Artificial photosynthesis reaction device and reaction system for enhancing catalytic performance

Abstract

The invention provides an artificial photosynthesis reaction device and reaction system for enhancing catalytic performance, the reaction device comprises a pretreatment unit, a mixing transmission unit, a photocatalytic regeneration unit and a separation unit, the pretreatment unit is used for activating received carbon dioxide in a supercritical state; the mixing and conveying unit is used for mixing all gas raw materials according to a preset proportion and conveying the mixed gas raw materials to the photocatalytic regeneration unit; the photocatalytic regeneration unit is used for preheating, activating and regenerating a photocatalyst and generating a chemical reaction; and the separation unit is used for separating the reacted mixture and sending the unreacted mixed gas back to the photocatalytic regeneration unit. According to the technical scheme, through industrial treatment, the chemical inertness of carbon dioxide can be reduced, the reaction energy consumption is reduced, and meanwhile the catalytic reaction efficiency and the overall chemical reaction conversion rate are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical conversion and reaction engineering, and particularly relates to an artificial photosynthesis reaction device and reaction system with enhanced catalytic performance. Background Art

[0002] With the global emphasis on carbon emissions and energy structure transformation, the conversion of carbon dioxide (CO2) resources into high-value chemicals (such as methanol) has become a research hotspot. Using the CO2 emitted by industries to prepare methanol not only helps reduce greenhouse gas emissions, but also provides a way for carbon cycle utilization and a renewable resource approach. In addition, methanol is an important chemical raw material, which can be used to produce a variety of chemicals and fuels and has broad industrial application prospects. The industrial process of converting carbon dioxide (CO2) into methanol can be simply expressed as: CO2 + 3H2 → CH3OH + H2O, and this reaction requires appropriate temperature, pressure, and an effective catalyst to improve the conversion efficiency and selectivity.

[0003] The existing CO2 hydrogenation to methanol process mainly relies on high-temperature and high-pressure catalytic reactions. However, due to the stable molecular structure and low reaction activity of CO2, the catalytic efficiency and selectivity are often limited. On the other hand, photocatalysis has been widely concerned due to its mild reaction conditions and environmental friendliness advantages. However, the activation degree of CO2 in traditional photocatalytic reactions is insufficient, which restricts the overall conversion rate.

[0004] Therefore, a technical solution is needed to reduce the chemical inertness of carbon dioxide through industrial treatment, reduce the reaction energy consumption, and improve the catalytic reaction efficiency and the overall chemical reaction conversion rate. Summary of the Invention

[0005] The present application aims to provide an artificial photosynthesis reaction device and reaction system with enhanced catalytic performance, which can reduce the chemical inertness of carbon dioxide through industrial treatment, reduce the reaction energy consumption, and improve the catalytic reaction efficiency and the overall chemical reaction conversion rate.

[0006] According to one aspect of the present application, there is provided an artificial photosynthesis reaction device with enhanced catalytic performance for preparing methanol using carbon dioxide and hydrogen as raw materials. The artificial photosynthesis reaction device includes: a pretreatment unit, a mixing and transmission unit, a photocatalytic regeneration unit, and a separation unit. Among them,

[0007] The pretreatment unit is used to activate the received carbon dioxide in a supercritical state and send the activated carbon dioxide into the mixing and transmission unit;

[0008] The mixed transmission unit receives hydrogen and the carbon dioxide after being activated by the pretreatment unit, mixes them in a predetermined ratio to obtain a mixed gas, and transmits the mixed gas to the photocatalytic regeneration unit;

[0009] The photocatalytic regeneration unit receives the mixed gas from the mixed transmission unit. The photocatalytic regeneration unit includes a light source for providing illumination for the chemical reaction. The photocatalytic regeneration unit is used for preheating and activating the regeneration of the photocatalyst, and for the chemical reaction of the mixed gas to occur under the action of light and the photocatalyst, obtaining a mixture of methanol and the unreacted mixed gas, and sending the mixture into the separation unit;

[0010] The separation unit separates the methanol and the unreacted mixed gas in the mixture, and sends the unreacted mixed gas back to the photocatalytic regeneration unit.

[0011] According to some embodiments, the pretreatment unit includes a first raw material delivery channel, a first throttle valve, and a reaction kettle, where,

[0012] The first raw material delivery channel is used to input the carbon dioxide into the reaction kettle and send the activated carbon dioxide into the mixed transmission unit;

[0013] The first throttle valve is arranged on the first raw material delivery channel for controlling the delivery amount of the carbon dioxide;

[0014] The reaction kettle is used for activating the received carbon dioxide in a supercritical state, and sending the activated carbon dioxide into the mixed transmission unit through the first raw material delivery channel.

[0015] According to some embodiments, a constant temperature control system is arranged inside the reaction kettle for ensuring the uniformity and stability of the temperature inside the reaction kettle.

[0016] According to some embodiments, the reaction kettle is made of a high-temperature and high-pressure resistant material, and the operating conditions of the reaction kettle are set as 35℃ 80 - 100 bar to ensure that the carbon dioxide is in a supercritical state.

[0017] According to some embodiments, the mixed transmission unit includes: a second raw material delivery channel, a second throttle valve, a third raw material delivery channel, a third throttle valve, and a gas mixer, where,

[0018] The second raw material delivery channel is used to input the hydrogen into the gas mixer;

[0019] The second throttle valve is arranged on the second raw material delivery channel for controlling the delivery amount of the hydrogen;

[0020] The gas mixer is used for mixing the activated carbon dioxide and the hydrogen to obtain the mixed gas;

[0021] The third raw material delivery channel is used for delivering the mixed gas into the mixing and transfer unit;

[0022] The third throttle valve is arranged on the third raw material delivery channel and is used for controlling the delivery amount of the mixed gas.

[0023] According to some embodiments, the photocatalytic regeneration unit further includes: a photocatalytic fluidized bed reactor and a regenerator, wherein,

[0024] The regenerator includes a feed inlet and a riser. The photocatalyst is added into the regenerator through the feed inlet. After preheating and regeneration of the photocatalyst in the regenerator, the photocatalyst is sent into the fluidized bed reactor through the riser;

[0025] The photocatalytic fluidized bed reactor receives the catalyst from the regenerator and the mixed gas from the mixing and transfer unit. In the photocatalytic fluidized bed reactor, the mixed gas undergoes a fluidized reaction under the action of the photocatalyst to obtain a mixture of methanol and the unreacted mixed gas, and the mixture is sent into the separation unit,

[0026] The photocatalytic fluidized bed reactor includes a first feedback channel arranged at the bottom of the photocatalytic fluidized bed reactor to recover the deactivated photocatalyst after the reaction and reflux it into the regenerator.

[0027] According to some embodiments, the separation unit includes: a separator and a second feedback channel,

[0028] The separator is used for separating methanol and the unreacted mixed gas in the mixture and externally delivering the methanol;

[0029] The second feedback channel connects the separator and the photocatalytic fluidized bed reactor and sends the unreacted mixed gas back into the photocatalytic fluidized bed reactor.

[0030] According to some embodiments, a throttle valve is arranged on the second feedback channel to prevent the reflux of the unreacted mixed gas.

[0031] According to some embodiments, the separator includes: a condenser, a gas separator or an adsorption device for separating methanol from the unreacted mixed gas.

[0032] According to another aspect of the present application, there is provided an artificial photosynthesis reaction system for enhancing catalytic performance, the system comprising: a control system and the artificial photosynthesis reaction device as described in any one of the above.

[0033] According to an embodiment of the present application, the design scheme of the present invention uses CO2 as a raw material for methanol preparation, and the produced methanol can be used as a clean energy and chemical raw material, which helps to reduce the atmospheric CO2 concentration. By adding a pretreatment unit to activate carbon dioxide in a supercritical state, its chemical inertness can be reduced, enabling the reaction to achieve methanol preparation through a photocatalytic reaction under milder conditions, greatly improving the subsequent photocatalytic reaction rate and reducing the energy consumption of traditional high-temperature and high-pressure reactions; by adding the mixing and transmission unit, the fully and uniformly mixed activated carbon dioxide and the hydrogen are realized, improving the utilization rate of raw materials and enhancing the stability and efficiency of the entire process flow; by adding the photocatalytic regeneration unit, the effective regeneration and recycling of the photocatalyst are realized, ensuring the efficient operation of the entire device, improving the utilization rate of the photocatalyst and reducing the preparation cost; by adding the separation unit, the effective separation and recycling of the unreacted mixed gas are realized, reducing the waste of raw materials and ensuring the efficient operation of the entire artificial photosynthesis reaction device.

[0034] It should be understood that the above general description and the following detailed description are only exemplary and do not limit the present application. Brief Description of the Drawings

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below.

[0036] Figure 1 Schematic diagram showing an artificial photosynthesis reaction device for enhancing catalytic performance according to an exemplary embodiment.

[0037] Figure 2 Schematic diagram showing an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment.

[0038] Figure 3 Schematic diagram showing the pretreatment unit and the mixing and transmission unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment.

[0039] Figure 4 Schematic diagram showing the photocatalytic regeneration unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment.

[0040] Figure 5 Schematic diagram showing the separation unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment. Detailed Implementation Modes

[0041] Example embodiments will now be described more fully with reference to the accompanying drawings. However, the example embodiments can be implemented in various forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this application will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art. Like reference numerals in the figures denote like or similar parts, and thus their repetitive description will be omitted.

[0042] In addition, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of the embodiments of this application. However, those skilled in the art will realize that the technical solutions of this application can be practiced without one or more of the specific details, or other methods, components, devices, steps, etc. may be used. In other cases, well-known methods, devices, implementations, or operations are not shown or described in detail to avoid obscuring aspects of this application.

[0043] The block diagrams shown in the drawings are only functional entities and do not necessarily correspond to physically independent entities. That is, these functional entities can be implemented in software form, or in one or more hardware modules or integrated circuits, or in different networks and / or processor devices and / or microcontroller devices.

[0044] The flowcharts shown in the drawings are merely illustrative and do not necessarily include all the content and operations / steps, nor do they necessarily have to be executed in the order described. For example, some operations / steps can be decomposed, while some operations / steps can be combined or partially combined, so the actual execution order may change according to the actual situation.

[0045] It should be understood that although terms such as first, second, and third may be used herein to describe various components, these components should not be limited by these terms. These terms are used to distinguish one component from another. Thus, the first component discussed below can be referred to as the second component without departing from the teachings of the concept of this application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0046] The user information (including but not limited to user device information, user personal information, etc.) and data (including but not limited to data for analysis, stored data, displayed data, etc.) involved in this application are all information and data that have been authorized by the user or fully authorized by all parties, and the collection, use, and processing of the relevant data need to comply with the relevant laws, regulations, and standards of the relevant countries and regions, and corresponding operation entrances are provided for the user to choose to authorize or refuse.

[0047] Those skilled in the art can understand that the accompanying drawings are only schematic diagrams of exemplary embodiments, and the modules or processes in the drawings are not necessarily essential for implementing this application, so they cannot be used to limit the protection scope of this application.

[0048] With the global emphasis on carbon emissions and energy structure transformation, the resource conversion of carbon dioxide (CO2) into high-value chemicals (such as methanol) has become a research hotspot. Using the CO2 emitted by industries to prepare methanol not only helps reduce greenhouse gas emissions but also provides a way for carbon recycling and a renewable resource approach. In addition, methanol is an important chemical raw material that can be used to produce various chemicals and fuels, with broad industrial application prospects. The process of converting carbon dioxide (CO2) into methanol in industry can be simply expressed as: CO2 + 3H2 → CH3OH + H2O, and this reaction requires appropriate temperature, pressure, and an effective catalyst to improve the conversion efficiency and selectivity.

[0049] Existing CO2 hydrogenation processes to methanol mainly rely on high-temperature and high-pressure catalytic reactions. However, due to the stable molecular structure and low reactivity of CO2 molecules, the catalytic efficiency and selectivity are often limited. On the other hand, photocatalysis has received extensive attention due to its mild reaction conditions and environmental friendliness advantages. However, the activation degree of CO2 in traditional photocatalytic reactions is insufficient, which restricts the overall conversion rate.

[0050] In recent years, supercritical fluid technology has shown great potential in the field of CO2 activation due to its excellent solubility and mass transfer characteristics. Pretreating CO2 in the supercritical state can cause partial dissociation of its molecular structure or generate intermediate active substances, thereby providing more favorable reaction conditions for subsequent photocatalytic reactions and improving the overall conversion efficiency.

[0051] To this end, the present application proposes an artificial photosynthesis reaction device and reaction system with enhanced catalytic performance, which can reduce the chemical inertness of carbon dioxide through industrial treatment, reduce the reaction energy consumption while improving the catalytic reaction efficiency and the overall conversion rate of chemical reactions. According to the embodiment, the design scheme of the present invention uses CO2 as a raw material for the preparation of methanol, and the produced methanol can be used as a clean energy and chemical raw material, which helps to reduce the atmospheric CO2 concentration and achieve the carbon neutrality goal. By adding a pretreatment unit to activate carbon dioxide in a supercritical state, its chemical inertness can be reduced, enabling the reaction to achieve the preparation of methanol through a photocatalytic reaction under milder conditions, greatly improving the subsequent photocatalytic reaction rate and reducing the energy consumption of traditional high-temperature and high-pressure reactions; by adding the mixing and transmission unit, the fully and evenly mixed activation of the carbon dioxide and the hydrogen is realized, improving the raw material utilization rate and enhancing the stability and efficiency of the entire process flow; by adding the photocatalytic regeneration unit, the effective regeneration and recycling of the photocatalyst are realized, ensuring the efficient operation of the entire device, improving the utilization rate of the photocatalyst and reducing the preparation cost; by adding the separation unit, the effective separation and recycling of the unreacted mixed gas are realized, reducing the waste of raw materials and ensuring the efficient operation of the entire artificial photosynthesis reaction device.

[0052] The exemplary embodiments of the present application will be described below with reference to the accompanying drawings.

[0053] Figure 1 Fig. shows a schematic diagram of an artificial photosynthesis reaction device with enhanced catalytic performance according to an exemplary embodiment.

[0054] See Figure 1 , in the figure, an artificial photosynthesis reaction device with enhanced catalytic performance is shown, which is used to prepare methanol from carbon dioxide and hydrogen. The artificial photosynthesis reaction device includes: a pretreatment unit 01, a mixing and transmission unit 02, a photocatalytic regeneration unit 03, and a separation unit 04.

[0055] According to some embodiments, the pretreatment unit is used to activate the received carbon dioxide in a supercritical state and send the activated carbon dioxide into the mixing and transmission unit 02. The pretreatment unit 01 is responsible for receiving and processing carbon dioxide to activate it in a supercritical state. The supercritical state means that carbon dioxide is heated and pressurized to specific conditions (temperature and pressure exceeding its critical point) to enhance the efficiency of subsequent chemical reactions. The processed carbon dioxide is then sent into the mixing and transmission unit 02.

[0056] According to some embodiments, the hybrid transmission unit 02 receives hydrogen and the carbon dioxide after being activated by the pretreatment unit 01 and mixes them in a predetermined ratio to obtain a mixed gas, and transmits the mixed gas to the photocatalytic regeneration unit 03. In the hybrid transmission unit 02, the activated carbon dioxide and hydrogen are mixed in a predetermined ratio to form a mixed gas. This precise ratio is crucial for ensuring the effectiveness of the chemical reaction. After mixing, the mixed gas is transmitted to the photocatalytic regeneration unit 03.

[0057] According to some embodiments, the photocatalytic regeneration unit 03 receives the mixed gas from the hybrid transmission unit 02. The photocatalytic regeneration unit 03 includes a light source 0303 for providing illumination for the chemical reaction. The photocatalytic regeneration unit 03 is used for preheating and activating the photocatalyst for regeneration and for the chemical reaction of the mixed gas under the action of light and the photocatalyst to obtain a mixture of methanol and the unreacted mixed gas, and sends the mixture into the separation unit 04. The photocatalytic regeneration unit 03 includes a light source 0303 to provide the necessary illumination conditions for the chemical reaction. The photocatalytic regeneration unit 03 is also used for preheating and activating the photocatalyst for regeneration. Among them, the photocatalyst can be modified titanium dioxide, cadmium sulfide, bismuth vanadate, etc. The photocatalyst is activated under the action of light to promote the chemical reaction between carbon dioxide and hydrogen to generate methanol and the unreacted mixed gas. The resulting mixture is then sent to the separation unit 04.

[0058] According to some embodiments, the separation unit 04 separates the methanol and the unreacted mixed gas in the mixture and sends the unreacted mixed gas back to the photocatalytic regeneration unit 03. The function of the separation unit 04 is to separate the methanol and the unreacted mixed gas in the mixture obtained from the photocatalytic regeneration unit 03. The pure methanol can be collected as the final product, while the unreacted mixed gas will be recycled back to the photocatalytic regeneration unit 03 to further participate in the reaction and improve the resource utilization rate.

[0059] According to some embodiments, the design of the present invention simulates the photosynthesis process in nature through artificial photosynthesis. Under artificial conditions, for example, by means of catalysts, light, high temperature and high pressure, etc., carbon dioxide (CO2) reacts with hydrogen (H2) to generate hydrocarbons. Through such an artificial photosynthesis reaction method, it is possible to effectively promote the green conversion of carbon dioxide (CO2), efficiently collect energy substances, avoid the energy loss of the natural system, and can take into account alleviating environmental pollution and coping with the shortage of fossil energy.

[0060] Figure 2 FIG. shows a schematic diagram of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment.

[0061] Figure 3 Schematic diagrams of a pretreatment unit and a hybrid transport unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment are shown.

[0062] See Figure 2 and Figure 3 , the pretreatment unit 01 includes a first raw material delivery channel 0101, a first throttle valve 0102, and a reaction kettle 0103.

[0063] According to some embodiments, the first raw material delivery channel 0101 is used to input the carbon dioxide into the reaction kettle 0103 and send the activated carbon dioxide into the hybrid transport unit 02. The first raw material delivery channel 0101 is responsible for two aspects of work. On the one hand, it inputs carbon dioxide into the reaction kettle 0103 for activation treatment; on the other hand, after the carbon dioxide is activated, it serves as a transmission path to send the activated carbon dioxide into the hybrid transport unit 02.

[0064] According to some embodiments, the first throttle valve 0102 is disposed on the first raw material delivery channel 0101 for controlling the delivery amount of the carbon dioxide. The first throttle valve 0102 is located on the first raw material delivery channel 0101 for precisely controlling the amount of carbon dioxide entering the reaction kettle 0103 to ensure that subsequent chemical reactions can proceed in an optimal ratio.

[0065] According to some embodiments, the reaction kettle 0103 is used to activate the received carbon dioxide in a supercritical state and send the activated carbon dioxide into the hybrid transport unit 02 through the first raw material delivery channel 0101. The reaction kettle 0103, as the core component of the pretreatment unit 01, its main task is to activate carbon dioxide in a supercritical state. Utilize the supercritical state (both the temperature and pressure reach or exceed the CO2 critical point, such as treating the feed CO2 at 31.1 °C and 73.8 bar). Under supercritical conditions, the CO2 molecular structure undergoes partial dissociation or forms excited-state intermediate species, enhancing its reactivity with hydrogen.

[0066] According to some embodiments, the reaction kettle 0103 made of high-temperature and high-pressure resistant materials is set with operating conditions of 35 °C and 80 - 100 bar to ensure that CO2 is in a supercritical state. The reaction kettle 0103 made of high-temperature and high-pressure resistant materials can work under the set operating conditions (35 °C, 80 - 100 bar) to ensure that carbon dioxide is in a supercritical state, thereby improving the efficiency of subsequent chemical reactions.

[0067] According to some embodiments, a constant temperature control system is provided inside the reactor, including a stirring system and a temperature control module, which are used to ensure that the temperature inside the reactor 0103 is uniform and stable. To ensure the effectiveness of this process, a constant temperature control system is equipped inside the reactor 0103 to ensure uniform and stable internal temperature.

[0068] In summary, through the design described above, the pretreatment unit 01 can effectively prepare carbon dioxide so that it can better react with hydrogen to produce methanol in the subsequent steps. Such a system design not only improves the raw material utilization rate but also lays a foundation for the smooth progress of the entire process flow. In addition, by precisely controlling the operating conditions, the reaction conditions can be optimized, thereby improving the quality and yield of the final product.

[0069] See Figure 2 and Figure 3 , the mixing and transfer unit 02 includes: a second raw material delivery channel 0202, a second throttle valve 0201, a third raw material delivery channel 0204, a third throttle valve 0203, and a gas mixer 0205. Among them, the second raw material delivery channel 0202 is used to input the hydrogen into the gas mixer 0205; the second throttle valve 0201 is arranged on the second raw material delivery channel 0202 to control the delivery amount of the hydrogen; the gas mixer 0205 is used for mixing the activated carbon dioxide and the hydrogen to obtain the mixed gas; the third raw material delivery channel 0204 is used to send the mixed gas into the mixing and transfer unit 02; the third throttle valve 0203 is arranged on the third raw material delivery channel 0204 to control the delivery amount of the mixed gas.

[0070] According to some embodiments, the artificial photosynthesis reaction device precisely adjusts the flow rates of the input hydrogen and the activated carbon dioxide through the second throttle valve 0201 and the third throttle valve 0203 to ensure that the two are mixed in a predetermined optimal ratio. The common ratio range can be set from 1:3 to 1:5. During the process of delivering the mixed gas to the photocatalytic reactor, through the second raw material delivery channel 0202, the second throttle valve 0201, the third raw material delivery channel 0204, and the third throttle valve 0203, it is ensured that the gas enters the reactor at a stable flow rate and a uniform pressure distribution, so that the gas can be dispersed as evenly as possible inside the reactor, which not only improves the raw material utilization rate but also enhances the stability and efficiency of the entire process flow.

[0071] According to some embodiments, the first, second, and third throttle valves can also prevent the backflow of the activated carbon dioxide, hydrogen, and the mixed gas, further ensuring that the subsequent chemical reactions can proceed in an optimal ratio.

[0072] Figure 4Schematic diagram of a photocatalytic regeneration unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment is shown.

[0073] See Figure 4 , in the figure, a photocatalytic regeneration unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment is shown. The photocatalytic regeneration unit 03 further includes: a photocatalytic fluidized bed reactor 0301 and a regenerator 0302.

[0074] According to some embodiments, the regenerator 0302 includes a feed inlet 03021 and a riser 03022. The photocatalyst is added into the regenerator 0302 through the feed inlet 03021. After preheating and regeneration of the photocatalyst in the regenerator 0302, the photocatalyst is sent into the fluidized bed reactor through the riser 03022. The feed inlet 03021 is an inlet for adding new or regenerated photocatalyst into the regenerator 0302. Through this inlet, the catalyst can be replenished or replaced regularly to ensure that there is always enough active catalyst in the reactor to participate in the reaction. The riser 03022 is used to transport the preheated and regenerated photocatalyst from the regenerator 0302 to the photocatalytic fluidized bed reactor 0301, ensuring that the catalyst can be smoothly transported into the photocatalytic fluidized bed reactor 0301 to continuously participate in the chemical reaction.

[0075] According to some embodiments, new photocatalyst is added into the regenerator 0302 through the feed inlet 03021. Inside the regenerator 0302, the photocatalyst is preheated to remove possible impurities and at the same time enhance the activity of the photocatalyst, enabling it to participate more effectively in subsequent chemical reactions. After preheating, the activated photocatalyst is sent to the photocatalytic fluidized bed reactor 0301 through the riser 03022 to participate in the chemical reaction.

[0076] According to some embodiments, inside the regenerator 0302, the deactivated photocatalyst that needs to be regenerated will undergo a preheating and regeneration process. The regeneration process aims to restore the activity of the catalyst, while the preheating step helps to remove possible impurities or adsorbed by-products and at the same time enhance the activity of the photocatalyst, enabling it to effectively participate in subsequent chemical reactions. After preheating and regeneration, similarly, the photocatalyst is sent back into the photocatalytic fluidized bed reactor 0301 through the riser 03022 to re-participate in the reaction of converting carbon dioxide and hydrogen into methanol.

[0077] According to some embodiments, through the application of the regenerator 0302 in the design of the present invention, preheating, regeneration and reuse of the photocatalyst are realized, providing a stable and efficient catalyst source for the whole system and supporting the continuous chemical conversion process.

[0078] According to some embodiments, through the preheating and regeneration processes, the service life of the photocatalyst in the device can be effectively extended, the need for frequent catalyst replacement can be reduced, thereby lowering the production cost. Through the preheating and regeneration processes, it can be ensured that the photocatalyst always maintains a high activity state, improving the selectivity and yield of chemical reactions, promoting the effective utilization of the photocatalyst, and reducing the production cost.

[0079] According to some embodiments, the photocatalytic fluidized bed reactor 0301 receives the catalyst from the regenerator 0302 and the mixed gas from the mixing and transfer unit 02. In the photocatalytic fluidized bed reactor 0301, the mixed gas undergoes a fluidized reaction under the action of the photocatalyst to obtain a mixture of the methanol and the unreacted mixed gas, and the mixture is sent to the separation unit 04.

[0080] According to some embodiments, the photocatalytic fluidized bed reactor 0301 receives the activated photocatalyst after preheating and regeneration treatment from the regenerator 0302, and at the same time receives the mixed gas from the mixing and transfer unit 02. Inside the photocatalytic fluidized bed reactor 0301, the mixed gas comes into full contact with the photocatalyst and undergoes a chemical reaction under the action of light with a specific wavelength. Under the action of the photocatalyst (such as modified titanium dioxide TiO2, cadmium sulfide CdS, bismuth vanadate BiVO4, etc.), a chemical reaction of converting carbon dioxide and hydrogen into methanol occurs, generating a mixture of the methanol and the unreacted mixed gas, and the generated mixture (methanol and unreacted mixed gas) is sent to the separation unit 04 for further separation.

[0081] According to some embodiments, the photocatalytic fluidized bed reactor 0301 includes a first feedback channel 03011 disposed at the bottom of the photocatalytic fluidized bed reactor 0301, which recovers the deactivated photocatalyst after the reaction and returns it to the regenerator 0302. The first feedback channel 03011 is disposed at the bottom of the reactor, recovers the deactivated photocatalyst after the reaction, and returns it to the regenerator 0302 for regeneration treatment, ensuring that the photocatalyst can continuously maintain high efficiency and activity, thereby supporting the continuous operation of the system.

[0082] According to some embodiments, the photocatalytic fluidized bed reactor 0301 receives the active photocatalyst from the regenerator 0302 and the mixed gas from the mixing and transfer unit 02. Inside the reactor, the mixed gas and the photocatalyst undergo a chemical reaction under light irradiation to generate a mixture of methanol and the unreacted mixed gas. The mixture is sent to the separation unit 04 for separation, so that the unreacted gas can be recycled. Through the first feedback channel 03011, the deactivated photocatalyst after the reaction is recovered and returned to the regenerator 0302 for regeneration, and then re-enters the reactor through the riser 03022 for recycling, improving the efficiency of converting carbon dioxide into methanol while maintaining a low operating cost.

[0083] According to some embodiments, the photocatalyst is pretreated and surface-modified, having a high specific surface area and good light responsiveness. The light source 0303 can adopt an LED or a high-efficiency solar heat collector supplemented with a reflector and a light-transmitting window design to improve the light energy utilization rate and enhance the sustainability and economy of the entire process.

[0084] Figure 5 The schematic diagram of the separation unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment is shown.

[0085] See Figure 5 , in the figure, the separation unit of an artificial photosynthesis reaction device for enhancing catalytic performance according to another exemplary embodiment is shown. The separation unit 04 includes: a separator 0401 and a second feedback channel 0402. The separator 0401 is used to separate the methanol and the unreacted mixed gas in the mixture and externally transport the methanol; the second feedback channel 0402 connects the separator 0401 and the photocatalytic fluidized bed reactor 0301 to send the unreacted mixed gas back to the photocatalytic fluidized bed reactor 0301.

[0086] According to some embodiments, the separator 0401 receives the mixture from the photocatalytic fluidized bed reactor 0301 for separation, which is usually achieved by physical or chemical methods, such as condensation, adsorption, or membrane separation techniques. The separated pure methanol is externally transported as the final product and can be used for subsequent industrial applications or other purposes. The second feedback channel 0402 connects the separator 0401 and the photocatalytic fluidized bed reactor 0301 to send the unreacted mixed gas (mainly carbon dioxide and hydrogen) back to the photocatalytic fluidized bed reactor 0301 so that these gases can participate in the reaction again, improving the raw material utilization rate and reducing waste.

[0087] According to some embodiments, a fourth throttle valve 0403 is provided on the second feedback channel 0402 to prevent the reflux of the unreacted mixed gas. The remaining unreacted mixed gas after separation returns to the photocatalytic fluidized bed reactor 0301 through the second feedback channel 0402 and participates in the chemical reaction process again. To prevent the reverse flow of the unreacted gas, a fourth throttle valve 0403 is provided on the second feedback channel 0402 to ensure the unidirectional flow of the gas, maintain the stability and efficient operation of the system, thereby improving the efficiency of the overall process and the resource utilization rate.

[0088] According to some embodiments, the separator 0401 includes a condenser, a gas separator or an adsorption device for separating the methanol from the unreacted mixed gas. Inside the separator 0401, through appropriate separation techniques, such as a condenser, a gas separator or an adsorption device, methanol is separated from the mixed gas. The condenser condenses gaseous methanol into a liquid form by lowering the temperature. Since methanol has a relatively high boiling point (about 64.7 °C), methanol can be condensed from the mixed gas by cooling, effectively removing most of the methanol, thereby reducing the load of subsequent treatment steps. The gas separator is used to further separate trace amounts of methanol and other impurity gases that are not completely captured by the condenser. Membrane separation technology, pressure swing adsorption (PSA) or other physical or chemical separation methods can also be selected according to the actual production scenario to provide higher separation accuracy, ensure that the purity of the finally output methanol meets the requirements, and recover as much unreacted carbon dioxide and hydrogen as possible so that they can re-enter the photocatalytic fluidized bed reactor 0301 for reaction.

[0089] According to some embodiments, the mixed gas (containing methanol and unreacted carbon dioxide and hydrogen) from the photocatalytic fluidized bed reactor 0301 is sent to a condenser. In the condenser, most of the methanol is condensed into a liquid form by lowering the temperature and then collected. The remaining gas continues to enter the gas separator. Specifically, membrane separation, PSA or other technologies can be used to further separate the residual methanol and other impurity gases to ensure the purity of the gas. If higher purity is required, the gas can be further purified through an adsorption device to remove any remaining trace amounts of methanol or other impurities. The separated pure methanol is collected and transported out as a product, while the unreacted mixed gas returns to the photocatalytic fluidized bed reactor 0301 through the second feedback channel 0402 to participate in the reaction process again to improve the raw material utilization rate.

[0090] According to some embodiments, through a multi-level separation design, combining a condenser, a gas separator, and an adsorption device, not only is the separation efficiency and purity of methanol improved, but also the effective recovery and reuse of unreacted gases are achieved, enhancing the resource utilization efficiency and economy of the entire system. Users can also flexibly select the condenser according to the actual scenario requirements, such as a flash tank, a packed distillation column, a tray distillation column, etc., which can reduce energy consumption and operating costs while achieving high-efficiency product separation.

[0091] To more intuitively demonstrate the advantages of this patent, experimental data is provided for verification:

[0092] Number <![CDATA[CO2 activation]]> Light source Methanol selectivity <![CDATA[CO2 conversion rate]]> Methanol yield 1 Yes Yes 80.9％ 32.5％ 0.2629 2 Yes No 68.7％ 23％ 0.1580 3 No Yes 56.4％ 5.4％ 0.3045 4 No No 54％ 2％ 0.0108

[0093] Note: The experimental results here conform to the control variable, and other conditions remain the same.

[0094] According to some embodiments, the design solution of the present invention can also be applied to the design of an artificial photosynthesis reaction system for enhancing catalytic performance. The system includes: a control system and the artificial photosynthesis reaction device described in any one of the above, which can achieve the hydrogenation of CO2 to methanol through a photocatalytic reaction under milder conditions, reducing the energy consumption of traditional high-temperature and high-pressure reactions, achieving the goal of carbon neutrality, and at the same time, the produced methanol can be used as a clean energy and chemical raw material.

[0095] According to some embodiments, the design solution of the present invention can activate carbon dioxide in a supercritical state by adding a pretreatment unit 01, which can reduce its chemical inertness, enabling the reaction to prepare methanol through a photocatalytic reaction under milder conditions, greatly improving the subsequent photocatalytic reaction rate, and reducing the energy consumption of traditional high-temperature and high-pressure reactions. Using CO2 as a raw material to prepare methanol, the produced methanol can be used as a clean energy and chemical raw material, helping to reduce the atmospheric CO2 concentration and achieve the goal of carbon neutrality.

[0096] According to some embodiments, the design solution of the present invention realizes the full and uniform mixing of the activated carbon dioxide and the hydrogen by adding the mixing and transmission unit, and ensures that the gas enters the reactor at a stable flow rate and a uniform pressure distribution, so that the mixed gas can be dispersed as evenly as possible in the reactor, improving the raw material utilization rate, and also enhancing the stability and efficiency of the entire process flow.

[0097] According to some embodiments, the design solution of the present invention realizes the effective regeneration and recycling of the photocatalyst by adding the photocatalytic regeneration unit, ensuring the efficient operation of the entire device, improving the utilization rate of the photocatalyst, and reducing the preparation cost.

[0098] According to some embodiments, the design solution of the present invention realizes the effective separation and recycling of the unreacted mixed gas by adding the separation unit, improves the resource utilization rate, reduces the waste of raw materials, and also ensures the efficient operation of the entire artificial photosynthesis reaction device.

[0099] It should be noted that for the foregoing method embodiments, for the sake of simple description, they are all expressed as a series of action combinations. However, those skilled in the art should know that this application is not limited by the described action sequence, because according to this application, certain steps can be performed in other sequences or simultaneously. Secondly, those skilled in the art should also know that the embodiments described in the specification are all preferred embodiments, and the actions and modules involved are not necessarily essential to this application.

[0100] In the above embodiments, the descriptions of the respective embodiments have their own emphases. For the parts not detailed in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0101] In several embodiments provided by the present application, it should be understood that the disclosed device can be implemented in other ways. For example, the device embodiments described above are only illustrative. For example, the division of units is only a logical function division. In actual implementation, there may be other division methods. For example, multiple units or components can be combined or integrated into another system, or some features can be ignored or not executed. Another point is that the displayed or discussed coupling or direct coupling or communication connection between each other can be through some service interfaces. The indirect coupling or communication connection of the device or unit can be in an electrical or other form.

[0102] The unit described as a separation component may or may not be physically separated. The component displayed as a unit may or may not be a physical unit, that is, it can be located in one place, or it can be distributed to multiple network units. Some or all of the units can be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0103] In addition, in each embodiment of the present application, the functional units can be integrated in a processing unit, or each unit can exist physically alone, or two or more units can be integrated in one unit.

[0104] In the above embodiments, the descriptions of the respective embodiments have their own emphases. For the parts not detailed in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0105] The above has specifically shown and described exemplary embodiments of the present application. It should be understood that the present application is not limited to the detailed structures, settings or implementation methods described herein; on the contrary, the present application is intended to cover various modifications and equivalent settings included within the spirit and scope of the appended claims.

Claims

1. An artificial photosynthesis reaction device with enhanced catalytic performance, characterized in that, For the preparation of methanol using carbon dioxide and hydrogen as raw materials, the artificial photosynthesis reaction device includes: a pretreatment unit, a mixing and transmission unit, a photocatalytic regeneration unit, and a separation unit. Among them, The pretreatment unit is used to activate the received carbon dioxide in a supercritical state and send the activated carbon dioxide into the mixing and transmission unit; The mixing and transmission unit receives hydrogen and the carbon dioxide activated by the pretreatment unit and mixes them in a predetermined ratio to obtain a mixed gas, and transmits the mixed gas to the photocatalytic regeneration unit; The photocatalytic regeneration unit receives the mixed gas from the mixing and transmission unit. The photocatalytic regeneration unit includes a light source for providing illumination for the chemical reaction. The photocatalytic regeneration unit is used for preheating and activating the photocatalyst and for the chemical reaction of the mixed gas to occur under the action of light and the photocatalyst, obtaining a mixture of methanol and the unreacted mixed gas, and sending the mixture into the separation unit; The separation unit separates the methanol and the unreacted mixed gas in the mixture and sends the unreacted mixed gas back into the photocatalytic regeneration unit.

2. The artificial photosynthesis reaction device according to claim 1, characterized in that The pretreatment unit includes a first raw material delivery channel, a first throttle valve, and a reaction kettle. Among them, The first raw material delivery channel is used to input the carbon dioxide into the reaction kettle and send the activated carbon dioxide into the mixing and transmission unit; The first throttle valve is arranged on the first raw material delivery channel to control the delivery amount of the carbon dioxide; The reaction kettle is used to activate the received carbon dioxide in a supercritical state and send the activated carbon dioxide into the mixing and transmission unit through the first raw material delivery channel.

3. The artificial photosynthesis reaction device according to claim 2, characterized in that, A constant temperature control system is arranged inside the reaction kettle to ensure that the temperature inside the reaction kettle is uniform and stable.

4. The artificial photosynthesis reaction device according to claim 2, characterized in that, The reaction kettle is made of high-temperature and high-pressure resistant materials, and the operating conditions of the reaction kettle are set to 35°C, 80 - 100 bar to ensure that the carbon dioxide is in a supercritical state.

5. The artificial photosynthesis reaction device according to claim 1, characterized in that, The mixing and transmission unit includes: a second raw material delivery channel, a second throttle valve, a third raw material delivery channel, a third throttle valve, and a gas mixer. Among them, The second raw material delivery channel is used to input the hydrogen into the gas mixer; The second throttle valve is arranged on the second raw material delivery channel to control the delivery amount of the hydrogen; The gas mixer is used for mixing the activated carbon dioxide and the hydrogen to obtain the mixed gas; The third raw material delivery channel is used to send the mixed gas into the mixing and transmission unit; The third throttle valve is arranged on the third raw material delivery channel to control the delivery amount of the mixed gas.

6. The artificial photosynthesis reaction device according to claim 1, wherein The photocatalytic regeneration unit further includes: a photocatalytic fluidized bed reactor and a regenerator. Among them, The regenerator includes a feed inlet and a riser. The photocatalyst is added into the regenerator through the feed inlet. After preheating and regeneration of the photocatalyst in the regenerator, the photocatalyst is sent into the fluidized bed reactor through the riser; The photocatalytic fluidized bed reactor receives the catalyst from the regenerator and the mixed gas from the mixing and transfer unit. In the photocatalytic fluidized bed reactor, the mixed gas undergoes a fluidized reaction under the action of the photocatalyst to obtain a mixture of the methanol and the unreacted mixed gas, and the mixture is sent to the separation unit; The photocatalytic fluidized bed reactor includes a first feedback channel, which is arranged at the bottom of the photocatalytic fluidized bed reactor to recover the deactivated photocatalyst after the reaction and reflux it to the regenerator.

7. The artificial photosynthesis reaction device according to claim 1, characterized in that, The separation unit includes a separator and a second feedback channel, The separator is used to separate the methanol and the unreacted mixed gas in the mixture and externally transport the methanol; The second feedback channel connects the separator and the photocatalytic fluidized bed reactor to send the unreacted mixed gas back to the photocatalytic fluidized bed reactor.

8. The artificial photosynthesis reaction device according to claim 7, characterized in that, A throttle valve is arranged on the second feedback channel to prevent the reflux of the unreacted mixed gas.

9. The artificial photosynthesis reaction device according to claim 7, wherein, The separator includes a condenser, a gas separator or an adsorption device for separating the methanol from the unreacted mixed gas.

10. An artificial photosynthesis reaction system with enhanced catalytic performance, characterized in that, The system includes a control system and the artificial photosynthesis reaction device according to any one of claims 1-9 above.

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