A continuous flow conversion system coupling solar light concentration, catalysis and energy storage

Abstract

The present application relates to a kind of coupling solar light concentration catalysis and energy storage continuous flow conversion system, including reactor, heat storage tank, electric heating device and gas separation device.The system utilizes solar energy and converts it into heat energy and light energy, part is used to heat reactor, to provide the energy required for a variety of gas-solid phase photo-thermal catalytic reaction and high temperature condition, another part is used to store, in the condition without light total reactor realizes thermal catalysis.The present application provides a kind of coupling solar light concentration catalysis and energy storage continuous flow conversion system by the design and manufacture of reaction system, realizes the utilization of energy flow and material flow matching of solar energy.

Description

Technical Field

[0001] This invention relates to the field of solar energy utilization technology, and in particular to a continuous flow conversion system that couples solar concentrating catalysis and energy storage. Background Technology

[0002] Solar energy is clean and inexhaustible, but it suffers from uneven temporal distribution, making it largely unsuitable for stable photothermal catalysis.

[0003] Methane, a major component of natural gas and combustible ice, has vast reserves on Earth and holds the promise of replacing fossil fuels as a cleaner energy source. Furthermore, high-value-added products synthesized from methane play a crucial role in the chemical industry, such as ethylene, methanethiol, and syngas. Currently, most solar-powered catalytic materials are cerium oxide and zinc oxide, and the catalytic reactions are primarily thermal catalysis of methane to syngas, with temperatures mostly exceeding 700 degrees Celsius. However, catalysts for catalyzing methane to other high-value-added products are diverse, and the required reaction conditions are mostly photocatalysis or photothermal catalysis. The high temperature of 700 degrees Celsius may cause sintering of the catalytic materials. Developing a new reactor that can effectively control the reactor temperature, enabling its application in various methane catalytic reactions, and simultaneously converting excess solar energy into heat energy for reuse, would organically combine solar photothermal chemical energy storage with solar heat generation, bringing about a significant transformation in the field of solar thermal utilization.

[0004] Northwest my country is rich in solar energy resources. Therefore, if a new reactor can be developed that can organically combine the high-value utilization of methane with solar photothermal catalysis, it will bring about tremendous changes to the field of solar photothermal energy. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a continuous flow conversion system that couples solar concentrating catalysis and energy storage, which combines the high-value utilization of methane with solar photothermal catalysis, and can realize the stable and continuous utilization of solar energy.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A continuous flow conversion system coupling solar concentrating catalysis and energy storage, characterized in that it comprises:

[0008] a) A reactor 1 capable of absorbing heat and reacting, which can collect solar energy and the heat generated by solar energy to supply the process of methane-carbon dioxide conversion;

[0009] b) An energy storage system comprising a thermal storage tank 2, which uses excess energy generated by solar energy in the reactor system to heat the molten metal and regenerate the reaction heat for the reactor under dark conditions;

[0010] c) A compensation system, which includes an electric heating system 3 for compensating for the heat lost in the energy storage system, and by accurately measuring and controlling the heating of molten metal, the molten metal can flow into the reactor 1 at a constant temperature to react.

[0011] d) A gas separation system consisting of a hydrogen separator 15 and a carbon monoxide separator 16, which can separate the outflowing gas through a double-tube casing and collect the required chemical products;

[0012] Reactor 1 is equipped with a quartz tube of the appropriate size, which can be loaded or replaced with a fixed bed of solid particulate catalyst. The operating temperature is 550℃-650℃.

[0013] The gas inlet 13 of the quartz tube is connected to carbon dioxide and methane cylinders, and the total pressure in the reaction system is controlled to be less than 0.1 MPa by a pressure divider valve.

[0014] The reactor has internal heat transfer medium channels that enter and exit from the side of the reactor, and circulate around the middle of the reactor. The inlet and outlet have water head threads of matching size.

[0015] A solar concentrator is installed at the corresponding position of reactor 1 to focus sunlight onto reactor 1.

[0016] The energy storage system includes a thermal storage tank, liquid metal, thermal storage tank outlets AB, an insulated outer shell, a cooling fan, and a bidirectional high-temperature pump.

[0017] The liquid metal contains a large number of ceramic particles 8, which enhance the heat storage capacity of the liquid metal, reduce heat loss, and reduce volume.

[0018] There is a cooling air duct 7 between the heat storage tank 2 and the insulation shell 9, which allows the cooling fan 10 to dissipate excess heat from the heat storage tank; the top of the heat storage tank has a rain cover of appropriate specifications.

[0019] The outlet of the thermal storage tank is equipped with a filter screen 11 to filter ceramic particles.

[0020] The bidirectional high-temperature pump 4 is computer-controlled. When the temperature of reactor 1 is higher than the rated value, the bidirectional high-temperature pump 4 flows in the forward direction, and the heat storage salt flows out from outlet 6 and in from outlet 5, while the electric heating wire 3 does not work. When the temperature of 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 outlet 5 and in from outlet 6. When both the temperature of heat storage tank 2 and the temperature of reactor 1 are 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 surface temperature of reactor 1 and is controlled by a computer program.

[0021] The gas separation system consists of a hydrogen separator 15 and a carbon monoxide separator 16. The gas separator is composed of two 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 allows the specific gas to pass through in a directional manner. The outer cylinder is connected to a gas detection device.

[0022] A continuous flow conversion system coupling solar concentrating catalysis and energy storage includes the following steps:

[0023] When solar radiation is sufficient, gas inlet 13 introduces reactive gas into the quartz tube of reactor 1. Reactor 1 begins to react under photothermal stimulation. The product flows out through gas outlet 14 to the inner tubes of gas collection devices 15 and 16. The inner tube wall has a corresponding palladium film adsorbing the product gas. The product gas passes through the inner tube into the outer tube and flows out through the outer tube outlet for chromatographic quantitative analysis. Unreacted gas continues to be introduced into the reactor's gas inlet 13 from the inner tube outlet for further reaction. The horseshoe-shaped heat exchange tubes inside reactor 1 use excess energy from the solar catalytic reaction to heat the molten metal, which then flows into the heat storage tank 2. At this time, the electric heating system 3 is not working, and the bidirectional high-temperature pump 4 flows in the forward direction. The molten metal flows out through outlet 6, and its specific flow rate is monitored by an external temperature probe and controlled directionally by a computer program to ensure the reactor temperature is between 550℃ and 650℃. When the internal temperature probe of heat storage tank 2 detects that the tank temperature is higher than the rated value, the cooling fan will start to ensure safe operation. The cycle is complete.

[0024] 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. Then, the bidirectional high-temperature pump 4 flows in reverse, and the molten metal flows out from the outlet 5. The temperature of the molten metal heated by sufficient solar radiation is used to heat the reactor. The gas inlet 13 introduces 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 through the corresponding palladium film on the inner tube wall that adsorbs the product gas. The product gas passes through the inner tube into the outer tube and flows out from the outer tube outlet 12 to the gas storage tank for collection. The unreacted gas continues to be introduced into the gas inlet 13 of the reactor from the inner tube outlet to react, completing the cycle.

[0025] When there is no solar radiation and the temperature probe detects that the temperature of the heat storage tank and the reactor are both below the rated value, the electric heater 3 starts to work, the bidirectional high temperature pump 4 flows in reverse, and 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 entering the reactor is greater than 600°C, thus completing the cycle. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of a solar photothermal catalytic reaction system.

[0027] Figure 2 This is a schematic diagram of a solar photothermal catalytic reactor.

[0028] Figure 3 This is a schematic diagram of a gas separation device.

[0029] Figure 4 This is a yield and activity diagram of tetrahedral Ni1 / CeO2 applied to solar concentrated photocatalysis.

[0030] The beneficial effects of this invention are:

[0031] The solar photothermal catalytic reactor based on high-value utilization of methane described in this invention heats the molten metal using solar energy through a concentrator or an electric heating device, controlling the internal temperature of the reactor to remain constant within a certain range. The reactants in the tubes undergo catalytic reaction after absorbing heat and light, thereby achieving an organic combination of high-value utilization of methane and stable solar photothermal catalysis. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only used to explain this invention and are not intended to limit this invention.

[0033] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be apparent to those skilled in the art that these specific details are not necessary to practice the invention. In other embodiments, well-known structures, materials, or methods have not been specifically described in order to avoid obscuring the invention.

[0034] Throughout this specification, references to "an embodiment," "an example," or "an example" mean that a particular feature, structure, or characteristic described in connection with that embodiment or example is included in at least one embodiment of the present invention. Therefore, the phrases "an embodiment," "an example," "an example," or "an example" appearing in various places throughout the specification do not necessarily refer to the same embodiment or example. Furthermore, specific features or characteristics can be combined in one or more embodiments or examples in any suitable combination and / or sub-combination. Moreover, those skilled in the art will understand that the illustrations provided herein are for illustrative purposes and are not necessarily drawn to scale. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0035] Example 1: Solar photothermal catalysis was carried out by introducing 99.99% methane and carbon dioxide into a reactor.

[0036] In this embodiment, methane and carbon dioxide flow through reactor 1 and gas separation device to form a cycle. The hydrogen and carbon monoxide products of methane dry reforming are separated alternately, which causes the equilibrium of the methane dry reforming reaction to shift to the positive direction, and the methane conversion rate is greatly improved compared with the conversion rate of a single reaction.

[0037] The solar concentrator concentrates the solar energy to a temperature of over 1200℃, and the temperature is maintained at 600℃ through energy exchange with molten metal.

[0038] This example uses tetrahedral Ni1 / CeO2 as a catalyst in solar concentrated photocatalysis. Methane and carbon dioxide flow into reactor 1 at a total flow rate of 30 sccm. The catalyst, Ni1 / CeO2, is granulated and screened into 30-70 mesh particles, with a total mass of 200 mg, and placed in a quartz tube in the middle of reactor 1. The calculated light intensity focused by the concentrator corresponding to reactor 1 is 17.25 W. The reaction products are analyzed by gas chromatography-7900, and the product yield is calculated. In this example, the activity of the Ni1 / CeO2 catalyst was measured over 1000 hours, producing approximately 1300 L of carbon monoxide and 1200 L of hydrogen. The specific hourly yield is shown below. Figure 4 As shown.

[0039] Example 2: A long-term test of 200 hours was conducted by introducing 20% ​​methane and carbon dioxide into the reactor.

[0040] In this embodiment, methane and carbon dioxide with a purity of 20% flow through reactor 1 and gas separation device to form a cycle. The hydrogen and carbon monoxide products of methane dry reforming are alternately separated and finally enter the Shimadzu GC-7900 chromatograph for quantitative analysis.

[0041] The solar concentrator concentrates the solar energy to a temperature of over 1200℃, and the temperature is maintained at 600℃ through energy exchange with molten metal.

[0042] This example uses rod-shaped Ni1 / CeO2 as a catalyst in solar concentrated photocatalysis. Methane and carbon dioxide flow into reactor 1 at a total flow rate of 20 sccm. The Ni1 / CeO2 catalyst, after granulation and screening into 30-70 mesh particles with a total mass of 30 mg, is placed in a quartz tube in the middle of reactor 1. The calculated light intensity focused by the concentrator corresponding to reactor 1 is 17.25 W. The reaction products are analyzed by gas chromatography-7900, and the product yield is calculated. In this example, the activity of the Ni1 / CeO2 catalyst is measured for a continuous reaction of 250 hours to observe the stability of the catalyst and the system under solar photothermal catalysis. The system can operate stably for a long time.

[0043] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the substantive technical content of the present invention. The substantive technical content of the present invention is broadly defined within the scope of the claims. Any technical entity or method completed by others that is completely identical to or an equivalent modification of the claims is considered to be covered within the scope of the claims.

Claims

1. A continuous flow conversion system coupling solar concentrating catalysis and energy storage, characterized in that, include: The reactor 1, which absorbs heat and reacts, collects solar energy and the heat generated by solar energy to supply the methane-carbon dioxide conversion process; an energy storage system, including a heat storage tank 2, uses excess energy generated by solar energy in the reactor system to heat the molten metal and re-supply the reactor under light-free conditions; a compensation system, including an electric heating system 3, is used to compensate for the heat lost in the energy storage system by precisely measuring and controlling the heating of the molten metal to ensure that the molten metal flows into the reactor 1 at a constant temperature for reaction; and a gas separation system, consisting of a hydrogen separator 15 and a carbon monoxide separator 16, separates the outflowing gas through a double-pipe casing and collects the required chemical products. The reactor is equipped with a quartz tube of the appropriate size, which is loaded with or replaced with a solid particulate catalyst. The reactor has internal heat transfer medium channels that enter and exit from the side of the reactor and surround the middle of the reactor; the inlet and outlet have water head threads of matching size. The energy storage system includes a thermal storage tank, liquid metal 2, thermal storage tank outlet 5, 6, insulation shell 9, cooling fan 10, and bidirectional high-temperature pump 4; the liquid metal contains a large number of ceramic particles 8 to improve the thermal storage capacity of the liquid metal 2, reduce heat loss, and reduce volume; there is a cooling air duct 7 between the thermal storage tank and the insulation shell, which allows the cooling fan 10 to transfer excess heat from the thermal storage tank; the top of the thermal storage tank has a rain cover 12 of appropriate specifications; the outlet of the thermal storage tank has a filter screen 11 to filter the ceramic particles 8; The bidirectional high-temperature pump 4 is computer-controlled. When the temperature of reactor 1 is higher than the rated value, the bidirectional high-temperature pump 4 flows in the forward direction, and the heat storage salt flows out from outlet 6 and in from outlet 5, while the electric heating wire does not work. When the temperature of 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 outlet 5 and in from outlet 6. When both the temperature of the heat storage tank and the temperature of the reactor are 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 surface temperature of the reactor 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 is composed of two 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, allowing the specific gas to pass through in a directional manner. The outer cylinder is connected to a gas detection device.

2. A continuous flow conversion method coupling solar concentrating photocatalysis and energy storage, applied to the continuous flow conversion system coupling solar concentrating photocatalysis and energy storage as described in claim 1, characterized in that, include: Methane and carbon dioxide are reacted in a reactor system to produce syngas, which then enters a gas separation system. Simultaneously, heat energy is input into an energy storage system via heat exchange to provide the heat required for the methane reforming reaction; the reforming reaction temperature is 600°C. The continuous flow conversion method further includes: using solar energy to provide light and heat to transport the syngas produced in the reactor system to the gas separation system to obtain and recover the syngas; the unreacted reaction gas flows back into the reactor through the inner tube of the gas separation device to continue the reaction as a reactant, thereby achieving material balance; The continuous flow conversion method further includes: utilizing the thermal energy provided by solar energy to store excess energy in an energy storage system; and maintaining the reaction temperature in the reactor at a constant 600°C through intelligent regulation of the energy storage system, thereby ensuring constant conditions for the solar photothermal catalytic conversion of methane into high-value-added products and achieving stable and continuous utilization of solar energy.

Images