CN105597642B - A kind of film reaction system and method converting solar energy into chemical energy - Google Patents
A kind of film reaction system and method converting solar energy into chemical energy Download PDFInfo
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- CN105597642B CN105597642B CN201510727413.4A CN201510727413A CN105597642B CN 105597642 B CN105597642 B CN 105597642B CN 201510727413 A CN201510727413 A CN 201510727413A CN 105597642 B CN105597642 B CN 105597642B
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- membrane reactor
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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
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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
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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
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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
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Abstract
The present invention discloses a kind of film reaction system and method converting solar energy into chemical energy, belongs to field of new energy technologies.Including solar concentrator and the membrane reactor in one side is set, is respectively zoneofoxidation and reducing zone in the both sides of membrane reactor, zoneofoxidation is equipped with oxidant side heat exchanger and oxidant side cooler, and reducing zone is equipped with reducing zone cooler.Control side is low-oxygen environment, and when side is oxidation environment, with both sides gas redox reaction can occur for membrane reactor, while play the role of that both sides gas and pressure is isolated, and transmit lateral oxonium ion.Compared to other reaction systems in the field, which can realize the continuous production of fuel gas, while avoiding solid material and transporting the problem of need to consuming mechanical energy.The system can realize higher energy conversion efficiency, have very high promotional value.
Description
Technical field
The invention belongs to field of new energy technologies, and in particular to a kind of film reaction system converting solar energy into chemical energy
And method.
Background technology
The cleaning and exploitation of regenerative resource, conversion and utilization are worldwide research hotspots, long to human society
Phase sustainable development is of great significance.In many regenerative resources, solar energy rich reserves are widely distributed, clean without dirt
Dye has huge potentiality to be exploited.Using metal oxide as medium, by two step thermochemical cycle decomposition water or carbon dioxide,
To convert solar energy into one of the important channel that chemical energy is solar energy conversion.The principle of the cycle is using more active
(such as Fe between (such as Zn/ZnO) or the different valence state oxide of metal between metal and its oxide3O4/ FeO) oxidation also
The decomposition of water and carbon dioxide is realized in original reaction.The first step is reduction reaction, and metal oxide is in high temperature (1300 DEG C of ＞) hypoxemia
Oxygen is released under partial pressure conditions, metal ion is reduced to simple substance or compared with lower valency.Second step is oxidation reaction, can be compared with low temperature
It is carried out under degree (400-1000 DEG C), the metal oxide being reduced and vapor or carbon dioxide exposure simultaneously obtain one of those
Oxygen atom, generates hydrogen or carbon monoxide, and metal ion is then oxidizing to the state before reduction.Some metal oxides, such as cerium
Oxide (the ABO of base oxide (cerium oxide and the cerium oxide doped with other metal ions) and some perovskite structures3Type oxygen
Compound), different number of Lacking oxygen is can behave as in lattice under the conditions of different temperature and partial pressure of oxygen, using this property,
It can realize that two steps recycle in the case where the variation of non-stoichiometry number occurs in it.
The energy conversion efficiency of raising system is the core objective of the area research.Thermodynamic analysis shows gas phase heat loss
It is the main energy loss in such conversion process with solid phase heat loss, there is decisive meaning to overall energy conversion efficiency
Justice.Gas phase heat loss refers to that the gas of discharge is down to the heat of room temperature releasing by reaction temperature, this partial heat is not if being subject to
Recycling then shows as energy loss.To take the oxygen generated in first step reaction process out of reaction zone, it is low to keep reaction zone
Partial pressure of oxygen environment, the method that inert gas purge is all made of in existing experimental study, this will expend a large amount of inert gases, be made
At thermal loss occupy maximum specific weight in whole gas phase heat loss.Solid phase heat loss refers to the gold completed after first step reaction
Belong to oxide and be down to the heat released in second step reaction temperature process, this part energy also will performance if do not recycled
For energy loss.For gas phase heat loss, heat exchanger can be added in system, the gas heating being discharged with reactor enters system
The gas of system, to realize the recycling of most of gas phase heat.To eliminate solid phase heat loss, scholars propose the side of isothermal circulation
Second step reaction controlling is being reacted identical temperature with the first step by method, only change oxide surrounding atmosphere and improve partial pressure of oxygen
To achieve the purpose that oxidation reaction is promoted to carry out.Heating and cooling can be carried out to material to avoid between two-step reaction in this way, also just kept away
Solid phase heat loss is exempted from.However currently without the report related to the method for operation of the concrete form about isothermal circulation reaction system
Road.Reaction system stands good used by non-isothermal cycle, however, according to the reactor of single cavity, two-step reaction is handed over
For progress, the continuous production of fuel gas is cannot achieve, according to the reaction system of two reaction chambers, such as rotary or cycle is defeated
Send formula reactor, be still unavoidable from metal oxide transport need to consume mechanical work, metal oxide materials are continuously being moved through
Mechanical strength is difficult to ensure the problems such as sealing difficulty is big between two reaction chambers in journey.In addition, the use of a large amount of inert gases is not
The cost of reaction system is increased only, and greatly limits further increasing for system capacity transformation efficiency.
Invention content
In order to overcome the problems of the above-mentioned prior art, the purpose of the present invention is to provide one kind to convert solar energy into
The film reaction system and method for chemical energy, the film reaction system structure design is reasonable, can improve the energy conversion efficiency of system.
The present invention is to be achieved through the following technical solutions：
A kind of film reaction system converting solar energy into chemical energy disclosed by the invention, which is characterized in that including the sun
Can concentrator and the membrane reactor in one side be set, be respectively zoneofoxidation and reducing zone, zoneofoxidation in the both sides of membrane reactor
Equipped with oxidant side heat exchanger and oxidant side cooler, reducing zone is equipped with reducing zone cooler；
The cold fluid outlet of oxidant side heat exchanger is connected with the oxidation side entrance of membrane reactor, and the oxidant side of membrane reactor goes out
Mouth is connected with the thermal fluid inlet of oxidant side heat exchanger, the entrance of the hot fluid outlet ports and oxidant side cooler of oxidant side heat exchanger
It is connected；The reduction side outlet of membrane reactor is connected with the entrance of reduction side cooler.
Vacuum pump is additionally provided in zoneofoxidation, the outlet of reduction side cooler is connected with the entrance of vacuum pump.
The film of the membrane reactor is using dense membrane structure made of metal oxide.
The metal oxide is the cerium base oxide of cerium oxide, perovskite structure oxide or doped metal ion.
The invention also discloses a kind of methods converting solar energy into chemical energy, which is characterized in that converts solar energy
For the film reaction system of chemical energy, including：
Solar concentrator is used for focused solar energy；
Membrane reactor, the carbon dioxide decomposition for that will flow into generates carbon monoxide, or the water vapour of inflow is decomposed
Generate hydrogen；
Oxidant side heat exchanger is preheated for gas recovery heat and to gas；
Side cooler and oxidant side cooler are restored, the gas for the outflow of heat exchanging device cools down；
The method for converting solar energy into chemical energy based on above-mentioned film reaction system is：
The oxygen that membrane reactor generates is cold by entering reduction side cooler progress after the reduction side outlet outflow of membrane reactor
But, it is then discharged out system；
Carbon dioxide or water enter oxidant side heat exchanger by the cold fluid inlet of oxidant side heat exchanger, enter film after preheated
The oxidant side of reactor, it is preheated by entering the hot-fluid body end of oxidant side heat exchanger after the oxidant side outlet outflow of membrane reactor
Oxidant side heat exchanger is flowed out afterwards, is cooled to room temperature subsequently into oxidant side cooler, last discharge system.
The film reaction system further includes the vacuum pump for extracting the oxygen that reduction side generates out, and carbon dioxide or water are through pressure
The cold flow body end for entering oxidant side heat exchanger after the pressurization of contracting machine is preheated.
The film of the membrane reactor is using dense membrane structure made of metal oxide.
The metal oxide is the cerium base oxide of cerium oxide, perovskite structure oxide or doped metal ion.
Compared with prior art, the present invention has technique effect beneficial below：
Film reaction system disclosed by the invention using solar energy production gaseous fuel is respectively in the both sides of membrane reactor
Reducing zone and zoneofoxidation, reducing zone are equipped with reduction side cooler, and zoneofoxidation is equipped with oxidant side heat exchanger and oxidant side cooler.Control
Reducing zone processed is low oxygen partial pressure environment, and zoneofoxidation will then be passed through oxidizing gas (vapor or carbon dioxide).Membrane reactor is not only
Redox reaction is carried out with both sides gas, also acts as isolation both sides gas and pressure, while the effect of lateral transport oxonium ion.
The film reaction system generation oxidation reaction of the present invention is identical with the reaction temperature of reduction reaction, eliminates consolidating in not isothermal circulation
Body heat content loses, and oxidation reaction and reduction reaction are carried out at the same time the continuous production, it can be achieved that fuel gas.Compared in the field
Other reaction systems, this system obviates solid material transport need to consume mechanical energy the problem of, the energy of system can be effectively improved
Transformation efficiency is measured, there is very high promotional value.
The invention also discloses the method for converting solar energy into chemical energy based on above-mentioned film reaction system, oxidation reaction and
Reduction reaction is carried out at the same time the continuous production, it can be achieved that fuel gas, and oxidation reaction is identical with the reaction temperature of reduction reaction,
Eliminate the solid thermal loss in not isothermal circulation.
Further, the film of inventive film reactor can be isolated two using dense membrane structure made of metal oxide
The gas and pressure of side simplify sealing problem, while can change two reaction zone pressures respectively to further increase system
Energy conversion efficiency.
Further, use vacuum pump in time by mode that the oxygen that reducing zone generates is extracted out in time to maintain reducing zone
Low-oxygen environment avoids the use of inert gas, further improves the energy conversion efficiency of system.
Description of the drawings
Fig. 1 is the film reaction system structure diagram of the present invention.
Wherein, 1 is solar concentrator；2 be membrane reactor；3 be oxidant side heat exchanger；4 be reduction side cooler；5 are
Oxidant side cooler；6 be vacuum pump.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Referring to Fig. 1, film reaction system solar concentrating system 1, membrane reactor 2, the oxygen of chemical energy are converted solar energy into
Change side heat exchanger 3, reduction side cooler 4, oxidant side cooler 5 and vacuum pump 6.Solar concentrating system 1 is for focusing the sun
Energy；The carbon dioxide or water vapour that membrane reactor 2 is used to promote to flow into, which decompose, generates carbon monoxide or hydrogen；Oxidant side heat exchanger
3 for recycling the heat of membrane reactor oxidant side eluting gas, at the same to flow into the gas of membrane reactor oxidant side into
Row preheating；Reduction side cooler 4 is used to cool down the oxygen that membrane reactor 2 restores side outflow；Oxidant side side cooler 5 is used for convection current
The gas for going out oxidant side heat exchanger is further cooled down；Vacuum pump 6 is used to extract out the oxygen that reduction side generates and keeps in it
Portion's pressure is in reduced levels.
Restoring the side order of connection is：Reduction side outlet connection reduction 4 entrance of side cooler of membrane reactor 2；It is cold to restore side
But the outlet of device 4 connection 6 entrance of vacuum pump.
The oxidant side order of connection is：The cold fluid outlet of oxidant side heat exchanger 3 connects with the oxidation side entrance of membrane reactor 2
It connects；The oxidation side outlet of membrane reactor 2 is connect with the thermal fluid inlet of oxidant side heat exchanger 3；The hot fluid of oxidant side heat exchanger 3
Outlet is connect with the entrance of oxidant side cooler 5.
To use cerium oxide for the film reaction system of membrane material.Cerium oxide is made into dense membrane structure, and as
Core material makes membrane reactor.Reactor is isolated into two regions by cerium oxide, and wherein side is reduction side, uses vacuum pump
By the timely extraction area of the oxygen of generation to maintain its internal low-oxygen environment；The other side is oxidant side, and leading to oxidizing gas, (water steams
Gas or carbon dioxide).Cerium oxide can not only carry out redox reaction with ambient gas, also act as isolation both sides gas and pressure
Strong and lateral transport oxonium ion effect.
The method for converting solar energy into chemical energy using the film reaction system of the present invention, including：
Side gas flow is restored when operation is：The oxygen that 2 reducing zone of membrane reactor generates restores side by membrane reactor 2
Enter reduction side cooler 4 after outlet outflow to be cooled down, system is extracted out through vacuum pump 6.Oxidant side gas flow is：Two
Carbonoxide or water (liquid water or water vapour) enter oxidant side heat exchanger by 3 cold flow body end of oxidant side heat exchanger, and oxidized side is changed
Enter 2 oxidant side of membrane reactor after hot device preheating, by entering 3 heat of oxidant side heat exchanger after 2 oxidant side of membrane reactor outlet outflow
Fluid end preheats inflow gas, and room is cooled further into oxidant side cooler 5 after outflow oxidant side heat exchanger 3
Temperature, last discharge system.
Table 1 is film reaction system in different reduction sides stagnation pressure, i.e. energy conversion efficiency under the conditions of partial pressure of oxygen, calculating when institute
Select parameter referring to table 2.
1 film reaction system of table partial pressure of oxygen at different temperatures (T) and reduction side entranceUnder the conditions of energy conversion
Efficiency (%)
Note：Lack part and belongs to the region that cannot achieve normal reaction because of the limitation of conditions.
Each variable-value that need to be given when 2 efficiency calculation of table
In conclusion the film reaction system of the present invention, can convert solar energy into the chemical energy of carbon monoxide or hydrogen.
Metal oxide film is played occurs redox reaction respectively with both sides gas, and both sides gas and pressure and lateral transport oxygen is isolated
The effect of ion；It is exchanged heat to the gas of inflow and outflow reactor oxidant side with gas heat exchanger, realizes gas heat
Recycling；The oxygen extraction in time that side generates will be restored to keep its internal low-oxygen environment with vacuum pump.Compared in the field its
His reaction system, the system can realize the continuous production of fuel gas, and asking for mechanical energy need to be consumed by avoiding solid material and transporting
Topic, while the energy conversion efficiency that system is further improved using inert gas is avoided, there is very high promotional value.
Claims (2)
1. a kind of film reaction system converting solar energy into chemical energy, which is characterized in that including solar concentrator（1）With set
Set the membrane reactor in one side（2）, in membrane reactor（2）Both sides be respectively zoneofoxidation and reducing zone, zoneofoxidation is equipped with oxygen
Change side heat exchanger（3）With oxidant side cooler（5）, reducing zone is equipped with reduction side cooler（4）And vacuum pump（6）；
Oxidant side heat exchanger（3）Cold fluid outlet and membrane reactor（2）Oxidation side entrance be connected, membrane reactor（2）Oxygen
Change side outlet and oxidant side heat exchanger（3）Thermal fluid inlet be connected, oxidant side heat exchanger（3）Hot fluid outlet ports and oxidant side
Cooler（5）Entrance be connected；
Membrane reactor（2）Reduction side outlet with reduction side cooler（4）Entrance be connected, restore side cooler（4）Outlet
With vacuum pump（6）Entrance be connected；
Membrane reactor（2）Film using dense membrane structure made of metal oxide, metal oxide is cerium oxide or doping gold
Belong to the cerium base oxide of ion.
2. a kind of method converting solar energy into chemical energy, which is characterized in that convert solar energy into the film reaction of chemical energy
System, including：
Solar concentrator（1）, it is used for focused solar energy；
Membrane reactor（2）, the carbon dioxide decomposition for that will flow into generates carbon monoxide, or the water vapour of inflow is decomposed production
Raw hydrogen；
Oxidant side heat exchanger（3）, preheated for gas recovery heat and to gas；
Restore side cooler（4）With oxidant side cooler（5）, for heat exchanging device outflow gas cool down；
Vacuum pump is additionally provided in reducing zone（6）, membrane reactor（2）Reduction side outlet with reduction side cooler（4）Entrance
It is connected, restores side cooler（4）Outlet and vacuum pump（6）Entrance be connected；
Membrane reactor（2）Film using dense membrane structure made of metal oxide, metal oxide is cerium oxide or doping gold
Belong to the cerium base oxide of ion；
The method for converting solar energy into chemical energy based on above-mentioned film reaction system is：
Membrane reactor（2）The oxygen of generation is by membrane reactor（2）Reduction side outlet outflow after enter reduction side cooler（4）Into
Row cooling, through vacuum pump（6）Discharge system；
Carbon dioxide or vapor are by oxidant side heat exchanger（3）Cold fluid inlet enter oxidant side heat exchanger（3）, after preheated
Into membrane reactor（2）Oxidant side, by membrane reactor（2）Oxidant side outlet outflow after enter oxidant side heat exchanger（3）'s
Hot-fluid body end flows out oxidant side heat exchanger after being preheated to inflow gas（3）, subsequently into oxidant side cooler（5）It is cooling
To room temperature, last discharge system.
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| CN201510727413.4A CN105597642B (en) | 2015-10-30 | 2015-10-30 | A kind of film reaction system and method converting solar energy into chemical energy |
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| CN201510727413.4A CN105597642B (en) | 2015-10-30 | 2015-10-30 | A kind of film reaction system and method converting solar energy into chemical energy |
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| CN105597642A CN105597642A (en) | 2016-05-25 |
| CN105597642B true CN105597642B (en) | 2018-09-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1554569A (en) * | 2003-12-25 | 2004-12-15 | 吴佶伟 | System and its device for producing hydrogen and oxygen using solar energy |
| CN102660340B (en) * | 2012-04-24 | 2014-06-11 | 武汉凯迪工程技术研究总院有限公司 | Process and equipment for converting carbon dioxide in flue gas into natural gas by using dump power energy |
| US9238598B2 (en) * | 2013-01-04 | 2016-01-19 | Saudi Arabian Oil Company | Carbon dioxide conversion to hydrocarbon fuel via syngas production cell harnessed from solar radiation |
| CN104163399B (en) * | 2014-09-01 | 2016-06-08 | 中国科学院工程热物理研究所 | The device of oxygen permeable film, permeable hydrogen membrane alternate decomposition water hydrogen making |
| CN104649227B (en) * | 2015-02-13 | 2017-01-18 | 中国科学院工程热物理研究所 | Comprehensive solar energy utilization system based on oxygen permeating membrane |
| CN104724673B (en) * | 2015-02-15 | 2017-03-22 | 中国科学院工程热物理研究所 | System and method for improving preparation speed and efficiency of solar thermo-chemical fuel |
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