dress described in the present embodiment
Putting also includes being arranged on the CO2The CO of gas tank 11 and the reversible SOFC devices 82The 3rd on connection line between import
Magnetic valve 20, the 4th be arranged on the connection line between the water inlet of the water tank 13 and the reversible SOFC devices 8
Magnetic valve 21, it is arranged on the enter on the connection line between hydrogen mouth and the hydrogen container 4 the 5th electricity of the reversible SOFC devices 8
The 6th magnetic valve 23 on magnet valve 22, and the connection line being arranged between the water tank 13 and the tank body 14,
And opening/breaking for above-mentioned six magnetic valves is controlled by the controller, to realize CO2Gas, hydrogen, water vapour and water it is automatic
Change supply, so as to be also beneficial to improve the hydrogen manufacturing energy storage efficiency of the present embodiment described device.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (9)
1. one kind coupling CO2The hydrogen manufacturing energy storage method of recycling, for controlling the generating dress using wind energy and solar power generation
Put, device for producing hydrogen and reversible SOFC devices, it is characterised in that：
Obtain the generated energy Q1 of the TRT, power consumption Q2, the reversible SOFC needed for the device for producing hydrogen electrolysis water
The common electrolysis water of device and CO2Required power consumption Q3；
Work as Q1>During Q2+Q3, the TRT is powered to the device for producing hydrogen and the reversible SOFC devices respectively, so that institute
Device for producing hydrogen production hydrogen and oxygen are stated, while the reversible SOFC devices are made into SOEC mode of operations and contain H2、CO、CH4
And C2H4Mixed gas；
Work as Q2+Q3>Q1>During Q2, the TRT is only powered to the device for producing hydrogen；
Work as Q2>During Q1, the reversible SOFC devices enter SOFC mode of operations, are generated electricity using fuel and air, caused electric energy
Powered for the device for producing hydrogen.
2. coupling CO according to claim 12The hydrogen manufacturing energy storage method of recycling, it is characterised in that work as Q1>Q2+Q3
When, in addition to electric energy caused by the TRT is incorporated into the power networks.
3. coupling CO according to claim 1 or 22The hydrogen manufacturing energy storage method of recycling, it is characterised in that work as Q2>Q1
When, in addition to electric energy caused by the reversible SOFC devices is incorporated into the power networks.
4. coupling CO according to claim 12The hydrogen manufacturing energy storage method of recycling, it is characterised in that the fuel is
Hydrogen or reversible SOFC devices obtained mixed gas under SOEC mode of operations.
5. coupling CO according to claim 42The hydrogen manufacturing energy storage method of recycling, it is characterised in that the hydrogen by
The device for producing hydrogen electrolysis water and obtain.
6. according to the coupling CO described in claim 1,2,4 or 52The hydrogen manufacturing energy storage method of recycling, it is characterised in that profit
With the water needed for mixed gas heating electrolysis.
7. according to the coupling CO described in claim 1,2,4 or 52The hydrogen manufacturing energy storage method of recycling, it is characterised in that profit
With water of the reversible SOFC devices under SOFC mode of operations needed for caused cathode exhaust gas heating electrolysis.
8. coupling CO according to claim 12The hydrogen manufacturing energy storage method of recycling, it is characterised in that described reversible
In SOFC devices, hydrogen electrode material is Ni-YSZ, Ni-SDC, Ni-GDC, LSCM or SFM, Oxygen Electrode Material BSCF, LSCF or
One or more in SSC, electrolyte YSZ, SDC, GDC or LSGM.
9. coupling CO according to claim 12The hydrogen manufacturing energy storage method of recycling, it is characterised in that deposited in catalyst
Under the conditions, the common electrolysis water of the reversible SOFC devices and CO2The mixed gas is made, the catalyst is nanometer copper system
Catalyst.
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| CN109837553B (en) * | 2019-03-20 | 2023-10-27 | 宁波大学 | Power generation and hydrogen production integrated device of marine diesel engine coupling solid oxide electrolytic cell |
| CN111663150B (en) * | 2020-07-15 | 2022-02-01 | 全球能源互联网研究院有限公司 | Wave type power input hydrogen production method by electrolyzing water and device thereof |
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