CN109704276A - A kind of hydrogen production of chemical chain and power generation cycle system of Driven by Solar Energy - Google Patents
A kind of hydrogen production of chemical chain and power generation cycle system of Driven by Solar Energy Download PDFInfo
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- CN109704276A CN109704276A CN201811566994.8A CN201811566994A CN109704276A CN 109704276 A CN109704276 A CN 109704276A CN 201811566994 A CN201811566994 A CN 201811566994A CN 109704276 A CN109704276 A CN 109704276A
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
- Y02E10/46—Conversion of thermal power into mechanical power, e.g. Rankine, Stirling or solar thermal engines
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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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
- 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
Abstract
The present invention relates to a kind of hydrogen production of chemical chain of Driven by Solar Energy and power generation cycle systems, comprising: fuel reaction device: being used for CH4And Fe3O4Reaction generates FeO, CO2And H2O；Solar heater (3): for heating Fe3O4And whereabouts fuel reaction device；Steam reaction device: it is used for H2O and FeO reaction, generates Fe3O4And H2, the FeO that the FeO is generated from fuel reaction device, the Fe3O4Whereabouts solar heater (3)；Heat engine device: acting power generation is carried out using the heat that fuel reaction device and steam reaction device generate；Heat-exchanger rig: for collecting the heat of fuel reaction device and steam reaction device and treating reaction CH4And H2O is preheated；Cooling device: for cooling down the reaction product of fuel reaction device and steam reaction device, and H is respectively obtained2With CO2.Compared with prior art, invention introduces clean solar energy to carry out hydrogen making, and the CO after burning is captured in the way of low energy consumption2, it is CO in a kind of reduction atmosphere2The effective way of concentration.
Description
Technical field
The present invention relates to a kind of hydrogen manufacturing circulatory systems, hydrogen production of chemical chain and power generation more particularly, to a kind of Driven by Solar Energy
The circulatory system.
Background technique
As increasingly reducing and on the growing interest that environment caused by global warming influences, renewable energy for fossil energy
Source is the strong candidate for meeting world energy sources demand.CO2It is the change for causing the main greenhouse gas of global warming, and traditional
Stone fuel combustion is the main source for generating greenhouse gases.According to IPCC's (Intergovernmental Panel on Climate Change)
Report, compared with before the industrial revolution, CO in atmosphere2Concentration improves twice, and earth surface temperature has also improved 2 DEG C~4 DEG C.Face
To such problems, energy industry needs to find the new solution of one kind to overcome these challenges, and mitigates fuel combustion production
Raw CO2Influence to environment.Using renewable energy and cleaning combustion system is combined, can efficiently solve and to face instantly
Problem.
In the state of the art, burning chemistry chains can capture the CO of higher concentration under lower energy consumption condition2,
Huge potentiality thus are shown in the production field of the energy, it is considered to be 21 century most potential new combustion mode.Change
Learning chain burning (Chemical Looping Combustion, abbreviation CLC) basic principle is that traditional fuel and air is direct
Catalytic burning is decomposed into 2 gas-solid reactions, fuel and air by means of the effect of oxygen carrier (Oxygen Carrier)
Without contact, the oxygen in air is transmitted in fuel by oxygen carrier.
High concentration CO can be realized by burning chemistry chains2Collection, but how by hydrogen manufacturing, power generation and burning chemistry chains knot
Need to consider various factors altogether, including the selection of oxygen carrier, the optimization of hot-fluid energy level, heat exchanger arrangement
Deng.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of Driven by Solar Energy
Hydrogen production of chemical chain and power generation cycle system.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of hydrogen production of chemical chain and power generation cycle system of Driven by Solar Energy, comprising:
Fuel reaction device: it is used for CH4And Fe3O4Reaction generates FeO, CO2And H2O；
Solar heater: for heating Fe3O4And whereabouts fuel reaction device；
Steam reaction device: it is used for H2O and FeO reaction, generates Fe3O4And H2, the FeO is from fuel reaction device
The FeO of generation, the Fe3O4Whereabouts solar heater；
Heat engine device: acting power generation is carried out using the heat that fuel reaction device and steam reaction device generate；
Heat-exchanger rig: for collecting the heat of fuel reaction device and steam reaction device and treating reaction CH4And H2O into
Row preheating；
Cooling device: for cooling down the reaction product of fuel reaction device and steam reaction device, and H is respectively obtained2With
CO2。
Further, the steam reaction device includes first reactor and the first separator, first reaction
Device is used for H2O is reacted with FeO, and first separator is for isolating Fe in the product of first reactor3O4And H2
And H2The mixture of O.
Further, the fuel reaction device includes second reactor and the second separator, second reaction
Device is used for Fe3O4With CH4Reaction, and generate FeO, CO2And H2O, the Fe3O4From the first separator, described second
Separator, which is used to generate in product in second reactor, isolates FeO and CO2And H2The mixture of O, it is described to isolate
FeO whereabouts first reactor.
Further, the hydrogen production of chemical chain and power generation cycle system further include solar heater, solar energy heating
Device is used for the Fe for isolating the first separator3O4Second reactor is delivered to after being heated again.
Further, the heat engine device include the first Stirling thermal engine operating and the second Stirling thermal engine operating, described first
The H that Stirling thermal engine operating is isolated using the first separator2With H2The thermal energy of O mixture, which does work, to generate electricity, the second Stirling heat
The CO that machine is isolated using the second separator2And H2O acting power generation.
Further, the heat-exchanger rig includes First Heat Exchanger, the second heat exchanger and third heat exchanger, and described
One heat exchanger is used for the H to whereabouts first reactor2O carries out preliminary indirect heat exchange, and heat exchange heat source used is the second Stirling
The CO exported after heat engine acting power generation2And H2O, second heat exchanger are used for the CH to whereabouts second reactor4It carries out indirect
Heat exchange, heat exchange heat source used are the CO that the second separator is isolated2And H2O, the third heat exchanger are used for whereabouts first
The H of reactor2O carries out secondary indirect heat exchange, and heat exchange heat source used is the H exported after the acting of the first Stirling thermal engine operating generates electricity2
And H2O。
Further, the cooling device includes the first cooler and the second cooler, and first cooler is used
In the CO of First Heat Exchanger will be passed through2And H2O carries out refrigerated separation, and second cooler will be for that will pass through third heat exchanger
H2And H2O carries out refrigerated separation.
Further, first separator and the second separator are cyclone separator.
A method of utilizing hydrogen production of chemical chain and power generation, comprising the following steps:
Step 1, by CH4And Fe3O4Reaction generates FeO, CO2And H2O；
Step 2, by H2O and FeO reaction, generates Fe3O4And H2, the FeO that the FeO is generated from step 1 is described
Fe3O4Whereabouts step 1；
Step 3 carries out acting power generation using the heat generated in step 1 and step 2 reaction；
The heat that generates and respectively to being reacted in step 1 and step 2 in step 4, collection step one and step 2 reaction
Preceding CH4And H2O is preheated；
Step 5 is led to overcooled method and is separated to the reaction product of step 1 and step 2, and respectively obtains H2
With CO2。
Further, the H of generation is reacted in the step one2The H isolated in O and step 52O whereabouts step 2.
Further, the Fe in the step two3O4It is heated first by solar heater before the reaction.
Present invention mainly solves the cleaning burnings and the capture of carbon dioxide of methane, while utilizing solar energy preparing hydrogen
Gas, wherein metal oxide constantly recycles in systems.
Main chemical equation is as follows:
Combustion reaction: CH4+12Fe3O4=8FeO+CO2+2H2O；
Hydrogen production reaction: 3H2O+3FeO=Fe3O4+3H2
During burning chemistry chains, fuel is by metal oxide at CO2And H2O, metal oxide are reduced into gold
The metal oxide of category or low price, and the metal or metal suboxide that are reduced are oxidized to metal oxygen again in air
Compound, the oxygen in such fuel are not obtained from air directly, can effectively reduce the generation of NOx in combustion process.With it is such
Seemingly, during usual two-step method solar hydrogen making, metal is reacted at high temperature with water vapour first, metal is oxidized to metal
Oxide, and water is reduced into H2, concrete principle can be found in Fig. 2.
Compared with prior art, the present invention considers the metal circulation in solar hydrogen making and burning chemistry chains, by this two
Person organically combines, and reacts high-temperature vapor with FeO generate hydrogen first, and FeO is oxidized to Fe3O4, CH later4With Fe3O4?
Grain heats up in the solar heater of high temperature, and the metal oxide after heating is sent in reactor to react with fuel,
Burning chemistry chains are realized, the generation of nitrogen oxides and sulfide is reduced；The high-temperature gas that will be obtained in cyclic process
It is sent to Stirling thermal engine operating acting, high-temperature heat flux energy regenerating is realized with this, so that capacity usage ratio improves；It will be mixed after acting
It closes gas and vapor is removed by cooler, obtain the higher CO of purity2, realize the hydrogen gas production of low energy consumption；In addition, this hair
It is bright to introduce clean solar energy and carry out preparing high purity hydrogen, and the CO after burning is captured in the way of low energy consumption2, it is one
Kind reduces CO in atmosphere2The effective way of concentration.
Detailed description of the invention
Fig. 1 is the knot that Driven by Solar Energy hydrogen production of chemical chain couples the carbon dioxide capture cogeneration circulatory system in the present invention
Structure schematic diagram；
Fig. 2 is the principle of the present invention schematic diagram.
In figure: 1, first reactor, the 2, first separator, 3, solar heater, 4, second reactor, the 5, second separation
Device, the 6, first Stirling thermal engine operating, the 7, second heat exchanger, the 8, first blower, 9, pump, 10, third heat exchanger, the 11, second Stirling
Heat engine, 12, First Heat Exchanger, the 13, second cooler, the 14, first cooler.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment
Hydrogen production of chemical chain and power generation cycle system, referring to Fig. 1, comprising: fuel reaction device: it is used for CH4And Fe3O4Reaction,
Generate FeO, CO2And H2O；Solar heater 3: for heating Fe3O4And whereabouts fuel reaction device；Steam reaction device: it uses
In H2O and FeO reaction, generates Fe3O4And H2, the FeO that the FeO is generated from fuel reaction device, the Fe3O4Whereabouts is too
Positive energy heater 3；Heat engine device: acting power generation is carried out using the heat that fuel reaction device and steam reaction device generate；It changes
Thermal: for collecting the heat of fuel reaction device and steam reaction device and treating reaction CH4And H2O is preheated；It is cooling
Device: for cooling down the reaction product of fuel reaction device and steam reaction device, and H is respectively obtained2With CO2。
Main following reaction process in specific reaction system:
In the steam reaction stage: H2O passes through pump 9 first and is pressurized and is delivered at First Heat Exchanger 12 and be preheated to 90
DEG C, heat exchange heat source used is the CO exported after the acting of the second Stirling thermal engine operating 11 generates electricity2And H2O, H2O passes through First Heat Exchanger
It is passed through after 12 preheating at third heat exchanger 10 and is heated to be 300 DEG C, the heat exchange heat source of third heat exchanger 10 is the first Stirling heat
The H exported after the acting power generation of machine 62And H2O, the H heated by third heat exchanger2O enters the first reaction together with FeO particle
Hydrogen production reaction: 3H occurs for device 12O+3FeO=Fe3O4+3H2, the first separator 2 will generate in first reactor 1 later Fe3O4
Particle and H2With H2The separation of O mixture, and by the Fe after separation3O4Particle is delivered to solar heater 3, solar heater 3
The Fe that first separator 2 is isolated3O4It carries out being heated to being delivered to second reactor 4 after 1000 DEG C again.It is anti-wherein to enter first
Answer the H of device 12The molar ratio of O and FeO is greater than 2.
In the fuel reaction stage: the first blower 8 is to the CH being passed through4Pressurized delivered is carried out, later CH4First it is passed through the second heat exchange
Device 7 carries out being preheated to 700 DEG C, and heat exchange heat source used is the CO that the second separator 5 is isolated2And H2O, subsequent CH4With from the sun
Fe after the energy heating of heater 33O4Particle enters second reactor 4, and combustion reaction: CH occurs4+12Fe3O4=8FeO+CO2+
2H2O, the mixture for reacting generation enter the second separator 5, and second reactor 4 is used for Fe3O4Particle and CH4It reacts and generates
FeO particle, CO2And H2The FeO particle that second reactor 4 generates is separated and is delivered to first reactor 1 by O, the second separator 5
In, and by CO2And H2O is transferred back to the CH exported as heat source to the first blower 8 in the second heat exchanger 44It is heated, wherein into
Enter the Fe of second reactor 43O4The temperature of particle is 1000 DEG C, into the CH of second reactor 44With Fe3O4Molar ratio be less than
0.25。
The thermo-mechanical power generation stage: heat engine device includes the first Stirling thermal engine operating 6 and the second Stirling thermal engine operating 11, the first Stirling
600 DEG C of the H that heat engine 6 is isolated using the first separator 22With H2The thermal energy of O mixture, which does work, to generate electricity, later by 450 DEG C of H2
With H2O mixture is passed through in third heat exchanger 10 as heat source, and the second Stirling thermal engine operating 11 is isolated using the second separator 5
800 DEG C of CO2And H2O acting power generation.
Cooling stage: cooling device includes the first cooler 14 and the second cooler 13, and the first cooler 14 will be by the
100 DEG C of CO of one heat exchanger 122And H2O carries out refrigerated separation, the CO isolated2It can carry out pressurization to seal up for safekeeping, the second cooler 13
100 DEG C of H of third heat exchanger 10 will be passed through2And H2O carries out refrigerated separation, collects the H isolated2。
Claims (10)
1. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy characterized by comprising
Fuel reaction device: it is used for CH4And Fe3O4Reaction generates FeO, CO2And H2O；
Solar heater (3): for heating Fe3O4And whereabouts fuel reaction device；
Steam reaction device: it is used for H2O and FeO reaction, generates Fe3O4And H2, the FeO generates from fuel reaction device
FeO, the Fe3O4Whereabouts solar heater (3)；
Heat engine device: acting power generation is carried out using the heat that fuel reaction device and steam reaction device generate；
Heat-exchanger rig: for collecting the heat of fuel reaction device and steam reaction device and treating reaction CH4And H2O carries out pre-
Heat；
Cooling device: for cooling down the reaction product of fuel reaction device and steam reaction device, and H is respectively obtained2With CO2。
2. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy according to claim 1, which is characterized in that
The steam reaction device includes first reactor (1) and the first separator (2), and the first reactor (1) is used for H2O
It is reacted with FeO, first separator (2) is for isolating Fe in the product of first reactor (1)3O4And H2With
H2The mixture of O.
3. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy according to claim 2, which is characterized in that
The fuel reaction device includes second reactor (4) and the second separator (5), and the second reactor (4) is used for
Fe3O4With CH4Reaction, and generate FeO, CO2And H2O, the Fe3O4From the first separator (2), second separation
Device (5), which is used to generate in product in second reactor (4), isolates FeO and CO2And H2The mixture of O, described isolates
FeO whereabouts first reactor (1).
4. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy according to claim 3, which is characterized in that
The solar heater (3) is used for the Fe for isolating the first separator (2)3O4It is anti-that second is delivered to after being heated again
Answer device (4).
5. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy according to claim 3, which is characterized in that
The heat engine device includes the first Stirling thermal engine operating (6) and the second Stirling thermal engine operating (11), first Stirling thermal engine operating
(6) H isolated using the first separator (2)2With H2The thermal energy of O mixture, which does work, to generate electricity, second Stirling thermal engine operating
(11) CO isolated using the second separator (5)2And H2O acting power generation.
6. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy according to claim 5, which is characterized in that
The heat-exchanger rig includes First Heat Exchanger (12), the second heat exchanger (7) and third heat exchanger (10), first heat exchange
Device (12) is used for the H to whereabouts first reactor (1)2O carries out preliminary indirect heat exchange, and heat exchange heat source used is the second Stirling
The CO exported after heat engine (11) acting power generation2And H2O, second heat exchanger are used for the CH to whereabouts second reactor (4)4
Indirect heat exchange is carried out, heat exchange heat source used is the CO that the second separator (5) are isolated2And H2O, the third heat exchanger
(10) for the H to whereabouts first reactor (1)2O carries out secondary indirect heat exchange, and heat exchange heat source used is the first Stirling heat
The H exported after machine (6) acting power generation2And H2O。
7. the hydrogen production of chemical chain and power generation cycle system of a kind of Driven by Solar Energy according to claim 6, which is characterized in that
The cooling device includes the first cooler (14) and the second cooler (13), and first cooler (14) will be for that will lead to
Cross the CO of First Heat Exchanger (12)2And H2O carries out refrigerated separation, and second cooler (13) by third for that will be exchanged heat
The H of device (10)2And H2O carries out refrigerated separation.
8. a kind of using hydrogen production of chemical chain and the method for power generation, which comprises the following steps:
Step 1, by CH4And Fe3O4Reaction generates FeO, CO2And H2O；
Step 2, by H2O and FeO reaction, generates Fe3O4And H2, the FeO that the FeO is generated from step 1, the Fe3O4
Whereabouts step 1；
Step 3 carries out acting power generation using the heat generated in step 1 and step 2 reaction；
In step 4, collection step one and step 2 reaction the heat that generates and respectively to being reacted in step 1 and step 2 before
CH4And H2O is preheated；
Step 5 is led to overcooled method and is separated to the reaction product of step 1 and step 2, and respectively obtains H2With CO2。
9. according to claim 8 a kind of using hydrogen production of chemical chain and the method for power generation, which is characterized in that the step
The H of generation is reacted in one2The H isolated in O and step 52O whereabouts step 2.
10. according to claim 8 a kind of using hydrogen production of chemical chain and the method for power generation, which is characterized in that the step
Fe in rapid two3O4It is heated first by solar heater before the reaction.
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| CN114314509A (en) * | 2021-11-30 | 2022-04-12 | 西安交通大学 | System and process for preparing hydrogen-rich synthesis gas by liquid chemical chain gasification/reforming |
| CN114353063A (en) * | 2021-11-30 | 2022-04-15 | 西安交通大学 | Liquid chemical looping combustion cogeneration and carbon capture system and process |
| CN114988362A (en) * | 2022-05-27 | 2022-09-02 | 东北电力大学 | System and method for preparing formic acid by carbon capture of chemical-looping hydrogen production coupled fuel cell |
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| CN114353063A (en) * | 2021-11-30 | 2022-04-15 | 西安交通大学 | Liquid chemical looping combustion cogeneration and carbon capture system and process |
| CN114988362A (en) * | 2022-05-27 | 2022-09-02 | 东北电力大学 | System and method for preparing formic acid by carbon capture of chemical-looping hydrogen production coupled fuel cell |
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