CN115092888A - Continuous flow conversion system for coupling solar light-gathering catalysis and energy storage - Google Patents
Continuous flow conversion system for coupling solar light-gathering catalysis and energy storage Download PDFInfo
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Abstract
The invention relates to a continuous flow conversion system for coupling solar light-gathering catalysis and energy storage, which comprises a reactor, a heat storage tank, an electric heating device and a gas separation device. The system utilizes solar energy and converts the solar energy into heat energy and light energy, one part is used for heating the reactor to provide energy and high-temperature conditions required by various gas-solid phase photo-thermal catalytic reactions, the other part is used for storing, and the thermal catalysis is realized in the reactor under the condition of no light. The invention provides a continuous flow conversion system coupling solar light-gathering catalysis and energy storage through the design and manufacture of a reaction system, and realizes the utilization of solar energy flow and material flow in a matching way.
Description
Technical Field
The invention relates to the technical field of solar energy utilization, in particular to a continuous flow conversion system for coupling solar energy condensation catalysis and energy storage.
Background
Solar energy has the characteristics of cleanness, inexhaustibility and the like, but has the problem of uneven time distribution, and the solar energy cannot be basically used for stable photo-thermal catalysis.
Methane, which is a main component of natural gas and combustible ice, has a huge reserve on earth and is expected to replace fossil fuel as a cleaner energy source, and high value-added products based on methane synthesis also have an important position in chemical engineering, such as: ethylene, methyl mercaptan, syngas, and the like. Most of materials for catalyzing by using solar energy are cerium oxide and zinc oxide at present, most of catalytic reaction is methane thermocatalysis for preparing synthesis gas, the temperature is mostly higher than 700 ℃, but catalysts for catalyzing methane to prepare other products with high added values are various, conditions required by reaction are mostly photocatalysis or photothermal catalysis, and sintering of catalytic materials can be caused by the high temperature of 700 ℃. If a new reactor can be developed, the reactor can effectively control the temperature of the reactor, so that the reactor can be applied to various methane catalytic reactions, simultaneously convert redundant solar energy into heat energy for reutilization, organically combine solar energy thermochemistry energy storage with solar energy heat generation, and bring huge changes to the solar energy thermal utilization field.
In northwest areas of China, solar energy resources are abundant, so if a new reactor can be developed, the reactor can organically combine high value-added utilization of methane with solar photothermal catalysis, and huge changes can be brought to the field of solar photothermal.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a continuous flow conversion system for coupling solar light-gathering catalysis and energy storage, which combines high-added-value utilization of methane with solar photo-thermal catalysis and can realize stable and continuous utilization of solar energy.
In order to achieve the purpose, the invention adopts the technical scheme that:
a continuous flow conversion system coupling solar light-gathering catalysis and energy storage, comprising:
a) a reactor 1 capable of absorbing heat and reacting, which can collect solar energy and heat generated by the solar energy, thereby supplying the methane carbon dioxide conversion;
b) an energy storage system comprising a heat storage tank 2 for heating the molten metal by excess energy generated by solar energy in the reactor system and for providing reaction heat again to the reactor in the absence of light
c) A compensation system, which comprises an electric heating system 3 used for compensating the heat lost in the energy storage system, and making the molten metal flow into the reactor 1 for reaction at a constant temperature by accurately measuring the temperature and controlling the heating of the molten metal;
d) a gas separation system consisting of a hydrogen separator 15 and a carbon monoxide separator 16, which can separate the gas flowing out through a double-pipe type sleeve and collect the required chemical products
The reactor 1 is provided with a quartz tube with the same size, and the quartz tube can be loaded or replaced with a solid particle catalyst fixed bed, and the working temperature is 550-650 ℃.
The gas inlet 13 of the quartz tube is communicated with a carbon dioxide and methane gas cylinder, and the total pressure in the gas cylinder is controlled to be less than 0.1Mpa through a partial pressure valve.
The reactor is internally provided with a heat transfer medium water channel which enters and exits from the side surface of the reactor, the heat transfer medium water channel is surrounded in the middle of the reactor, and water head threads with matched sizes are arranged at the inlet and the outlet.
The reactor 1 is provided with a solar energy condensing device corresponding to the reactor 1 for focusing sunlight on the reactor 1.
The energy storage system comprises a heat storage tank, liquid metal, a heat storage tank outlet AB, a heat insulation shell, a cooling fan and a bidirectional high-temperature pump.
The liquid metal has a large number of ceramic particles 8 to improve the heat storage capacity of the liquid metal, reduce the heat loss and reduce the volume.
A cooling air channel 7 is arranged between the heat storage tank 2 and the heat preservation shell 9, so that the cooling fan 10 can transfer the redundant heat of the heat storage tank out; the top of the heat storage tank is provided with a rain shade with corresponding specification.
A filter screen 11 is arranged at the outlet of the heat storage tank to filter ceramic particles;
the bidirectional high-temperature pump 4 is controlled by a computer, when the temperature of the reactor 1 is higher than a rated value, the bidirectional high-temperature pump 4 flows in the positive direction, heat storage salt flows out of the outlet 6 and flows in from the outlet 5, and the electric heating wire 3 does not work; when the temperature of the reactor 1 is lower than a rated value, the bidirectional high-temperature pump 4 reversely flows, and the heat storage salt flows out from the outlet 5 and flows in from the outlet 6; when the temperature of the heat storage tank 2 and the temperature of the reactor 1 are both lower than the rated value, the electric heating wire 3 starts to work; the specific flow rate of the bidirectional high-temperature pump 4 is determined by the actual temperature of the surface of the reactor 1 and is controlled by a computer program.
The gas separation system consists of a hydrogen separator 15 and a carbon monoxide separator 16, the gas separator consists of two cylinders, a gas outlet of the reactor is connected with an inner cylinder of the separator, a permeable membrane of corresponding gas is attached to the wall of the inner cylinder and can be directionally permeated by the specific gas, and the outer cylinder is connected with a gas detection device.
A continuous flow conversion system for coupling solar light-gathering catalysis and energy storage comprises the following steps:
when the solar radiation is sufficient, the gas inlet 13 fills the reaction gas into the quartz tube of the reactor 1, the reactor 1 starts to react by the photo-thermal effect, the product flows out to the inner tubes of the gas collecting device systems 15 and 16 through the gas outlet 14, the wall of the inner tube is provided with a corresponding palladium membrane for absorbing the product gas, the product gas enters the outer tube through the inner tube and flows out from the outlet of the outer tube to the chromatographic quantitative analysis, and the unreacted gas continues to be introduced into the gas inlet 13 of the reactor for reaction through the outlet of the inner tube. The horseshoe-shaped heat exchange tube in the reactor 1 uses the redundant energy in the solar catalytic reaction to heat the molten metal and then flows into the heat storage tank 2. At the moment, the electric heating system 3 does not work, the bidirectional high-temperature pump 4 is in forward flow, the molten metal flows out from the outlet 6, the specific flow rate of the molten metal is monitored by the external temperature probe of the reactor, and the temperature of the reactor is ensured to be 550-650 ℃ through directional control of a computer program. When the temperature probe in the heat storage tank 2 detects that the temperature of the heat storage tank is higher than the rated value, the cooling fan is started to ensure the use safety. Completing the circulation;
when no solar radiation exists, the temperature probe detects that the temperature of the molten metal in the heat storage tank 2 is higher than the surface temperature of the reactor, the bidirectional high-temperature pump 4 reversely flows, the molten metal flows out from the outlet 5, the reactor is heated by the temperature of the heated molten metal when the solar radiation is sufficient, reaction gas is filled into the quartz tube of the reactor 1 through the gas inlet 13, the reactor 1 is heated for reaction, products pass through the inner tubes of the gas collecting devices 15 and 16 and pass through the corresponding palladium membranes adsorbing the product gas on the wall of the inner tubes, the product gas enters the outer tubes through the inner tubes and flows out from the outlet 12 of the outer tubes to the gas storage tank for collection, and unreacted gas is continuously introduced into the gas inlet 13 of the reactor through the outlet of the inner tubes for reaction, so that the circulation is completed.
When no solar radiation exists and the temperature probe detects that the temperature of the heat storage tank and the temperature of the reactor are lower than the rated value, the electric heater 3 starts to work, the bidirectional high-temperature pump 4 reversely flows, the molten metal flows out from the outlet 5, the electric heater compensates for the missing energy to ensure that the temperature of the molten metal led into the reactor is higher than 600 ℃, and the circulation is completed.
Drawings
FIG. 1 is a schematic diagram of a solar photo-thermal catalytic reaction system
FIG. 2 is a schematic view of a solar photo-thermal catalytic reactor
FIG. 3 is a schematic view of a gas separation apparatus
FIG. 4 shows tetrahedral Ni 1 /CeO 2 Yield activity diagram using solar light-gathering catalysis
The invention has the beneficial effects that:
when the solar photo-thermal catalytic reactor based on high added-value utilization of methane works specifically, the condenser is used for heating molten metal by using solar energy or an electric heating device is used for heating molten metal, the temperature in the reactor is controlled to be constant in an interval, and reactants in a tube pass absorb heat and light and then perform catalytic reaction, so that organic combination of high added-value utilization of methane and stable solar photo-thermal catalysis is realized.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known structures, materials, or methods have not been described in detail in order to avoid obscuring the present invention.
Throughout the specification, reference to "one embodiment," "an embodiment," "one example," or "an example" means: the particular features, structures, or characteristics described in connection with the embodiment or examples are included in at least one embodiment of the invention. Thus, the appearances of the phrase "one embodiment," "an embodiment," "one example" or "an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features or characteristics may be combined in any suitable combinations and/or sub-combinations in one or more embodiments or examples. Further, those of ordinary skill in the art will appreciate that the illustrations provided herein are for illustrative purposes and are not necessarily drawn to scale. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1: 99.99 percent of methane and carbon dioxide are introduced into the reactor for solar photo-thermal catalysis.
In this embodiment, the methane and carbon dioxide pipelines flow through the reactor 1 and the gas separation device to form a circulation, and the dry reforming products of methane, hydrogen and carbon monoxide, are alternately separated to promote the equilibrium of the dry reforming reaction of methane to move in the forward direction, so that the conversion rate of methane is greatly increased compared with the conversion rate of a single reaction.
Wherein, the temperature of the converged solar condenser reaches over 1200 ℃, and the temperature is maintained at 600 ℃ through the energy exchange of the molten metal.
This example uses tetrahedral Ni 1 /CeO 2 Solar light-gathering catalysis is applied as a catalyst. Methane and carbon dioxide were flowed into the reactor 1 at a total flow rate of 30sccm with Ni as the catalyst 1 /CeO 2 After granulation, 30-70 mesh granules are screened, the total mass is 200mg, and the granules are placed in a quartz tube in the middle of the reactor 1. The intensity of the illumination collected by the condenser corresponding to the reactor 1 was 17.25W. The product after the reaction was analyzed by gas chromatography GC-7900 and the product yield was calculated. In this example for Ni 1 /CeO 2 The activity of the catalyst was evaluated for 1000h, and about 1300L of carbon monoxide and 1200L of hydrogen were produced in 1000 h. The specific hourly production is shown in figure 4.
Example 2: the reactor was charged with 20% methane and carbon dioxide for a long period of 200 hours.
In this example, the methane and carbon dioxide with a purity of 20% are circulated through the reactor 1 and the gas separation device, and the dry methane reforming products, hydrogen and carbon monoxide, are alternately separated and finally subjected to quantitative analysis by Shimadzu GC-7900 chromatography.
Wherein the temperature of the converged solar condenser reaches over 1200 ℃, and the temperature is maintained at 600 ℃ through energy exchange of molten metal.
This example uses a rod-like Ni 1 /CeO 2 Solar light-gathering catalysis is applied as a catalyst. Methane and carbon dioxide were flowed into reactor 1 at a total flow rate of 20sccm, catalyst Ni 1 /CeO 2 After granulation, 30-70 mesh granules are screened, the total mass is 30mg, and the granules are placed in a quartz tube in the middle of the reactor 1. Through measurement and calculation, the illumination intensity collected by the condenser corresponding to the reactor 1 is 17.25W. The product after the reaction was analyzed by gas chromatography GC-7900 and the product yield was calculated. In this example for Ni 1 /CeO 2 The catalyst is continuously reacted for 2 timesAnd (3) measuring and calculating the activity within 50 hours, and observing the stability of the catalyst and the system under the solar photo-thermal catalysis state, wherein the system can stably run for a long time.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.
Claims (8)
1. A continuous flow conversion system coupling solar light-gathering catalysis and energy storage, comprising: a reactor 1 capable of absorbing heat and reacting, which can collect solar energy and heat generated by the solar energy, thereby supplying the methane carbon dioxide conversion; an energy storage system comprising a heat storage tank 2 for heating the molten metal by excess energy generated by solar energy in the reactor system and for providing reaction heat again to the reactor in the absence of light; a compensation system, which comprises an electric heating system 3 for compensating the heat lost in the energy storage system, and the molten metal can flow into the reactor 1 for reaction at a constant temperature by accurately measuring the temperature and controlling the heating of the molten metal; and the gas separation system consists of a hydrogen separator 15 and a carbon monoxide separator 16, and can separate the effluent gas through a double-pipe sleeve and collect the required chemical products.
2. The reactor of claim 1, wherein the reactor is configured to couple a solar light-concentrating catalytic and energy-storing continuous-flow conversion system, and comprises: the reactor is provided with a quartz tube with a proper size, and the quartz tube can be loaded with or replaced by solid particle catalysts; a heat transfer medium water channel is arranged in the reactor, enters and exits from the side surface of the reactor and surrounds the middle part of the reactor; the inlet and outlet are provided with water head threads with matched sizes.
3. The heat storage system of claim 1, wherein the heat storage system comprises: the energy storage system comprises a heat storage tank, liquid metal 2, heat storage tank outlets 5 and 6, a heat insulation shell 9, a cooling fan 10 and a bidirectional high-temperature pump 4; the liquid metal contains a large amount of ceramic particles 8 so as to improve the heat storage capacity of the liquid metal 2, reduce the heat loss and reduce the volume; a cooling air channel 7 is arranged between the heat storage tank and the heat preservation shell, so that the cooling fan 10 can transfer the redundant heat of the heat storage tank out; the top of the heat storage tank is provided with a rain shade 12 with corresponding specification; the outlet of the heat storage tank is provided with a filter screen 11 for filtering the ceramic particles 8.
4. The continuous-flow conversion system coupling solar concentration catalysis and energy storage according to claim 2, wherein: the bidirectional high-temperature pump 4 is controlled by a computer, when the temperature of the reactor 1 is higher than a rated value, the bidirectional high-temperature pump 4 is in forward flow, heat storage salt flows out of the outlet 6 and flows in from the outlet 5, and the electric heating wire does not work; when the temperature of the reactor is lower than a rated value, the bidirectional high-temperature pump 4 reversely flows, and the heat storage salt flows out from the outlet 5 and flows in from the outlet 6; when the temperature of the heat storage tank and the temperature of the reactor are lower than the rated values, the electric heating wire 3 starts to work; the specific flow rate of the bidirectional high-temperature pump is determined by the actual temperature of the surface of the reactor and is controlled by a computer program.
5. The gas separation system of claim 1, wherein the gas separation system is coupled to a solar light concentrating, catalyzing and energy storing continuous flow conversion system, and comprises: the gas separation system is composed of a hydrogen separator 15 and a carbon monoxide separator 16, the gas separator is composed of two cylinders, a gas outlet of the reactor is connected with an inner cylinder of the separator, a permeable membrane of corresponding gas is attached to the inner cylinder wall and can be used for specific gas to directionally permeate, and the outer cylinder is connected with a gas detection device.
6. The continuous flow conversion system coupled with solar light-gathering catalysis and energy storage, which adopts the system of claim 1, is characterized in that the method comprises the following steps of utilizing methane and carbon dioxide to react in a reactor system to generate synthesis gas, then entering a gas separation system, and simultaneously inputting heat energy into the energy storage system in a heat exchange manner to provide heat required by the reaction for methane reforming reaction; the reforming reaction temperature was 600 ℃.
7. The continuous flow conversion system coupled with solar light-gathering catalysis and energy storage, which adopts the system of claim 1, is characterized in that the method comprises the following steps of utilizing solar energy to provide light and heat energy to convey the synthesis gas produced in the reactor system to a gas separation system, obtaining the synthesis gas and recycling the synthesis gas; unreacted reaction gas flows into the reactor again through the inner pipe of the gas separation device to be used as a reactant to continue reacting, so that material balance is realized.
8. The continuous flow conversion system for coupling solar light-gathering catalysis and energy storage, which adopts the system of claim 1, is characterized in that the method comprises the following steps of utilizing the heat energy provided by the solar energy, storing the redundant energy in the energy storage system, maintaining the reaction temperature in the reactor to be constant at 600 ℃ through the intelligent regulation and control of the energy storage system, ensuring the high-added-value conversion condition of the solar photo-thermal catalysis methane to be constant, and realizing the stable and continuous utilization of the solar energy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116443815A (en) * | 2023-04-18 | 2023-07-18 | 西南石油大学 | Circulation system and method for realizing carbon dioxide production by solar energy |
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