CN109114825A - Solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes method - Google Patents
Solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes method Download PDFInfo
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- CN109114825A CN109114825A CN201810760221.7A CN201810760221A CN109114825A CN 109114825 A CN109114825 A CN 109114825A CN 201810760221 A CN201810760221 A CN 201810760221A CN 109114825 A CN109114825 A CN 109114825A
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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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Abstract
The present invention relates to application of solar, it is desirable to provide a kind of solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes method.It is the TiO that there is Heat-collecting effect in the bottom of suprasil reactor arrangement2Base film, in TiO2Under the action of base film and UV, visible light light wave, CO2With H2Photo-thermal chemical looping reaction occurs for O gaseous mixture, is sent to separation equipment after generating hydrocarbon fuel；The TiO simultaneously2Base film carries out thermal-arrest using the infrared band in sunlight, and conducts heat to thermally conductive cavity, and the heat-conducting medium after heat absorption is sent to storage tank or heat exchange equipment.Present invention combination solar energy utilizes and heat utilization means, distinguishes wave band to sunlight and utilizes, and realizes that the classification sub-prime of solar energy utilizes.Compared with the prior art expand solar spectrum energy utilization scope；High energy storaging product is further produced on the basis of original thermal reservoir, improves solar conversion efficiency.Integral energy utilization efficiency is improved, cascaded utilization of energy theory is embodied, improves energy utilization quality.
Description
Technical field
The invention belongs to application of solar, and in particular to the sun based on heat collection type photo-thermal chemical cycle material
Sub-prime can be classified and utilize method.
Background technique
With social development, the mankind improve energy demand.Currently, global non-renewable energy is constituted based on fossil fuel
Body.However, fossil fuel has non-renewable, and pollute the environment in use process.This promote people find it is renewable and
Renewable energy free from environmental pollution.In numerous energy, expense is low, source is wide, free from environmental pollution etc. excellent because having for solar energy
It puts and is paid close attention to by people.Meanwhile the CO that a large amount of combustion of fossil fuels generate in human development process2Negative shadow is generated to environment
It rings, CO2Emission reduction becomes the topic that countries in the world government pays close attention to jointly.CO at present2There are two types of Technology Ways, i.e. carbon dioxide for emission reduction
Trapping storage (CO2Capture Storage, CCS) with the photosynthesis of manual simulation's nature Green plant carry out CO2's
Convert (CO2Capture Conversion, CCC).Wherein, CCC technology can be by CO2Available hydrocarbon fuel is converted to, is one
The environmental-friendly Energy Conversion Technology of item.
Solar energy is a kind of from a wealth of sources, environmental-friendly non-renewable energy, and energy figure can be determined by spectral wavelength.
The spectral wavelength of solar energy is distinguished by 280nm to 2500nm according to wave band, and 280nm to 380nm belongs to ultraviolet band, and 380nm is arrived
760nm is visible waveband, and the above are infrared bands by 760nm.UV, visible light band of light has high-energy, can be realized solar energy
It utilizes；Infrared band light has fuel factor, can be realized solar thermal utilization.
It is utilized and two class of heat utilization currently, the utilization technology of solar energy can be divided into light.
Solar energy, which is utilized, prepares the technologies such as solar energy fuel including photovoltaic power generation, photochemistry.Solar energy utilization technology
The problem of be, such technology mainly uses UV, visible light wave band, and the light of infrared band can hardly be used, solar spectrum
Utilization scope reduces, and causes the waste of energy.
Solar thermal utilization includes that photo-thermal power generation, heat chemistry prepare the technologies such as solar energy fuel.Solar energy utilization technique
Solar energy can be theoretically fully converted to thermal energy, but during conversion, the high-frequency energy product of UV, visible light wave band
Matter can reduce.
It can be seen that main solar utilization technique does not carry out classification sub-prime utilization to each wave band of solar energy at present, and
It is unreasonable, halfway to lead to the problem of energy utilization.For this technical problem, the present invention proposes a kind of novel based on thermal-arrest
The solar energy hierarchical sub-prime Land use systems of type photo-thermal chemical cycle.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of based on heat collection type photo-thermal
The solar energy hierarchical sub-prime of chemical cycle material utilizes method.
In order to solve the technical problem, solution of the invention is:
A kind of method that the solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes is provided, is to pass through area
Divide the wave band of sunlight and utilized with the classification sub-prime for realizing solar energy, specifically included: being arranged in the bottom of suprasil reactor
TiO with Heat-collecting effect2Base film；In TiO2Under the action of base film and UV, visible light light wave, CO2And H2O gaseous mixture occurs
Photo-thermal chemical looping reaction is sent to separation equipment after generating hydrocarbon fuel；The TiO simultaneously2Base film base film utilizes the sun
Infrared band in light carries out thermal-arrest, and conducts heat to thermally conductive cavity, and the heat-conducting medium after heat absorption is sent to storage tank or changes
Hot equipment.
In the present invention, the TiO2Base film is grown on reactor bottom surface by vapour deposition process, can respond the sun simultaneously
UV, visible light and infrared part in light realize thermal-arrest.
In the present invention, by controlling the flow of heat-conducting medium in thermally conductive cavity, maintain photo-thermal chemistry in quartz reactor anti-
The temperature answered is 200~600 DEG C.
In the present invention, by changing CO2Temperature adds pure CO by ventilation bypass2Mode, guarantee enter quartz reactor
CO2And H2In O gaseous mixture, CO2And H2The mass ratio of O is 100: 1.
In the present invention, the heat-conducting medium is fuse salt or conduction oil.
In the present invention, specifically includes the following steps:
(1) by CO2Unstripped gas, which introduces, is equipped with H2The bubbler of O, the CO of discharge2And H2O gaseous mixture is laggard through gas flowmeter
Enter quartz reactor；
(2) in quartz reactor, CO2And H2O gaseous mixture 200~600 DEG C, normal pressure and full spectrum light shine under the conditions of, with
TiO2Base film contacts concurrent third contact of a total solar or lunar eclipse thermochemical cycles reaction, generates hydrocarbon fuel；
Chemical equation involved in the process are as follows:
1/xTiO2→1/x TiO2-x+1/2O2
1/x TiO2-x+CO2→1/xTiO2+CO
1/x TiO2-x+H2O→1/xTiO2+H2
Reaction product obtains gaseous product and product liquid after gas-liquid separation；
(3) during photo-thermal chemical looping reaction, heat-conducting medium is introduced into thermally conductive cavity using circulating pump；TiO2Base
The heat that film is absorbed, to thermally conductive cavity, carries out heat with the heat-conducting medium wherein flowed by the bottom conductive of quartz reactor
Amount exchange；Flow by controlling heat-conducting medium guarantees that photo-thermal chemical reaction temperature maintains 200~600 DEG C, after absorbing photo-thermal
Heat-conducting medium be sent to storage tank or heat exchange equipment.
Inventive principle description:
Sunlight divides into infrared band, visible light wave range and ultraviolet light wave band according to wave band, and photo-thermal chemical cycle is base
In the solar energy preparation of fuel technology of photic Lacking oxygen mechanism, realized by high energy ultraviolet and visible light wave range driving.To utilize
TiO2Decompose CO2And H2O prepares CO and H2Reaction for, detailed process are as follows: utilize sunlight high energy ultraviolet and visible light wave range
In TiO2Surface generates photic Lacking oxygen, subsequent CO2And H2The mixed gas of O passes through TiO2Surface is reacted with photic Lacking oxygen, raw
At CO and H2, form complete cycle.
The present invention distinguishes sunlight according to wavelength and applies, real in conjunction with photo-thermal chemical cycle technology and photo-thermal power generation technology
The classification sub-prime of existing solar energy utilizes.Core is that photo-thermal chemical cycle is combined to prepare solar energy fuel and solar energy thermal-power-generating, with
TiO2On the one hand base film responds UV, visible light wave under the conditions of full spectrum light shines as heat collection type photo-thermal chemical cycle material
Section light carries out photo-thermal chemical cycle and converts CO2And H2The mixed gas of O generates hydrocarbon fuel, by the high-quality of UV, visible light wave band
Energy is stored in the form of hydrocarbon fuel；The unused ultraviolet-visible of another aspect response light thermochemical cycles and infrared band light
Fuel factor, generate heat, while maintaining photo-thermal chemical cycle required temperature (200 DEG C~600 DEG C), by heat-conducting medium
(conduction oil or fuse salt) passes into heat-conducting medium storage tank and carries out photo-thermal power generation.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention combines solar energy utilization and heat utilization means, distinguishes wave band to sunlight and utilizes, realizes solar energy
Classification sub-prime utilize, the UV, visible light optical band in sunlight is utilized by photo-thermal chemical cycle technology, by this portion
Energy is divided to fix with the fuel forms easily stored；By solar energy heating part to can not by the ultraviolet of photo-thermal chemical recycling
Light-exposed and infrared band is utilized, this portion of energy is fixed in the form of heat power generation or other heat utilizations.
2, the present invention realizes that solar energy hierarchical sub-prime utilizes by photo-thermal chemical cycle and solar energy techniques, compares existing
There is technology to expand solar spectrum energy utilization scope；High energy storaging product is further produced on the basis of original thermal reservoir,
Improve solar conversion efficiency.Integral energy utilization efficiency is improved, cascaded utilization of energy theory is embodied, improves energy utilization product
Matter.
Detailed description of the invention
Fig. 1 is that the solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material in the present invention is illustrated using system
Figure.
In figure: 1CO2And H2The air supply pipe of O gaseous mixture；2 gas flowmeters；3 photo-thermal chemical looping reaction devices；4 gas-liquid separations
Device；5 gaseous product discharge pipes；6 product liquid discharge pipes；7 liquid collection tanks；8 heat-conducting medium input pipes；9 fluid flowmeters；10
Thermally conductive cavity；11 heat-conducting medium storage tanks；(its surface is TiO to 12 reactor bottoms2Base film).
Specific embodiment
The method that the solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material in the present invention utilizes, is to pass through
It distinguishes the wave band of sunlight and is utilized with the classification sub-prime for realizing solar energy, specifically included: at the reactor bottom of suprasil material
The arrangement of portion 12 has the TiO of Heat-collecting effect2Base film；In TiO2Under the action of base film and UV, visible light light wave, CO2With H2O is mixed
It closes gas and photo-thermal chemical looping reaction occurs, be sent to separation equipment after generating hydrocarbon fuel；The TiO simultaneously2Base film base film
Thermal-arrest is carried out using the infrared band in sunlight, and conducts heat to thermally conductive cavity, the heat-conducting medium after heat absorption is sent to
Storage tank or heat exchange equipment.TiO2Base film is grown on the inner surface of reactor bottom 12 by vapour deposition process, can respond simultaneously
UV, visible light and infrared part in sunlight realize thermal-arrest.TiO2The vapour deposition process growth of base film belongs to the prior art.
This method specifically includes the following steps:
(1) by CO2Unstripped gas, which introduces, is equipped with H2The bubbler of O, the CO of discharge2With H2O gaseous mixture is laggard through gas flowmeter
Enter quartz reactor；By changing CO2Temperature adds pure CO by ventilation bypass2Mode, guarantee to enter quartz reactor
CO2With H2In O gaseous mixture, CO2And H2The mass ratio of O is 100: 1.
(2) in quartz reactor, CO2And H2O gaseous mixture 200~600 DEG C, normal pressure and full spectrum light shine under the conditions of, with
TiO2Base film contacts concurrent third contact of a total solar or lunar eclipse thermochemical cycles reaction, generates hydrocarbon fuel；
Chemical equation involved in the process are as follows:
1/xTiO2→1/x TiO2-x+1/2O2
1/x TiO2-x+CO2→1/xTiO2+CO
1/x TiO2-x+H2O→1/xTiO2+H2
Reaction product obtains gaseous product and product liquid after gas-liquid separation；
(3) during photo-thermal chemical looping reaction, heat-conducting medium (fuse salt is introduced into thermally conductive cavity using circulating pump
Or conduction oil)；TiO2The heat that base film is absorbed and is wherein flowed by the bottom conductive of quartz reactor to thermally conductive cavity
Heat-conducting medium carry out heat exchange；Flow by controlling heat-conducting medium guarantee photo-thermal chemical reaction temperature maintain 200~
600 DEG C, the heat-conducting medium after absorbing photo-thermal is sent to storage tank or heat exchange equipment.
The present invention is described in further details with example with reference to the accompanying drawing.
It as shown in the picture, is a kind of to apply to the solar energy hierarchical of the invention based on heat collection type photo-thermal chemical cycle material
Sub-prime utilizes system, the thermally conductive cavity 10 of the photo-thermal chemical looping reaction device 3 including suprasil material and stainless steel material.
Photo-thermal chemical looping reaction device 3 be in hollow tubular structure, be used for photo-thermal chemical looping reaction, arrival end with
CO2And H2The air supply pipe 1 of O gaseous mixture connects, and outlet end is connected by pipeline with gas-liquid separator 4；In CO2And H2O gaseous mixture
Gas flowmeter 2 is set on air supply pipe 1.The top of gas-liquid separator 4 sets gaseous product discharge pipe 5, and bottom passes through product liquid
Discharge pipe 6 is connected to liquid collection tank 7.Reactor bottom 12 is a flat surface, and inner surface is equipped with TiO2Base film；
TiO with Heat-collecting effect2Base film is grown on quartz reactor bottom by vapour deposition process., thickness model
It is trapped among between 5nm~5um.
Thermally conductive cavity 10 is in hollow tubular structure, is used for heat transfer medium flows temperature control, and arrival end is defeated with heat-conducting medium
Enter pipe 8 to connect, outlet end is connected by output pipe with heat-conducting medium storage tank 11, and liquid is arranged on heat-conducting medium input pipe 8
Flowmeter 9；The top of thermally conductive cavity 10 is a flat surface, and the top planes and the bottom plane of photo-thermal chemical looping reaction device 3 are tight
Closely connected conjunction is to realize that heat conducts.
The outlet end of the arrival end of photo-thermal chemical looping reaction device 3 and thermally conductive cavity 10 is located at the same side, and photo-thermal chemistry follows
The arrival end of the outlet end of loop reactor 3 and thermally conductive cavity 10 is located at the same side.With photo-thermal chemical looping reaction device 3 and thermally conductive
Valve is respectively set on the connected each pipeline of cavity 10.
Specific embodiment:
(1) under full spectrum light source irradiation condition, first it is passed through N2Deng creation oxygen-free atmosphere condition, reacted 1.；Then
It is depressed in 27 DEG C of saturated vapors, CO2Carry H2The mixed gas of O is that 30ml/min is passed through photo-thermal chemical looping reaction with total flow
In device 3；Reach 550 DEG C of reaction temperature using illumination, is reacted under normal pressure 2., 3., finally obtain CO, H2Hydrocarbon combustion
Material, chemical equation are as follows:
1/xTiO2→1/x TiO2-x+1/2O2 ①
1/x TiO2-x+CO2→1/xTiO2+CO ②
1/x TiO2-x+H2O→1/xTiO2+H2 ③
Finally, photo-thermal chemical cycle product is passed through in storage tank and is stored.
(2) while carrying out preparation of fuel, the TiO with Heat-collecting effect2Base film responds the infrared waves in incident light
Section, the fluidised form heat-conducting medium (such as fuse salt, conduction oil) for generating heat and being transferred in thermally conductive cavity 10.Guaranteeing reaction temperature
Under the premise of for 550 DEG C, the flow 0.5m of heat-conducting medium is controlled by fluid flowmeter 93/ h is sent after absorbing heat heating to storage
Tank storage, or it is fed directly to heat exchange equipment.
The above enumerated are only specific embodiments of the present invention for finally, it should also be noted that.Obviously, the present invention is unlimited
In above embodiments, acceptable there are many deformations.The present invention can be with other without prejudice to spirit or central characteristics of the invention
Concrete form is summarized.Therefore, in all respects, the embodiment above of the invention can only all be considered to the present invention
Explanation and the present invention cannot be limited.Claims indicate the scope of the present invention, and above-mentioned explanation does not point out this hair
Therefore bright range any change within the meaning and scope equivalent to the claims of the present invention, is all considered as wrapping
It includes within the scope of the claims.
Claims (6)
1. a kind of method that the solar energy hierarchical sub-prime based on heat collection type photo-thermal chemical cycle material utilizes, which is characterized in that be
It is utilized, is specifically included: at the bottom of suprasil reactor with the classification sub-prime for realizing solar energy by distinguishing the wave band of sunlight
Portion's arrangement has the TiO of Heat-collecting effect2Base film；In TiO2Under the action of base film and UV, visible light light wave, CO2With H2O mixing
Photo-thermal chemical looping reaction occurs for gas, is sent to separation equipment after generating hydrocarbon fuel；The TiO simultaneously2Base film utilizes the sun
Infrared band in light carries out thermal-arrest, and conducts heat to thermally conductive cavity, and the heat-conducting medium after heat absorption is sent to storage tank or changes
Hot equipment.
2. the method according to claim 1, wherein the TiO2Base film is grown on instead by vapour deposition process
Device bottom surface is answered, the UV, visible light and infrared part that can be responded simultaneously in sunlight realize thermal-arrest.
3. the method according to claim 1, wherein being tieed up by the flow for controlling heat-conducting medium in thermally conductive cavity
Holding the temperature that photo-thermal chemically reacts in quartz reactor is 200~600 DEG C.
4. the method according to claim 1, wherein by changing CO2Temperature adds pure CO by ventilation bypass2
Mode, guarantee enter quartz reactor CO2And H2In O gaseous mixture, CO2And H2The mass ratio of O is 100: 1.
5. the method according to claim 1, wherein the heat-conducting medium is fuse salt or conduction oil.
6. the method according to claim 1, wherein specifically includes the following steps:
(1) by CO2Unstripped gas, which introduces, is equipped with H2The bubbler of O, the CO of discharge2And H2O gaseous mixture enters stone after gas flowmeter
English reactor；
(2) in quartz reactor, CO2And H2O gaseous mixture is under the conditions of 200~600 DEG C, normal pressure and full spectrum light shine, with TiO2
Base film contacts concurrent third contact of a total solar or lunar eclipse thermochemical cycles reaction, generates hydrocarbon fuel；
Chemical equation involved in the process are as follows:
1/xTiO2→1/x TiO2-x+1/2O2
1/x TiO2-x+CO2→1/xTiO2+CO
1/x TiO2-x+H2O→1/xTiO2+H2
Reaction product obtains gaseous product and product liquid after gas-liquid separation；
(3) during photo-thermal chemical looping reaction, heat-conducting medium is introduced into thermally conductive cavity using circulating pump；TiO2Base film
The heat absorbed, to thermally conductive cavity, carries out heat friendship with the heat-conducting medium wherein flowed by the bottom conductive of quartz reactor
It changes；Flow by controlling heat-conducting medium guarantees that photo-thermal chemical reaction temperature maintains 200~600 DEG C, leading after absorbing photo-thermal
Thermal medium is sent to storage tank or heat exchange equipment.
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| CN201810760221.7A CN109114825B (en) | 2018-07-11 | 2018-07-11 | Solar energy grading and quality-grading utilization method based on heat collection type photo-thermal chemical circulation material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1705615A (en) * | 2003-03-26 | 2005-12-07 | 松下电器产业株式会社 | Water photolysis system and process |
| CN203731723U (en) * | 2014-01-26 | 2014-07-23 | 陈兴邦 | Frequency division heat collection tube and independent frequency division photovoltaic and photo-thermal combined device |
| CN104101113A (en) * | 2014-06-26 | 2014-10-15 | 同济大学 | Solar photothermal and photoelectric frequency division utilization system |
| CN204063622U (en) * | 2014-07-31 | 2014-12-31 | 陈兴邦 | Solar energy frequency division Accumulated Heat Units and there is its solar power system |
| CN105836703A (en) * | 2016-03-18 | 2016-08-10 | 浙江大学 | Method for preparing synthetic gas through photo-thermal chemical circulation decomposition of carbon dioxide |
-
2018
- 2018-07-11 CN CN201810760221.7A patent/CN109114825B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1705615A (en) * | 2003-03-26 | 2005-12-07 | 松下电器产业株式会社 | Water photolysis system and process |
| CN203731723U (en) * | 2014-01-26 | 2014-07-23 | 陈兴邦 | Frequency division heat collection tube and independent frequency division photovoltaic and photo-thermal combined device |
| CN104101113A (en) * | 2014-06-26 | 2014-10-15 | 同济大学 | Solar photothermal and photoelectric frequency division utilization system |
| CN204063622U (en) * | 2014-07-31 | 2014-12-31 | 陈兴邦 | Solar energy frequency division Accumulated Heat Units and there is its solar power system |
| CN105836703A (en) * | 2016-03-18 | 2016-08-10 | 浙江大学 | Method for preparing synthetic gas through photo-thermal chemical circulation decomposition of carbon dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 李培俊: "《无机功能材料》", 30 April 1981 * |
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