A system and method for hydrogen production by carbon capture conversion and plasma enhanced thermal conversion of biomass and energetic waste

Abstract

The application discloses a kind of carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system and method, to improve biomass gasification hydrogen production efficiency, reduce by-product generation, reduce greenhouse gas emissions, and realize the continuous and stable operation of system. The system mainly includes biomass continuous feeding unit and energetic waste batch feeding unit, water vapor generation and transportation unit, thermal conversion reactor, dust removal unit, plasma enhanced catalysis unit, liquid product separation and collection unit and hydrogen separation and storage unit. Plasma enhanced catalysis unit is the core part, the synergistic effect of plasma reactor and multifunctional catalyst not only promotes the reforming reaction of biomass volatile and water vapor, but also can strengthen hydrogen production and reduce CO2 emission through carbon capture technology. This unit contains two sets of plasma power supply and reactor working alternately, one set of reforming reaction can carry out catalyst regeneration, plasma has the same strengthening effect on CO2 desorption and dry reforming in regeneration stage and catalyst regeneration, which ensures the continuous operation of the system. The application can be widely applied to efficient gasification hydrogen production of various biomass energy, and can also flexibly use various new energy power generation to supply power for plasma reactor, which can improve the conversion efficiency of biomass energy, save energy and reduce emissions, realize efficient and clean treatment of solid waste and resource utilization.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biomass energy and chemical industry and hydrogen production, and particularly relates to a system and method for hydrogen production by thermal conversion of biomass and energetic waste with carbon capture and plasma enhancement. BACKGROUND

[0002] With the increasing demand for renewable energy and growing concern about greenhouse gas emissions, developing efficient carbon capture, utilization and storage (CCUS) technologies and innovative energy conversion systems has become a key to solving environmental problems and achieving sustainable development goals. As one of the most abundant renewable organic resources on Earth, biomass can be converted into valuable chemicals and fuels, including hydrogen, through thermal conversion technologies such as gasification and pyrolysis. However, there are some challenges in traditional biomass thermal conversion processes, such as low gasification efficiency, multiple by-products, low hydrogen purity, and high carbon emissions. In addition, energetic waste can produce syngas and release heat during thermal conversion, which also has potential energy value, but their effective utilization is usually limited by pollution control and technical feasibility.

[0003] In recent years, in order to overcome the above challenges, researchers have proposed various improvement schemes. For example, catalysts are used to promote gasification reactions, improve hydrogen production rates, advanced separation technologies are used to remove impurities in syngas, and hydrogen purity is improved, and carbon capture technologies are combined to reduce greenhouse gas emissions. Although these methods have improved the effect of biomass gasification for hydrogen production to some extent, they still cannot meet the requirements of industrial application. In addition, plasma technology is applied in many fields due to its high energy density, fast heating rate and good chemical activity, including waste treatment, material synthesis, etc. Its introduction into the biomass gasification process can effectively increase the gasification temperature, accelerate the reaction rate, and further enhance the hydrogen production and quality, and can be more flexible in the application of various new energy. However, how to reasonably design the plasma system to ensure its effective combination with the gasification hydrogen production process, while achieving efficient carbon capture, is still a key problem to be solved.

[0004] In summary, developing a biomass and energetic waste gasification system and method for producing high-purity hydrogen efficiently and environmentally is of great significance to the development of clean energy. Based on this background, the present application proposes an innovative solution, that is, by integrating carbon capture technology and plasma enhancement means, a high-efficiency biomass and energetic waste gasification hydrogen production system is constructed to improve hydrogen production rate and reduce environmental pollution. SUMMARY

[0005] In view of the problems of low gasification efficiency, many by-products, low hydrogen purity and large carbon emissions, the purpose of this invention is to provide a biomass and energy-containing waste gasification system and method that can efficiently and environmentally produce high-purity hydrogen and flexibly apply various new energy sources.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] This invention proposes a biomass and energetic waste thermal conversion hydrogen production system with carbon capture and conversion and plasma enhancement, including a biomass feed screw feeder, an energetic waste batch feeder, a plunger metering pump, a steam generator, a thermal conversion reactor, an intelligent controller, a cyclone dust collector, an ash collector, a plasma power supply, a plasma-enhanced catalytic reactor, an external electrode (ground electrode), an internal electrode (high-voltage electrode), a catalyst bed, a thermal insulation sleeve, a condensation device, a liquid product collector, a gas detection and distribution device, a hydrogen separator, and a hydrogen storage tank;

[0008] The outlet of the biomass raw material screw feeder and the outlet of the energetic waste batch feeder are connected to the thermal conversion reactor. The plunger metering pump is connected to the steam generator and fed into the thermal conversion reactor. The gas outlet of the thermal conversion reactor is connected to the gas inlet of the cyclone dust collector. The particulate matter outlet of the dust collector is connected to the ash collector.

[0009] The gas outlet of the cyclone dust collector is connected to the gas inlet of the plasma-enhanced catalytic reactor, and the gas outlet of the plasma-enhanced catalytic reactor is connected to the gas inlet of the condenser. The liquid generated after the gas is condensed is collected by the liquid phase product collector. The gas outlet of the condenser is connected to the gas detection and distribution device, which is connected to the thermal conversion reactor and the hydrogen separator respectively. The generated hydrogen-rich gas enters the hydrogen storage tank for storage.

[0010] The plasma-enhanced catalytic reactor is connected to a plasma power source, which can catalyze the reforming reaction of biomass pyrolysis volatiles and water vapor after solid particles are removed to generate hydrogen-rich gas. At the same time, it reduces greenhouse gas emissions through carbon capture and promotes dry reforming reaction to enhance hydrogen production during the catalyst regeneration stage. Two sets of plasma-enhanced catalytic units are connected in parallel.

[0011] The gas detection and distribution device is connected to the thermal conversion reactor or hydrogen separator and hydrogen storage tank respectively. It can detect the gas product components and distribute the gas according to the hydrogen content of the gas product. The hydrogen-rich gas enters the subsequent hydrogen separation and storage, and the hydrogen-poor gas enters the burner for combustion to supply heat energy to the aforementioned thermal conversion reactor.

[0012] In some embodiments, the biomass feed screw feeder can crush biomass feedstock and ensure continuous feeding to the thermal conversion reactor, and the energetic waste batch feeder can add energetic waste into the thermal conversion reactor in batches at intervals.

[0013] In some embodiments, the thermal conversion reactor is connected to a carrier gas supply, which can control the gas flow rate and ensure the pyrolysis atmosphere of the downstream reactor.

[0014] In some embodiments, the plasma-enhanced catalytic reactor is two parallel dielectric barrier discharge plasma-enhanced catalytic reactors, with the two systems operating alternately.

[0015] In some embodiments, during the alternating operation of the plasma-enhanced catalytic reactor, one set performs carbon capture and plasma-enhanced catalytic reforming of biomass volatiles and steam (reforming mode). In this process, the plasma can promote the reforming reaction and catalyze the reforming and cracking of tar molecules into smaller molecule products. On the other hand, it can promote the adsorption of carbon dioxide by the multifunctional catalyst, thereby enhancing hydrogen production and reducing greenhouse gas emissions. After the catalyst is saturated with carbon dioxide adsorption, it switches to regeneration mode. Under plasma assistance, carbon dioxide is desorbed and reacted with the introduced methane gas in a dry reforming reaction to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass volatiles to ensure continuous operation of the system.

[0016] In some embodiments, the plasma-enhanced catalytic reactor is composed of multiple longitudinal tubular plasma reactors connected in parallel. Each plasma reactor has an outer electrode (ground electrode) and an inner electrode (high-voltage electrode), and plasma discharge can be generated in its middle region to promote hydrogen production and carbon capture and conversion.

[0017] In some embodiments, the plasma-enhanced catalytic reactor is filled with a multifunctional catalyst that can simultaneously synergistically catalyze the pyrolysis volatiles of biomass and the reforming of steam to produce hydrogen, the adsorption of carbon dioxide during the reaction, and the desorption of carbon dioxide from the catalyst and dry reforming reaction during the regeneration stage.

[0018] In some embodiments, each individual longitudinal plasma reactor in the plasma-enhanced catalytic reactor is covered with an insulating and heat-insulating layer. The insulating and heat-insulating layer can ensure that each plasma reactor is mutually insulated and can maintain the temperature of the reaction gas therein, thereby achieving an energy-saving effect.

[0019] In some embodiments, the plasma power source is capable of generating a plasma discharge region in the reforming reactor and controlling the discharge power of the reaction region by controlling the applied voltage. The high-voltage electrode and the ground electrode in each plasma reactor are connected to the positive and negative terminals of the plasma power source.

[0020] In some embodiments, the plasma-enhanced catalytic reforming reactor is connected to a methane gas supply. In the reactor reforming mode, the system atmosphere is nitrogen. When the reactor is switched to regeneration mode, the atmosphere is changed to methane gas and desorbed carbon dioxide for dry reforming reaction to enhance hydrogen production.

[0021] In some embodiments, the intelligent control device can control the feed rate, gas flow rate, fluidized bed reaction residence time, reaction temperature, plasma reactor power, and the alternating operation time of the two plasma-enhanced catalytic reforming reactors.

[0022] Another aspect of this application proposes a method for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement, utilizing the aforementioned system and including the following steps:

[0023] S1, after pretreatment such as crushing and splitting, the biomass raw material is conveyed to the thermal conversion reactor by the biomass raw material screw feeder. The energetic waste is added to the thermal conversion reactor in batches by the energetic waste batch feeder, and steam is introduced at the same time.

[0024] S2, the volatiles of the product after the reaction is treated by a cyclone dust collector and then enter the plasma-enhanced catalytic reactor in operation along with water vapor;

[0025] S3, a plasma-enhanced catalytic reactor for the catalytic production of hydrogen from biomass and energetic waste volatiles and steam under the action of a multifunctional catalyst bed and plasma discharge.

[0026] S4. After the carbon dioxide adsorption in the multifunctional catalyst bed is saturated, the reactor is switched to regeneration mode. Under plasma assistance, carbon dioxide is desorbed and reacted with the introduced methane gas in a dry reforming reaction to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass and volatile components of energetic waste. The two sets of plasma-enhanced catalytic reactors are used alternately to ensure continuous operation of the system.

[0027] S5, after the catalytic reaction, the remaining small amount of large molecular liquid phase products in the volatiles are cooled and condensed by the condenser and separated and collected in the liquid phase product collector. The gas detection and distribution device detects the gas product components and distributes the gas according to the hydrogen content of the gas product and feeds back the signal to control the plasma-enhanced catalytic reactor to switch to the regeneration state. The hydrogen-rich gas enters the subsequent hydrogen separation and storage, and the hydrogen-poor gas enters the burner to burn and supply heat energy to the aforementioned thermal conversion reactor.

[0028] In some embodiments, in step S1, the temperature of the thermal conversion reactor is maintained at 650℃-850℃, and the steam flow rate is 3-5 ml / h / g material.

[0029] In some embodiments, in steps S3 and S4, the multifunctional catalyst bed is filled with a multifunctional catalyst possessing catalytic reforming activity, carbon capture and conversion activity, and synergistic effect with plasma. The multifunctional catalyst is one or more of the following: 40-60 mesh particles, 0.5-1.0 mm diameter spheres, or monolithic catalysts. The multifunctional catalyst consists of a support, a catalytically active component, a carbon dioxide capture agent, and a co-catalyst. The support is one or more of activated alumina, molecular sieve, and silicon carbide. The catalytically active component is one or more of nickel, cobalt, iron, and manganese. The carbon dioxide capture agent is one or more of calcium oxide, magnesium oxide, and hydrotalcite. The co-catalyst is one or two of cerium and lanthanum. Based on the mass of the catalyst support, the total content of the catalytically active component, carbon dioxide capture agent, and co-catalyst is 1-40 wt%.

[0030] In some embodiments, in steps S3 and S4, the carrier gas in the thermal conversion reactor and the plasma-enhanced catalytic reactor in the catalytic reforming stage is high-purity nitrogen or argon. When entering the regeneration stage, the carrier gas in the plasma-enhanced catalytic reactor is cut off, and 15% CH4 / N2 or 15% CH4 / Ar is introduced as a regeneration atmosphere to carry out a dry reforming reaction with the desorbed carbon dioxide.

[0031] This invention provides a method for hydrogen production from biomass and energy-containing waste through carbon capture and conversion and plasma enhancement. This method not only enhances hydrogen production efficiency and reduces tar generation by catalytically reforming the volatiles of biomass pyrolysis through the synergistic effect of plasma and catalyst, but also achieves greenhouse gas emission reduction and catalyst regeneration through catalyst carbon capture and conversion cycle. At the same time, it can flexibly utilize various new energy power generation methods to power the plasma reactor, thereby improving biomass energy conversion efficiency while saving energy and reducing emissions, and realizing efficient and clean treatment and resource utilization of solid waste.

[0032] Compared with existing technologies, the present invention provides a system and method for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement, which has the following advantages:

[0033] (1) Improve gasification efficiency and hydrogen purity: By catalyzing the reforming of biomass pyrolysis volatiles through the synergistic effect of plasma and catalyst, hydrogen production efficiency can be enhanced and tar generation can be reduced. At the same time, the hydrogen-rich syngas produced in the reforming process can be separated to obtain high-purity hydrogen.

[0034] (2) Reduce byproducts: The system is designed to effectively reduce common byproducts in traditional gasification processes, such as tar and other large molecular liquid products. These substances will be further processed or converted into useful products in this system.

[0035] (3) Environmental benefits: Greenhouse gas emissions are reduced through carbon capture technology, and hydrogen production is enhanced by dry reforming reaction in the catalyst regeneration stage, thereby realizing the recycling of carbon dioxide and reducing the environmental burden.

[0036] (4) Flexible application of new energy sources: The system can flexibly use various new energy sources to power the plasma reactor, which not only helps to reduce operating costs, but also improves the energy adaptability and sustainability of the system.

[0037] (5) Continuous operation capability: By setting up two sets of plasma-enhanced catalytic reforming units operating in parallel, one set of equipment can perform carbon capture and reforming while the other set of equipment performs catalyst regeneration, ensuring the continuous operation and stability of the system.

[0038] (6) Application of multifunctional catalysts: Using catalysts with multiple activities can not only improve the selectivity and efficiency of reforming reactions, but also promote the adsorption and desorption of carbon dioxide, realize the self-regeneration of catalysts, and reduce the cost of long-term operation. Attached Figure Description

[0039] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0040] Figure 1 This is a schematic diagram of a carbon capture and conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system according to an embodiment of this application.

[0041] Figure 2 The following are schematic diagrams of the plasma-enhanced catalytic reactor structure in the embodiments of this application: front view (top); top view (bottom).

[0042] Figure 3 This is a flowchart of a method for producing hydrogen from biomass and energetic waste through carbon capture and conversion and plasma enhancement, as described in an embodiment of this application.

[0043] Figure label:

[0044] 1-Biomass feed screw feeder; 2-Energetic waste batch feeder; 3-Plunger metering pump; 4-Steam generator; 5-Thermal conversion reactor; 6-Intelligent controller; 7-Cyclone dust collector; 8-Ash collector; 9-Plasma power supply; 10-Plasma-enhanced catalytic reactor; 11-External electrode (ground electrode); 12-Internal electrode (high-voltage electrode); 13-Catalyst bed; 14-Insulation sleeve; 15-Condensation device; 16-Liquid phase product collector; 17-Gas detection and distribution device; 18-Hydrogen separator; 19-Hydrogen storage tank. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0046] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0047] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0048] In the description of the embodiments of the present invention, it should be noted that if terms such as "upper," "lower," "horizontal," or "inner" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of the invention is in use, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention. Furthermore, terms such as "first" and "second" are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0049] Furthermore, the use of the term "horizontal" does not imply that the component must be absolutely horizontal, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0050] In the description of the embodiments of the present invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in the present invention according to the specific circumstances.

[0051] The present invention will now be described in further detail with reference to the accompanying drawings:

[0052] like Figure 1 As shown, one embodiment of this application proposes a biomass gasification hydrogen production system with carbon capture and conversion and plasma enhancement, including a biomass feed screw feeder 1, an energetic waste batch feeder 2, a plunger metering pump 3, a steam generator 4, a thermal conversion reactor 5, an intelligent controller 6, a cyclone dust collector 7, an ash collector 8, a plasma power supply 9, a plasma-enhanced catalytic reactor 10, an external electrode (ground electrode) 11, an internal electrode (high-voltage electrode) 12, a catalyst bed 13, a thermal insulation sleeve 14, a condensation device 15, a liquid product collector 16, a gas detection and distribution device 17, a hydrogen separator 18, and a hydrogen storage tank 19.

[0053] The biomass feed screw feeder 1 can crush biomass feedstock and ensure continuous feeding to the thermal conversion reactor 5. The energetic waste batch feeder 2 can add energetic waste into the thermal conversion reactor 5 in batches at intervals. The plunger metering pump 3 and the steam generator 4 are connected inside the thermal conversion reactor 5 to generate steam for pyrolysis and subsequent reforming reaction sections and to control the steam flow rate. After the thermal conversion reactor 5, a cyclone dust collector 7 and an ash collector 8 are connected to separate and collect solid particles in the product gas phase flow. After the cyclone dust collector 7, two sets of parallel plasma-enhanced catalytic reactors 10 are connected. After particulate matter separation, the pyrolysis volatiles of biomass and energetic waste enter the plasma-enhanced catalytic reactor 10 for enhanced catalytic hydrogen production. In this process, the plasma and the multifunctional catalyst bed 13 work synergistically to enhance the pyrolysis volatilization. The catalytic reforming process simultaneously enhances hydrogen production through in-situ carbon capture. Two plasma power supplies 9 are connected to two sets of plasma-enhanced catalytic reforming reactors 10 to generate plasma in the discharge region between the outer electrode 11 and the inner electrode 12 and control the corresponding discharge power. The plasma-enhanced catalytic reforming reactor 10 is then connected to a condenser 15 and a liquid product collector 16. The condensable liquid products in the reaction products can be condensed and collected in the liquid product collector 16. The gas detection and distribution device 17 detects the gas product components and distributes the gas according to the hydrogen content of the gas product, and feeds back the signal to control the plasma-enhanced catalytic reforming reactor 10 to switch to the regeneration state. The hydrogen-rich gas enters the subsequent hydrogen separation and is stored in the hydrogen storage tank 19, while the hydrogen-poor gas enters the burner for combustion to supply heat energy to the aforementioned thermal conversion reactor 5.

[0054] In some specific embodiments, the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 are made of 304 stainless steel, which is resistant to high temperature and corrosion.

[0055] In some specific embodiments, the shells of the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 are filled with a heat insulation layer, which also acts as an insulation layer between the individual plasma reactors in the plasma-enhanced catalytic reactor 10, thus insulating the individual reactors from each other.

[0056] Preferably, the insulation layer is made of ceramic fiber. Due to the excellent thermal insulation performance and extremely low heat capacity of ceramic fiber, it can greatly reduce the energy consumption and surface temperature of the equipment, and has a significant energy-saving effect.

[0057] In some specific embodiments, the individual dielectric barrier discharge plasma reactor within the plasma-enhanced catalytic reactor 10 may be made of high-temperature resistant quartz or corundum, and the external electrode or ground electrode material may be stainless steel or copper.

[0058] In some specific embodiments, temperature measuring devices are installed in the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 to monitor the temperature inside the reactor and feed it back to the intelligent controller 6.

[0059] System Electrical and Control System Description: Except for the plasma-enhanced catalytic reforming unit, this system is powered by a single 380V power supply, which is connected to the main power distribution cabinet via an intelligent control system to distribute power to all components of the system. The plasma-enhanced catalytic reforming unit is powered by a separate 380V power supply and generates plasma via a plasma power supply connected to the reactor. To facilitate the start-up and shutdown control of each system device and the adjustment of operating parameters, all control in this experiment is completed on the field control cabinet. The control cabinet integrates the control functions of each system device and the numerical display functions of each instrument.

[0060] Another aspect of this application proposes a method for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement, utilizing the aforementioned carbon capture and conversion and plasma enhancement system for hydrogen production from biomass and energetic waste, such as... Figure 3 As shown, it includes the following steps:

[0061] S1, after pretreatment such as crushing and splitting, the biomass raw material is conveyed to the thermal conversion reactor by the biomass raw material screw feeder. The energetic waste is added to the thermal conversion reactor in batches by the energetic waste batch feeder, and steam is introduced at the same time.

[0062] S2, the volatiles of the product after the reaction is treated by a cyclone dust collector and then enter the plasma-enhanced catalytic reactor in operation along with water vapor;

[0063] S3, a plasma-enhanced catalytic reactor for the catalytic production of hydrogen from biomass and energetic waste volatiles and steam under the action of a multifunctional catalyst bed and plasma discharge.

[0064] S4. After the carbon dioxide adsorption in the multifunctional catalyst bed is saturated, the reactor is switched to regeneration mode. Under plasma assistance, carbon dioxide is desorbed and reacted with the introduced methane gas in a dry reforming reaction to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass and volatile components of energetic waste. The two sets of plasma-enhanced catalytic reactors are used alternately to ensure continuous operation of the system.

[0065] S5, after the catalytic reaction, the remaining small amount of large molecular liquid phase products in the volatiles are cooled and condensed by the condenser and separated and collected in the liquid phase product collector. The gas detection and distribution device detects the gas product components and distributes the gas according to the hydrogen content of the gas product and feeds back the signal to control the plasma-enhanced catalytic reactor to switch to the regeneration state. The hydrogen-rich gas enters the subsequent hydrogen separation and storage, and the hydrogen-poor gas enters the burner to burn and supply heat energy to the aforementioned thermal conversion reactor.

[0066] This invention provides a method for hydrogen production from biomass and energy-containing waste through carbon capture and conversion and plasma enhancement. This method not only enhances hydrogen production efficiency and reduces tar generation by catalytically reforming the volatiles of biomass pyrolysis through the synergistic effect of plasma and catalyst, but also achieves greenhouse gas emission reduction and catalyst regeneration through catalyst carbon capture and conversion cycle. At the same time, it can flexibly utilize various new energy power generation methods to power the plasma reactor, thereby improving biomass energy conversion efficiency while saving energy and reducing emissions, and realizing efficient and clean treatment and resource utilization of solid waste.

[0067] The present invention will be further illustrated below through specific embodiments. Example

[0068] like Figure 1 As shown, one embodiment of this application proposes a method for producing hydrogen from biomass and energetic waste through carbon capture and conversion and plasma enhancement, including a biomass feed screw feeder 1, an energetic waste batch feeder 2, a plunger metering pump 3, a steam generator 4, a thermal conversion reactor 5, an intelligent controller 6, a cyclone dust collector 7, an ash collector 8, a plasma power supply 9, a plasma-enhanced catalytic reactor 10, an external electrode (ground electrode) 11, an internal electrode (high-voltage electrode) 12, a catalyst bed 13, a thermal insulation sleeve 14, a condensation device 15, a liquid product collector 16, a gas detection and distribution device 17, a hydrogen separator 18, and a hydrogen storage tank 19.

[0069] The biomass feed screw feeder 1 can crush biomass feedstock and ensure continuous feeding to the thermal conversion reactor 5. The energetic waste batch feeder 2 can add energetic waste into the thermal conversion reactor 5 in batches at intervals. The plunger metering pump 3 and the steam generator 4 are connected inside the thermal conversion reactor 5 to generate steam for use in the pyrolysis and subsequent reforming reaction sections and to control the steam flow rate. After the thermal conversion reactor 5, a cyclone dust collector 7 and an ash collector 8 are connected to separate and collect solid particles in the product gas phase flow. After the cyclone dust collector 7, two sets of parallel plasma-enhanced catalytic reactors 10 are connected. After particulate matter separation, the pyrolysis volatiles of biomass and energetic waste enter the plasma-enhanced catalytic reactor 10 for enhanced catalytic hydrogen production. In this process, the plasma and the multifunctional catalyst bed 13 work synergistically to enhance the pyrolysis volatiles. The plasma-enhanced catalytic reforming process simultaneously enhances hydrogen production through in-situ carbon capture. Two plasma power supplies 9 are connected to two sets of plasma-enhanced catalytic reactors 10 to generate plasma in the discharge region between the outer electrode 11 and the inner electrode 12 and control the corresponding discharge power. The plasma-enhanced catalytic reforming reactor 10 is then connected to a condenser 15 and a liquid product collector 16. The condensable liquid products in the reaction products can be condensed and collected in the liquid product collector 16. The gas detection and distribution device 17 detects the gas product components and distributes the gas according to the hydrogen content of the gas products, and feeds back the signal to control the plasma-enhanced catalytic reactor 10 to switch to the regeneration state. The hydrogen-rich gas enters the subsequent hydrogen separation and is stored in the hydrogen storage tank 19, while the hydrogen-poor gas enters the burner for combustion to supply heat energy to the aforementioned thermal conversion reactor 5.

[0070] In this embodiment, the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 are made of 304 stainless steel, which is resistant to high temperature and corrosion.

[0071] In this embodiment, the shells of the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 are filled with a heat insulation layer, which also acts as an insulation layer between the individual plasma reactors in the plasma-enhanced catalytic reactor 10, thus insulating the individual reactors from each other.

[0072] In this embodiment, the insulation layer is made of ceramic fiber. Due to the excellent thermal insulation performance and extremely low heat capacity of ceramic fiber, it can greatly reduce the energy consumption and surface temperature of the equipment, and has a significant energy-saving effect.

[0073] In this embodiment, the single dielectric barrier discharge plasma reactor within the plasma-enhanced catalytic reactor 10 may be made of high-temperature resistant quartz, and the external electrode or ground electrode material may be made of stainless steel.

[0074] In this embodiment, temperature measuring devices are installed in the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 to monitor the temperature inside the reactor and feed it back to the intelligent controller 6.

[0075] In this embodiment, the temperature of the thermal conversion reactor 5 and the plasma-enhanced catalytic reactor 10 is 650°C, and the water vapor flow rate is 3 ml / h / g. 物料 .

[0076] In this embodiment, the multifunctional catalyst is selected from 40-60 mesh NiCaCe / Al2O3 particles, with the contents of Ni, Ca and Ce being 10%, 30% and 5% respectively, based on the mass of the catalyst support.

[0077] In this embodiment, the carrier gas in the fluidized bed reactor and the plasma-enhanced catalytic reactor in the catalytic reforming stage is high-purity argon. When the plasma-enhanced catalytic reactor enters the regeneration stage, the carrier gas is cut off, and 15% CH4 / Ar is introduced as a regeneration atmosphere to carry out a dry reforming reaction with the desorbed carbon dioxide.

[0078] System Electrical and Control System Description: Except for the plasma-enhanced catalytic reforming unit, this system is powered by a single 380V power supply, which is connected to the main power distribution cabinet via an intelligent control system to distribute power to all components of the system. The plasma-enhanced catalytic reforming unit is powered by a separate 380V power supply and generates plasma via a plasma power supply connected to the reactor. To facilitate the start-up and shutdown control of each system device and the adjustment of operating parameters, all control in this experiment is completed on the field control cabinet. The control cabinet integrates the control functions of each system device and the numerical display functions of each instrument.

[0079] like Figure 3 As shown, a method for producing hydrogen from biomass and energetic waste through carbon capture and conversion and plasma enhancement, utilizing the aforementioned system for producing hydrogen from biomass and energetic waste through carbon capture and conversion and plasma enhancement, includes the following steps:

[0080] S1, after pretreatment, is a granular biomass raw material with a moisture content of less than 15 wt% and a size of 60 mesh. After pretreatment such as crushing and splitting, it is fed into the thermal conversion reactor by the feeder for pyrolysis. Energetic waste is added into the thermal conversion reactor in batches by the energetic waste batch feeder and steam is introduced.

[0081] The main reactions occurring in thermal conversion reactor 5 are:

[0082] Pyrolysis reaction: Biomass + Energy-containing waste + H2O → CO + CO2 + H2 + CH4 + Other hydrocarbons

[0083] Water-gas conversion reaction: C + H2O → CO + H2

[0084] CO + H2O → CO2 + H2

[0085] Methanation reaction: CO + 3H2 → CH4 + H2O

[0086] CO2 + 4H2 → CH4 + 2H2O

[0087] S2, the reaction products (mainly H2, CO, CH4, CO2 and a small amount of hydrocarbons) are treated by a cyclone dust collector and then enter the plasma-enhanced catalytic reactor in operation along with water vapor;

[0088] S3, a process for producing hydrogen from biomass energetic waste through co-pyrolysis of volatiles and steam catalytic reforming under the synergistic effect of a multifunctional catalyst bed (40-60 mesh NiCaCe / Al2O3 particles) and plasma discharge, involving carbon capture and plasma-enhanced process.

[0089] The main reactions occurring in plasma-enhanced catalytic reactor 10 (reforming stage) are:

[0090] H₂O + e → H + OH + e

[0091] Ar + e → Ar* + e

[0092] Ar* + H2O → Ar + OH + H

[0093] H + H → H2

[0094] CO + H2O → CO2 + H2

[0095] H₂O + e → H₂O-

[0096] C + H₂O → CO + H₂

[0097] C + CO2 → 2CO

[0098] CH4 + H2O → CO + 3H2

[0099] CaO + CO2 → CaCO3

[0100] S4. After the carbon dioxide adsorption in the multifunctional catalyst bed is saturated, the reactor is switched to regeneration mode. Under plasma assistance, carbon dioxide is desorbed and reacted with the introduced methane gas in a dry reforming reaction to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass and volatile components of energetic waste. The two sets of plasma-enhanced catalytic reactors are used alternately to ensure continuous operation of the system.

[0101] The main reactions occurring in plasma-enhanced catalytic reactor 10 (regeneration stage) are as follows:

[0102] CaCO3 → CaO + CO2

[0103] CO2 + CH4 → 2CO + 2H2 (under the synergistic effect of plasma and multifunctional catalyst)

[0104] S5, after the catalytic reaction, the remaining small amount of large molecular liquid phase products in the volatiles are cooled and condensed by the condenser and separated and collected in the liquid phase product collector. The gas detection and distribution device detects the gas product components and distributes the gas according to the hydrogen content of the gas product and feeds back the signal to control the plasma-enhanced catalytic reactor to switch to the regeneration state. The hydrogen-rich gas enters the subsequent hydrogen separation and storage, and the hydrogen-poor gas enters the burner to burn and supply heat energy to the aforementioned thermal conversion reactor.

[0105] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A system for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement, characterized in that, It includes a biomass feed screw feeder (1), an energetic waste batch feeder (2), a plunger metering pump (3), a steam generator (4), a thermal conversion reactor (5), an intelligent controller (6), a cyclone dust collector (7), an ash collector (8), a plasma power supply (9), a plasma-enhanced catalytic reactor (10), an external electrode (ground electrode) (11), an internal electrode (high-voltage electrode) (12), a catalyst bed (13), a thermal insulation sleeve (14), a condensation device (15), a liquid product collector (16), a gas detection and distribution device (17), a hydrogen separator (18), and a hydrogen storage tank (19). The outlet of the biomass raw material screw feeder (1) and the outlet of the energetic waste batch feeder (2) are connected to the thermal conversion reactor (5). The plunger metering pump (3) is connected to the steam generator (4) and fed into the thermal conversion reactor (5). The gas outlet of the thermal conversion reactor (5) is connected to the gas inlet of the cyclone dust collector (7). The particulate matter outlet of the dust collector (7) is connected to the ash collector (8). The gas outlet of the cyclone dust collector (7) is connected to the gas inlet of the plasma-enhanced catalytic reactor (10), and the gas outlet of the plasma-enhanced catalytic reactor (10) is connected to the gas inlet of the condenser (15). The liquid generated after the gas is condensed is collected by the liquid phase product collector (16). The gas outlet of the condenser (15) is connected to the gas detection and distribution device (17), which is connected to the thermal conversion reactor (5) and the hydrogen separator (18) respectively. The generated hydrogen-rich gas enters the hydrogen storage tank (19) for storage. The plasma-enhanced catalytic reactor (10) is connected to a plasma power source (9), which can catalyze the pyrolysis volatiles and water vapor after removing solid particles from biomass to undergo a reforming reaction to generate hydrogen-rich gas. At the same time, it reduces greenhouse gas emissions through carbon capture and promotes dry reforming reaction to enhance hydrogen production during the catalyst regeneration stage. The two plasma-enhanced catalytic units are connected in parallel. The gas detection and distribution device (17) is connected to the thermal conversion reactor (5) or the hydrogen separator (18) and the hydrogen storage tank (19) respectively. It can detect the gas product components and distribute the gas according to the hydrogen content of the gas product. The hydrogen-rich gas enters the subsequent hydrogen separation and storage, and the hydrogen-poor gas enters the burner for combustion to supply heat energy to the aforementioned thermal conversion reactor (5).

2. The system for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement according to claim 1, characterized in that, The biomass feed screw feeder (1) can crush biomass feed and ensure continuous feeding to the thermal conversion reactor (5), and the energetic waste batch feeder (2) can add energetic waste into the thermal conversion reactor (5) in batches at intervals. The thermal conversion reactor (5) is connected to a carrier gas supply, which can control the gas flow rate and ensure the pyrolysis atmosphere of the downstream reactor; the plasma-enhanced catalytic reactor (10) consists of two parallel dielectric barrier discharge plasma-enhanced catalytic reactors, and the two systems operate alternately.

3. The carbon capture and conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 2, characterized in that, During the alternating operation of the plasma-enhanced catalytic reactor (10), one set of equipment performs carbon capture and plasma-enhanced catalytic reforming of biomass volatiles and water vapor (reforming mode). In this process, the plasma can promote the reforming reaction and catalyze the reforming and cracking of tar molecules into small molecule products. On the other hand, it can promote the adsorption of carbon dioxide by the multifunctional catalyst, thereby enhancing hydrogen production and reducing greenhouse gas emissions. After the catalyst is saturated with carbon dioxide adsorption, it switches to regeneration mode. Under the assistance of plasma, carbon dioxide is desorbed and reacted with the introduced methane gas in a dry reforming reaction to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass volatiles to ensure continuous operation of the system.

4. The carbon capture and conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 2, characterized in that, The plasma-enhanced catalytic reactor (10) consists of multiple longitudinal tubular plasma reactors connected in parallel. Each plasma reactor has an outer electrode (ground electrode) (11) and an inner electrode (high-voltage electrode) (12). Plasma discharge can be generated in the middle region to promote hydrogen production and carbon capture and conversion. The plasma-enhanced catalytic reactor (10) is filled with a multifunctional catalyst (13), which can simultaneously synergistically catalyze the pyrolysis volatiles of biomass and the reforming of water vapor to produce hydrogen, the adsorption of carbon dioxide during the reaction process, and the desorption of carbon dioxide from the catalyst and dry reforming reaction during the regeneration stage.

5. A carbon capture and conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 2, characterized in that, Each longitudinal plasma reactor in the plasma-enhanced catalytic reactor (10) is covered with an insulating heat insulation layer (14). The insulating heat insulation layer (14) can ensure that each plasma reactor is mutually insulated and can maintain the temperature of the reaction gas in it, thus achieving energy saving. The plasma power supply (9) can generate a plasma discharge region in the plasma-enhanced catalytic reactor (10) and control the discharge power of the reaction region by controlling the applied voltage. The high-voltage electrode and the ground electrode in each plasma reactor are connected to the positive and negative terminals of the plasma power supply.

6. A carbon capture and conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 2, characterized in that, The plasma-enhanced catalytic reactor (10) is connected to a methane gas supply. In the reactor reforming mode, the system atmosphere is nitrogen. When the reactor is switched to regeneration mode, the methane gas is switched to dry reforming reaction with desorbed carbon dioxide to enhance hydrogen production.

7. The system for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement according to claim 1, characterized in that, The entire system is connected to an intelligent controller (6), which can control the feed rate, gas flow rate, fluidized bed reaction residence time, reaction temperature, plasma reactor power, and the alternating operation time of the two plasma-enhanced catalytic reactors (10).

8. A method for hydrogen production from biomass and energetic waste through carbon capture and conversion and plasma enhancement, characterized in that, A hydrogen production system for biomass and energetic waste thermal conversion using carbon capture and conversion and plasma enhancement as described in any one of claims 1 to 7 includes the following steps: S1, after pretreatment such as crushing and splitting, the biomass raw material is transported to the thermal conversion reactor (5) by the biomass raw material screw feeder (1), and the energetic waste is added into the thermal conversion reactor (5) in batches by the energetic waste batch feeder (2), while water vapor is introduced at the same time; S2, the volatiles of the product after the reaction are treated by the cyclone dust collector (7) and water vapor enter the plasma-enhanced catalytic reactor (10) in working condition. S3, In the plasma-enhanced catalytic reactor (10), carbon capture and plasma-enhanced catalytic hydrogen production from biomass and energetic waste volatiles and water vapor are carried out under the action of a multifunctional catalyst bed (13) and plasma discharge; S4. After the carbon dioxide adsorption in the multifunctional catalyst bed (13) is saturated, the reactor is switched to regeneration mode. The carbon dioxide is desorbed under plasma assistance and reacted with the introduced methane gas in a dry reforming reaction to enhance hydrogen production. At the same time, another set of equipment is used for catalytic reforming of biomass and volatile components of energetic waste. The two sets of plasma-enhanced catalytic reactors (10) are used alternately to ensure continuous operation of the system. S5, after the catalytic reaction, the remaining small amount of macromolecular liquid phase products in the volatiles are cooled and condensed by the condenser (15) and separated and collected in the liquid phase product collector (16). The gas detection and distribution device (17) detects the gas product components and distributes the gas according to the hydrogen content of the gas product and feeds back the signal to control the plasma enhanced catalytic reactor (10) to switch to the regeneration state. The hydrogen-rich gas enters the subsequent hydrogen separation and storage, and the hydrogen-poor gas enters the burner to burn and supply heat energy to the aforementioned thermal conversion reactor (5).

9. A method for producing hydrogen from biomass and energetic waste through carbon capture and conversion and plasma enhancement, as described in claim 8, is characterized in that... In step S1, the temperature of the thermal conversion reactor (5) is maintained at 650℃-850℃, and the steam flow rate is 3-5 ml / h / g. 物料 ; In steps S3 and S4, the multifunctional catalyst bed (13) is filled with a multifunctional catalyst that has catalytic reforming activity, carbon capture and conversion activity and synergistic effect with plasma. The multifunctional catalyst is one or more of the following: 40-60 mesh particles, 0.5-1.0 mm diameter spheres or monolithic catalyst. The multifunctional catalyst is composed of a support, catalytic active components, carbon dioxide capture agent and co-catalyst. The support is one or more of the following: activated alumina, molecular sieve, silicon carbide. The catalytic active components are one or more of the following: nickel, cobalt, iron, manganese. The carbon dioxide capture agent is one or more of the following: calcium oxide, magnesium oxide, hydrotalcite. The co-catalyst is one or two of the following: cerium, lanthanum. The total content of the catalytic active components, carbon dioxide capture agent and co-catalyst is 1-40 wt% based on the mass of the catalyst support.

10. A method for producing hydrogen from biomass and energetic waste through carbon capture and conversion and plasma enhancement, as described in claim 8, characterized in that, In steps S3 and S4, the carrier gas in the thermal conversion reactor (5) and the plasma-enhanced catalytic reactor (10) in the catalytic stage is high-purity nitrogen or argon. When the plasma-enhanced catalytic reactor (10) enters the regeneration stage, the carrier gas is cut off, and at the same time, 15% CH4 / N2 or 15% CH4 / Ar is introduced as a regeneration atmosphere to carry out a dry reforming reaction with the desorbed carbon dioxide.

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