CN115092888A - Continuous flow conversion system for coupling solar light-gathering catalysis and energy storage - Google Patents

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

A Continuous Flow Conversion System Coupled with Solar Concentrating Catalysis and Energy Storage

technical field

The invention relates to the technical field of solar energy utilization, in particular to a continuous flow conversion system coupled with solar energy concentrating catalysis and energy storage.

Background technique

Solar energy is clean and inexhaustible, but there is a problem of uneven time distribution, and solar energy cannot be used for stable photothermal catalysis.

As the main component of natural gas and combustible ice, methane has huge reserves on earth and is expected to replace fossil fuels as a cleaner energy source. At the same time, high value-added products based on methane synthesis also play an important role in chemical industry, such as: ethylene, methyl sulfide Alcohol, syngas, etc. At present, most of the materials catalyzed by solar energy are cerium oxide and zinc oxide. The catalytic reaction is mostly methane thermal catalysis to produce synthesis gas, and the temperature is mostly higher than 700 degrees Celsius. However, there are various catalysts for catalyzing methane to produce other high value-added products. , the conditions required for the reaction are mostly photocatalysis or photothermal catalysis, and the high temperature of 700 degrees Celsius may cause the sintering of the catalytic material. If a new reactor can be developed, the reactor can effectively control the temperature of the reactor, so that it can be applied to a variety of methane catalytic reactions, and at the same time convert excess solar energy into thermal energy for reuse, and convert solar thermal chemical storage into solar energy. It can be organically combined with solar heat generation, which will bring great changes to the field of solar thermal utilization.

In northwestern China, solar energy resources are abundant. Therefore, if a new reactor can be developed, which can organically combine the high value-added utilization of methane with solar photothermal catalysis, it will bring benefits to the solar photothermal field. Huge change.

SUMMARY OF THE INVENTION

In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a continuous flow conversion system coupled with solar energy concentrating catalysis and energy storage, which combines the high value-added utilization of methane with solar photothermal catalysis, which can realize the conversion of solar energy to solar energy. Smooth and continuous use.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A continuous flow conversion system coupled with solar energy concentrating catalysis and energy storage, is characterized in that, 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 to carbon dioxide conversion;

b) an energy storage system comprising a thermal storage tank 2 for heating the molten metal from the excess energy generated by solar energy in the reactor system and resupplying the reaction heat for the reactor in dark conditions;

c) a compensation system, which includes an electric heating system 3 for compensating for the heat lost in the energy storage system, by accurately measuring the temperature and controlling the heating of the molten metal, so that the molten metal can flow into the reactor 1 at a constant temperature for reaction;

d) A gas separation system, consisting of a hydrogen separator 15 and a carbon monoxide separator 16, the system can separate the outflowing gas through a double-tube casing to collect the required chemical products;

Reactor 1 is equipped with a quartz tube of suitable size, and the fixed bed of solid particle catalyst can be loaded or replaced in the quartz tube, and the working temperature is 550°C-650°C.

The gas inlet 13 of the quartz tube is communicated with carbon dioxide and methane gas cylinders, and the gas cylinders control the total pressure in the reaction system to be less than 0.1Mpa through a partial pressure valve.

There is a heat transfer medium water channel inside the reactor, which enters and exits from the side of the reactor and surrounds the middle of the reactor. The inlet and outlet are provided with water head threads of matching sizes.

A solar concentrating device for focusing sunlight on the reactor 1 is provided at a corresponding position of the reactor 1 .

The energy storage system includes heat storage tank, liquid metal, heat storage tank outlet AB, thermal insulation shell, cooling fan and bidirectional high temperature pump.

There are a large number of ceramic particles 8 in the liquid metal to improve the heat storage capacity of the liquid metal, reduce heat loss and reduce volume.

There is a cooling air duct 7 between the heat storage tank 2 and the thermal insulation shell 9, so that the cooling fan 10 can dissipate the excess heat of the heat storage tank; the top of the heat storage tank is provided with a rain cover of corresponding specifications.

There is a filter screen 11 at the outlet of the heat storage tank to filter the ceramic particles;

The two-way high-temperature pump 4 is controlled by a computer, when the temperature of the reactor 1 is higher than the rated value, the two-way high-temperature pump 4 flows forward, the heat storage salt flows out from 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 the rated value, the bidirectional high temperature pump 4 flows in the reverse direction, 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 Start 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 controlled by a computer program.

The gas separation system consists of a hydrogen separator 15 and a carbon monoxide separator 16. The gas separator is composed of double cylinders. The gas outlet of the reactor is connected to the inner cylinder of the separator. The inner cylinder wall is attached with a permeable membrane for the corresponding gas, which can be used for specific gas orientation. Permeable, the outer cylinder is connected to a gas detection device.

A continuous flow conversion system coupling solar energy concentrating catalysis and energy storage, comprising 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 is subjected to light and heat to start the reaction, and the product flows out to the inner tubes of the gas collection device systems 15 and 16 through the gas outlet 14. There is a corresponding palladium membrane for adsorbing the product gas on the tube wall, the product gas enters the outer tube through the inner tube and flows out to the chromatographic quantitative analysis from the outer tube outlet, and the unreacted gas continues to pass into the gas inlet 13 of the reactor from the inner tube outlet to react. . The horseshoe-shaped heat exchange tube inside the reactor 1 uses the excess energy in the solar catalytic reaction to heat the molten metal and then flows into the heat storage tank 2 . At this time, the electric heating system 3 does not work, the bidirectional high-temperature pump 4 flows forward, the molten metal flows out from the outlet 6, and its specific flow rate is monitored by the external temperature probe of the reactor, which is controlled by a computer program to ensure that the temperature of the reactor is at 550 ° C -650℃. When the temperature probe inside the heat storage tank 2 detects that the temperature of the heat storage tank is higher than the rated value, the cooling fan will start to ensure safe use. complete the cycle;

When there is no solar radiation, 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 flows in the reverse direction, the molten metal flows out from the outlet 5, and the molten metal heated when the solar radiation is sufficient The temperature is so as to heat the reactor, the gas inlet 13 fills the reaction gas into the quartz tube of the reactor 1, the reactor 1 is heated and reacts, the product passes through the inner tubes of the gas collection devices 15 and 16, and the product gas is adsorbed on the inner tube wall. The corresponding palladium membrane of the product gas permeates the inner tube and enters the outer tube and flows out from the outer tube outlet 12 to the gas storage tank for collection, and the unreacted gas continues to pass into the gas inlet 13 of the reactor from the inner tube outlet to react to complete the cycle.

When there is no solar radiation, and the temperature probe detects that the temperature of the heat storage tank and the reactor are both lower than the rated value, the electric heater 3 starts to work, the bidirectional high temperature pump 4 flows in the reverse direction, and the molten metal flows out from the outlet 5 and passes through the electric heater. The missing energy is compensated to ensure that the temperature of the molten metal entering the reactor is greater than 600°C, completing the cycle.

Description of drawings

Figure 1 is a schematic diagram of a solar photothermal catalytic reaction system device

Figure 2 is a schematic diagram of a solar photothermal catalytic reactor

Figure 3 is a schematic diagram of a gas separation device

Figure 4 is a graph of the yield activity of tetrahedral Ni ₁ /CeO ₂ applied to solar concentrating catalysis

Beneficial effects of the present invention:

The solar photothermal catalytic reactor based on the high value-added utilization of methane according to the present invention uses solar energy to heat the molten metal through a concentrator or an electric heating device to heat the molten metal during specific operation, and the internal temperature of the reactor is controlled to be constant. Within a certain interval, the reactants in the tube side undergo a catalytic reaction after absorbing heat and light, thereby realizing the organic combination of high value-added utilization of methane and stable solar photothermal catalysis.

Detailed ways

In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with the examples. limit.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one of ordinary skill in the art that these specific details need not be employed 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 this specification, references to "one embodiment," "an embodiment," "an example," or "an example" mean that a particular feature, structure, or characteristic described in connection with the embodiment or example is included in the present invention in at least one embodiment. Thus, appearances of the phrases "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 combination and/or subcombination in one or more embodiments or examples. Furthermore, those of ordinary skill in the art will appreciate that the drawings provided herein are for illustrative purposes and that the drawings 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: Passing 99.99% methane and carbon dioxide into the reactor for solar photothermal catalysis.

In the present embodiment, the methane and carbon dioxide pipelines flow through the reactor 1 and the gas separation device to form a cycle, and the hydrogen and carbon monoxide of the methane dry reforming product are alternately separated, so that the equilibrium of the methane dry reforming reaction is moved to the positive direction, so that the methane conversion rate is increased. Compared with a single reaction, the conversion rate is greatly improved.

Among them, the temperature of the solar concentrator reaches more than 1200 °C after concentrating, and the temperature is maintained at 600 °C through the energy exchange of molten metal.

In this example, tetrahedral Ni ₁ /CeO ₂ is used as a catalyst for solar concentrating catalysis. Methane and carbon dioxide flowed into Reactor 1 at a total flow rate of 30 sccm. The catalyst was Ni ₁ /CeO ₂ , which was granulated and screened for 30-70 mesh particles with a total mass of 200 mg, placed in a quartz tube in the middle of Reactor 1. After calculation, the light intensity collected by the concentrator corresponding to the reactor 1 is 17.25W. The product after the reaction enters into the gas chromatography GC-7900 for analysis and calculates the product yield. In this example, the activity of the Ni ₁ /CeO ₂ catalyst was measured for 1000 h, and a total of about 1300 L of carbon monoxide and 1200 L of hydrogen were produced in 1000 h. The specific output per hour is shown in Figure 4.

Example 2: A long-term 200-hour test was conducted with 20% methane and carbon dioxide into the reactor.

In this example, the methane and carbon dioxide pipelines with a purity of 20% flow through the reactor 1 and the gas separation device to form a cycle, and the hydrogen and carbon monoxide of the methane dry reforming products are alternately separated, and finally enter the Shimadzu GC-7900 chromatographic quantitative analysis.

Among them, the temperature of the solar concentrator reaches more than 1200 °C after concentrating, and the temperature is maintained at 600 °C through the energy exchange of molten metal.

In this example, rod-shaped Ni ₁ /CeO ₂ is used as a catalyst for solar concentrating catalysis. Methane and carbon dioxide flowed into Reactor 1 at a total flow rate of 20sccm. The catalyst Ni ₁ /CeO ₂ was granulated and screened for 30-70 mesh particles with a total mass of 30 mg, and placed in a quartz tube in the middle of Reactor 1. After calculation, the light intensity collected by the concentrator corresponding to the reactor 1 is 17.25W. The product after the reaction enters into the gas chromatography GC-7900 for analysis and calculates the product yield. In this example, the Ni ₁ /CeO ₂ catalyst was continuously reacted for a total of 250 hours, and the stability of the catalyst and the system was observed under the state of solar photothermal catalysis, and the system could run stably for a long time.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of the essential technical content of the present invention. The essential technical content of the present invention is broadly defined in the scope of the claims of the application, and any technical entity completed by others Or method, if it is exactly the same as that defined in the scope of the claims of the application, or an equivalent change, it will be deemed to be covered by the scope of the claims.

Claims (8)

1. A continuous flow conversion system coupled with solar energy concentrating catalysis and energy storage is characterized in that, comprising: a reactor 1 capable of absorbing heat and reacting, and the reactor can collect solar energy and the heat generated by solar energy, thereby supplying the conduct of methane carbon dioxide conversion; an energy storage system comprising a heat storage tank 2 that heats the molten metal from excess energy generated by solar energy in the reactor system and re-supplies the reaction heat to the reactor in dark conditions; a Compensation system, which includes an electric heating system 3 for compensating for the heat lost in the energy storage system, through accurate temperature measurement and control to heat the molten metal, so that the molten metal can flow into the reactor 1 at a constant temperature for reaction; a gas separation system , consisting of a hydrogen separator 15 and a carbon monoxide separator 16, the system can separate the outflowing gas through a double-pipe casing to collect the required chemical products. 2. The reactor of a continuous flow conversion system coupled with solar concentrating catalysis and energy storage according to claim 1, characterized in that: the reactor is equipped with a quartz tube conforming to the size, and the quartz tube can be loaded with or The solid particle catalyst is replaced; there is a heat transfer medium water channel inside the reactor, which enters and exits from the side of the reactor and surrounds the middle of the reactor; the inlet and outlet are provided with water head threads of matching sizes. 3. The heat storage system of a continuous flow conversion system coupled with solar concentrating catalysis and energy storage according to claim 1, wherein the energy storage system comprises a heat storage tank, a liquid metal 2, and an outlet of the heat storage tank 5 , 6. Thermal insulation shell 9, cooling fan 10 and two-way high temperature pump 4; a large number of ceramic particles 8 in liquid metal to improve the heat storage capacity of liquid metal 2, reduce heat loss and reduce volume; heat storage tank and thermal insulation shell There is a cooling air duct 7 between, so that the cooling fan 10 can transfer excess heat from the heat storage tank; the top of the heat storage tank is provided with a rain cover 12 of corresponding specifications; 4. A continuous flow conversion system coupled with solar energy concentrating catalysis and energy storage according to claim 2, is characterized in that: the two-way high temperature pump 4 is controlled by a computer, when the temperature of the reactor 1 is higher than the rated value, the two-way high temperature pump 4 is controlled by a computer. The high temperature pump 4 flows forward, the heat storage salt flows out from 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 the rated value, the bidirectional high temperature pump 4 flows in the reverse direction, and the heat storage salt flows out from the outlet 5 , flows in from the outlet 6; when the temperature of the heat storage tank and the reactor temperature 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 is determined by the actual temperature of the reactor surface and controlled by a computer program. 5 . The gas separation system of a continuous flow conversion system coupled with solar concentrating catalysis and energy storage according to claim 1 , wherein the gas separation system is composed of a hydrogen separator 15 and a carbon monoxide separator 16 . , The gas separator is composed of double cylinders, the gas outlet of the reactor is connected to the inner cylinder of the separator, the inner cylinder wall is attached with a permeable membrane of the corresponding gas, which can be directionally permeated by a specific gas, and the outer cylinder is connected to a gas detection device. 6. adopt the continuous flow conversion system of a kind of coupling solar energy concentrating catalysis and energy storage of system as claimed in claim 1, it is characterized in that this method comprises the steps: utilize methane and carbon dioxide to react in reactor system to produce synthesis gas, Then it enters the gas separation system, and meanwhile, heat energy is input into the energy storage system by means of heat exchange to provide the required heat for the methane reforming reaction; the reforming reaction temperature is 600°C. 7. adopt the continuous flow conversion system of a kind of coupling solar energy concentrating catalysis and energy storage of system as claimed in claim 1, it is characterized in that this method comprises the steps: utilize solar energy to provide light and thermal energy to make in the reactor system The synthesis gas is transported to the gas separation system to obtain the synthesis gas and recover it; the unreacted reaction gas flows back into the reactor through the inner pipe of the gas separation device as a reactant to continue the reaction to achieve material balance. 8. adopt the continuous flow conversion system of a kind of coupling solar energy concentrating catalysis and energy storage of system as claimed in claim 1, it is characterized in that this method comprises the steps: utilize the thermal energy that solar energy provides, excess energy is stored in energy storage In the system, through the intelligent regulation of the energy storage system, the reaction temperature in the reactor is kept constant at 600 °C, so that the conditions for the high value-added conversion of methane by solar photothermal catalysis are constant, and the stable and continuous utilization of solar energy is realized.

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