CN108954872B - Solar energy classification and mass utilization system based on heat-collecting photothermochemical recycling materials - Google Patents
Solar energy classification and mass utilization system based on heat-collecting photothermochemical recycling materials Download PDFInfo
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- CN108954872B CN108954872B CN201810789143.3A CN201810789143A CN108954872B CN 108954872 B CN108954872 B CN 108954872B CN 201810789143 A CN201810789143 A CN 201810789143A CN 108954872 B CN108954872 B CN 108954872B
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- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000004064 recycling Methods 0.000 title 1
- 230000000694 effects Effects 0.000 claims abstract description 5
- 239000010453 quartz Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 239000010409 thin film Substances 0.000 claims abstract 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000012263 liquid product Substances 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 13
- 239000000446 fuel Substances 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 229910003081 TiO2−x Inorganic materials 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 241001464837 Viridiplantae Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/40—Thermal components
- H02S40/44—Means to utilise heat energy, e.g. hybrid systems producing warm water and electricity at the same time
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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
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02E10/60—Thermal-PV hybrids
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Abstract
本发明涉及太阳能应用技术领域，旨在提供一种基于集热型光热化学循环材料的太阳能分级分质利用系统。包括呈中空管状结构的透明石英材质的光热化学循环反应器，其入口端与CO2和H2O混合气的供气管相接，底部平面上设置具有集热效果的TiO2基薄膜层；不锈钢材质的导热腔体呈中空的管状结构，其顶部平面与光热化学循环反应器的底部平面紧密贴合以实现热量传导；光热化学循环反应器的入口端与导热腔体的出口端位于同一侧。本发明结合太阳能光利用和热利用手段，对太阳光区分波段利用，实现太阳能的分级分质利用，相较现有技术扩大了太阳光谱能量利用范围，提高整体能量利用效率，体现能量梯级利用理念，提高能量利用品质。
The invention relates to the technical field of solar energy application, and aims to provide a solar energy graded and mass-separated utilization system based on a heat-collecting photothermochemical cycle material. It comprises a photothermochemical circulation reactor made of transparent quartz material in a hollow tubular structure, the inlet end of which is connected with the gas supply pipe of the mixed gas of CO 2 and H 2 O, and a TiO 2 -based thin film layer with heat collecting effect is arranged on the bottom plane; The heat-conducting cavity made of stainless steel has a hollow tubular structure, and its top plane is closely attached to the bottom plane of the photothermochemical circulation reactor to realize heat conduction; the inlet end of the photothermochemical circulation reactor and the outlet end of the heat conduction cavity are located at same side. The invention combines solar light utilization and thermal utilization means to differentiate the wavelengths of sunlight for utilization, realizes graded and qualitative utilization of solar energy, expands the utilization range of solar spectrum energy compared with the prior art, improves the overall energy utilization efficiency, and embodies the concept of energy cascade utilization , improve the quality of energy utilization.
Description
Technical Field
The invention belongs to the technical field of solar energy application, and particularly relates to a solar energy grading and quality-dividing utilization system based on a heat collection type photo-thermal chemical circulation material.
Background
As society develops, human needs for energy increase. Currently, the global primary energy source is constituted by fossil fuelThe material is the main body. However, fossil fuels are non-renewable and pollute the environment during use. This has prompted the search for renewable energy sources that are renewable and do not pollute the environment. Among the energy sources, solar energy is receiving attention because of its advantages of low cost, wide sources, no environmental pollution, etc. At the same time, the human development process burns a large amount of CO produced by fossil fuels2Has a negative influence on the environment, CO2Emission reduction becomes a common concern for governments of all countries in the world. At present, CO2There are two technical paths for emission reduction, namely carbon dioxide capture and storage (CO)2Capture Storage, CCS) and artificially simulating photosynthesis of green plants in nature to perform CO2Conversion (CO)2Capture Conversion, CCC). Wherein the CCC technique can convert CO2The fuel is converted into the available hydrocarbon fuel, and is an environment-friendly energy conversion technology.
Solar energy is a primary energy source with wide source and environmental friendliness, and the energy quality can be determined by the spectral wavelength. The spectral wavelength of solar energy is from 280nm to 2500nm and is distinguished according to wave bands, wherein 280nm to 380nm belong to an ultraviolet wave band, 380nm to 760nm are visible wave bands, and more than 760nm are infrared wave bands. The ultraviolet and visible band light has high energy, and can realize solar light utilization; the infrared band light has a thermal effect, and solar heat utilization can be realized.
At present, solar energy utilization technologies can be classified into light utilization and heat utilization.
Solar energy utilization comprises technologies of photovoltaic power generation, photochemical preparation of solar fuel and the like. The solar light utilization technology has the problems that the technology mainly uses ultraviolet and visible bands, light in an infrared band can not be used almost, the utilization range of solar spectrum is reduced, and energy is wasted.
Solar energy heat utilization comprises technologies of photo-thermal power generation, thermochemical preparation of solar energy fuel and the like. The solar heat utilization technology can theoretically completely convert solar energy into heat energy, but in the conversion process, the energy quality of an ultraviolet visible band is reduced.
Therefore, the current main solar energy utilization technology does not carry out grading and quality-grading utilization on each wave band of solar energy, and the problems of unreasonable and incomplete energy utilization are caused. Aiming at the technical problem, the invention provides a novel solar grading and quality-grading utilization mode based on heat collection type photo-thermal chemical circulation.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a solar graded and quality-divided utilization system based on a heat collection type photo-thermal chemical circulation material.
In order to solve the technical problem, the solution of the invention is as follows:
the solar energy grading and quality-grading utilization system based on the heat collection type photo-thermal chemical circulation material comprises a photo-thermal chemical circulation reactor made of transparent quartz materials; the photothermal chemical circulation reactor is of a hollow tubular structure and is used for photothermal chemical circulation reaction, and the inlet end of the photothermal chemical circulation reactor is connected with CO2And H2The air supply pipe of the O mixed gas is connected, and the outlet end of the O mixed gas is connected with the gas-liquid separator through a pipeline; the bottom of the photo-thermal chemical circulation reactor is a plane, and the inner side surface of the photo-thermal chemical circulation reactor is provided with TiO with heat collection effect2A base film layer of the TiO2The base film layer is grown on the bottom of the reactor by a vapor deposition method;
the system also comprises a heat conduction cavity made of stainless steel, wherein the heat conduction cavity is of a hollow tubular structure and is used for controlling the temperature of the flowing of the heat conduction medium, the inlet end of the heat conduction cavity is connected with a heat conduction medium input pipe, and the outlet end of the heat conduction cavity is connected with a heat conduction medium storage tank through an output pipeline; the top of the heat conduction cavity is a plane, and the top plane is tightly attached to the bottom plane of the photo-thermal chemical circulation reactor to realize heat conduction; the inlet end of the photothermal chemical circulation reactor and the outlet end of the heat conduction cavity are positioned on the same side, and the outlet end of the photothermal chemical circulation reactor and the inlet end of the heat conduction cavity are positioned on the same side.
In the invention, the upper part of the gas-liquid separator is provided with a gas product discharge pipe, and the bottom of the gas-liquid separator is connected to a liquid collecting tank through a liquid product discharge pipe.
In the present invention, in the CO2And H2And a gas flowmeter is arranged on an O mixed gas supply pipe, and a liquid flowmeter is arranged on a heat-conducting medium input pipe.
In the invention, valves are respectively arranged on pipelines connected with the photo-thermal chemical circulation reactor and the heat conduction cavity.
In the present invention, the TiO is2The thickness range of the base film layer is between 5nm and 5 um.
Description of the inventive principles:
sunlight is divided into an infrared band, a visible light band and an ultraviolet band according to wave bands, and photo-thermal chemical cycle is a solar fuel preparation technology based on a photo-induced oxygen vacancy mechanism and is realized by driving of high-energy ultraviolet and visible light bands. To utilize TiO2Decomposition of CO2And H2O to CO and H2The reaction is as an example, and the specific process is as follows: utilizing sunlight high energy ultraviolet and visible light wave band in TiO2Surface generation of photo-induced oxygen vacancies followed by CO2And H2Mixed gas of O through TiO2The surface reacts with the photo-induced oxygen vacancies to form CO and H2And forming a complete cycle.
The invention realizes the graded and quality-divided utilization of solar energy by applying sunlight according to wavelength difference and combining a photo-thermal chemical circulation technology and a photo-thermal power generation technology. The core is that the solar fuel and the solar thermal power generation are prepared by combining photo-thermal chemical circulation, and the invention uses TiO2The base film is used as a heat collection type photo-thermal chemical cycle material, and under the condition of full-spectrum illumination, on the one hand, the base film responds to light in an ultraviolet visible waveband to perform photo-thermal chemical cycle conversion on CO2And H2Generating hydrocarbon fuel by the O mixed gas, and storing high-quality energy in an ultraviolet and visible waveband in the form of the hydrocarbon fuel; on the other hand, the heat effect of ultraviolet visible light and infrared band light which are not utilized in the photo-thermal chemical cycle is responded to, heat is generated, and the heat is transferred into a heat-conducting medium storage tank from a heat-conducting medium (heat-conducting oil or molten salt) to carry out photo-thermal power generation while the temperature (200-600 ℃) required by the photo-thermal chemical cycle is maintained.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention combines the solar light utilization and heat utilization means, distinguishes the bands of sunlight for utilization, realizes the graded and quality-divided utilization of solar energy, utilizes the ultraviolet visible light bands in the sunlight through the photo-thermal chemical circulation technology, and fixes the energy in the form of easily stored fuel; the solar heat collection part utilizes ultraviolet visible and infrared bands which are not recycled by photo-thermal chemistry, and the energy is fixed in a thermal power generation or other heat utilization modes.
2. The invention realizes the graded and quality-divided utilization of solar energy by photo-thermal chemical circulation and solar photo-thermal technology, and enlarges the utilization range of solar spectrum energy compared with the prior art; high energy storage products are further produced on the basis of the original heat accumulation, and the solar energy conversion efficiency is improved. The overall energy utilization efficiency is improved, the concept of energy gradient utilization is embodied, and the energy utilization quality is improved.
Drawings
FIG. 1 is a schematic diagram of a solar energy grading and quality-grading utilization system based on a heat collection type photo-thermal chemical cycle material in the invention.
In the figure: 1CO2And H2An air supply pipe for O mixed gas; 2, a gas flow meter; 3 photo-thermal chemical circulation reactor; 4, a gas-liquid separator; 5 gas product discharge pipe; 6 liquid product discharge pipe; 7 a liquid collection tank; 8, a heat-conducting medium input pipe; 9 a liquid flow meter; 10 a heat conducting cavity; 11 a heat-conducting medium storage tank; 12 reactor bottom (with TiO on the inner surface)2A base film layer).
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
As shown in the attached drawing, the solar energy grading and quality-dividing utilization system based on the heat collection type photo-thermal chemical circulation material comprises a photo-thermal chemical circulation reactor 3 made of transparent quartz and a heat conduction cavity 10 made of stainless steel.
The photothermal chemical circulation reactor 3 is a hollow tubular structure and is used for photothermal chemical circulation reaction, and the inlet end of the photothermal chemical circulation reactor is connected with CO2And H2An air supply pipe 1 of the O mixed gas is connected, and the outlet end of the O mixed gas is connected with a gas-liquid separator 4 through a pipeline; in CO2And H2The gas flow meter 2 is provided in the gas supply pipe 1 for the O-gas mixture. A gas product discharge pipe 5 is provided at the upper part of the gas-liquid separator 4, and the bottom part is connected to the gas-liquid separator through a liquid product discharge pipe 6A liquid collection tank 7. The reactor bottom 12 is a flat surface with TiO on the inside surface2A base film layer; TiO 22The base film layer is grown on the inner surface of the reactor bottom 12 by vapor deposition method, and the thickness range is between 5nm and 5 um. TiO 22The vapor deposition growth of base film layer belongs to the prior art.
The heat conducting cavity 10 is a hollow tubular structure and is used for controlling the temperature of the flowing of the heat conducting medium, the inlet end of the heat conducting cavity is connected with a heat conducting medium input pipe 8, the outlet end of the heat conducting cavity is connected with a heat conducting medium storage tank 11 through an output pipeline, and a liquid flowmeter 9 is arranged on the heat conducting medium input pipe 8; the top of the heat conducting cavity 10 is a plane, and the top plane is closely attached to the bottom plane of the photothermal chemical circulation reactor 3 to realize heat conduction.
The inlet end of the photothermal chemical circulation reactor 3 and the outlet end of the heat conducting cavity 10 are located on the same side, and the outlet end of the photothermal chemical circulation reactor 3 and the inlet end of the heat conducting cavity 10 are located on the same side. Valves are respectively arranged on the pipelines connected with the photo-thermal chemical circulation reactor 3 and the heat conducting cavity 10.
The use method of the system comprises the following steps:
(1) introducing CO2Raw gas is introduced and charged with H2Bubbler of O, CO discharged2And H2The O mixed gas enters a photo-thermochemical circulating reactor 3 after passing through a gas flowmeter; by changing CO2Temperature or addition of pure CO by a vent bypass2In such a way as to ensure CO entering the photo-thermo-chemical circulation reactor2And H2In mixed gas of O and CO2And H2The mass ratio of O is 100: 1.
(2) In the photothermal chemical looping reactor 3, CO2And H2The O mixed gas is mixed with TiO under the conditions of 200-600 ℃, normal pressure and full spectrum illumination2The surface of the base film layer contacts and generates a photo-thermochemical cycle reaction to generate hydrocarbon fuel;
the chemical reaction equation involved in the process is:
1/xTiO2→1/x TiO2-x+1/2O2
1/x TiO2-x+CO2→1/xTiO2+CO
1/x TiO2-x+H2O→1/xTiO2+H2
the reaction product passes through a gas-liquid separator to obtain a gas product and a liquid product, and the gas product and the liquid product respectively enter a storage tank through respective discharge pipes;
(3) in the photo-thermal chemical circulation reaction process, a heat-conducting medium (molten salt or heat-conducting oil) is introduced into the heat-conducting cavity 10 by using a circulating pump; TiO 22The heat absorbed by the base film layer is conducted to the heat conducting cavity 10 through the bottom of the photo-thermal chemical circulation reactor 3, and is subjected to heat exchange with a heat conducting medium flowing in the heat conducting cavity; the flow of the heat-conducting medium is controlled to ensure that the temperature of the photo-thermal chemical reaction is maintained at 200-600 ℃, and the heat-conducting medium absorbing photo-thermal is sent to a storage tank or heat exchange equipment.
The specific implementation example is as follows:
(1) firstly introducing N under the irradiation condition of a full-spectrum light source2The reaction is carried out for ① under the condition of creating oxygen-free atmosphere, and then CO is carried out under the saturated vapor pressure of 27 DEG C2Carry H2Introducing O mixed gas into the photo-thermal chemical circulation reactor 3 at a total flow rate of 30ml/min, reacting ② and ③ at normal pressure by using light to reach a reaction temperature of 550 ℃ to finally obtain CO and H2The hydrocarbon fuel has a chemical reaction equation:
1/xTiO2→1/x TiO2-x+1/2O2①
1/x TiO2-x+CO2→1/xTiO2+CO ②
1/x TiO2-x+H2O→1/xTiO2+H 2③
and finally, introducing the photo-thermal chemical cycle product into a storage tank for storage.
(2) TiO with heat collection effect while fuel preparation is carried out2The base film layer responds to the infrared band light, generates heat and transfers the heat to a fluid heat-conducting medium (such as molten salt and heat-conducting oil) in the heat-conducting cavity 10. On the premise of ensuring that the reaction temperature is 550 ℃, the flow of the heat-conducting medium is controlled to be 0.5m by the liquid flowmeter 93H, absorbing heat and delivering after temperature riseAnd storing in a storage tank or directly sending to heat exchange equipment.
Finally, it should also be noted that the above-mentioned list is only a specific embodiment of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive. The scope of the invention is indicated by the appended claims, and the foregoing description is not intended to indicate the scope of the invention, and therefore, all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
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