Carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system and method

Abstract

The invention discloses a carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system and method, and aims to improve biomass gasification hydrogen production efficiency, reduce generation of byproducts, reduce greenhouse gas emission and realize continuous and stable operation of the system. The system mainly comprises a biomass continuous feeding unit, an energetic waste batch feeding unit, a water vapor generating and conveying unit, a thermal conversion reactor, a dust removal unit, a plasma enhanced catalysis unit, a liquid product separation and collection unit and a hydrogen separation and storage unit. The plasma enhanced catalysis unit is a core part, and the synergistic effect of the plasma reactor and the multifunctional catalyst not only promotes the reforming reaction of biomass volatile matter and water vapor, but also can enhance hydrogen production through a carbon capture technology and reduce CO2 emission at the same time. The unit comprises two sets of plasma power supplies and reactors which alternately work, one set of plasma power supplies and reactors can perform reforming reaction while the other set of plasma power supplies and reactors can perform catalyst regeneration, and plasmas also have a strengthening effect on CO2 desorption, dry reforming and catalyst regeneration in a regeneration stage, so that continuous operation of the system is ensured. The device can be widely applied to efficient gasification hydrogen production of various biomass energy sources, meanwhile, various new energy sources can be flexibly used for power generation to supply power to the plasma reactor, energy conservation and emission reduction are achieved while the biomass energy source conversion efficiency is improved, and efficient cleaning treatment and resource utilization of solid waste are achieved.

Description

Technical Field

[0001] The present invention relates to the field of biomass energy chemical industry and hydrogen production technology, and in particular to a carbon capture conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system and method. Background Art

[0002] With the growing global demand for renewable energy and increasing concerns about greenhouse gas emissions, the development of efficient carbon capture, utilization and storage (CCUS) technologies and innovative energy conversion systems have become key to solving environmental problems and achieving sustainable development goals. Biomass is one of the most abundant renewable organic resources on earth. Its thermal conversion technologies, such as gasification and pyrolysis, can convert biomass into valuable chemicals and fuels, including hydrogen. However, there are some challenges in the traditional biomass thermal conversion process, such as low gasification efficiency, many by-products, low hydrogen purity, and large carbon emissions. In addition, energetic waste can simultaneously produce syngas and release heat during the thermal conversion process, 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 a variety of improvement schemes. For example, using catalysts to promote gasification reactions and increase hydrogen yields; using advanced separation technology to remove impurities in synthesis gas and improve hydrogen purity; and combining carbon capture technology to reduce greenhouse gas emissions. Although these methods have improved the effect of biomass gasification hydrogen production to a certain extent, it is still difficult to meet the requirements of industrial applications. In addition, plasma technology is used in many fields, including waste treatment and material synthesis, because it can provide high energy density, fast heating rate and good chemical activity. Introducing it into the biomass gasification process can effectively increase the gasification temperature and accelerate the reaction rate, thereby further enhancing the hydrogen production and quality, and can flexibly apply various new energy sources. However, how to rationally design the plasma system to ensure its effective combination with the gasification hydrogen production process and achieve efficient carbon capture is still a key issue that needs to be solved.

[0004] In summary, the development of a biomass and energetic waste gasification system and method that can efficiently and environmentally friendly produce high-purity hydrogen is of great significance to the development of clean energy. Based on this background, the present invention proposes an innovative solution, that is, by integrating carbon capture technology and plasma enhancement means, an efficient biomass and energetic waste gasification hydrogen production system is constructed, in order to achieve the purpose of increasing hydrogen yield and reducing environmental pollution. Summary of the invention

[0005] In response to the above-mentioned problems such as low gasification efficiency, large number of by-products, low hydrogen purity and large carbon emissions, the purpose of the present invention is to provide a biomass and energetic waste gasification system and method that can efficiently and environmentally friendly produce high-purity hydrogen and can flexibly apply various types of new energy supplies.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: On the one hand, the present invention provides a carbon capture conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system, including a biomass raw material 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 outer electrode (ground electrode), an inner electrode (high-voltage electrode), a catalyst bed, a thermal insulation sleeve, a condensing device, a liquid product collector, a gas detection and distribution device, a hydrogen separator and a hydrogen storage tank; 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 passed into the thermal conversion reactor, the gas outlet of the thermal conversion reactor is connected to the gas inlet of the cyclone dust collector, and the particle outlet of the dust collector is connected to the ash collector; The gas outlet of the cyclone dust collector is connected to the gas inlet of the plasma enhanced catalytic reactor, the gas outlet of the plasma enhanced catalytic reactor is connected to the gas inlet of the condensing device, and the liquid generated after the gas is condensed is collected by the liquid phase product collector; the gas outlet of the condensing device is connected to the gas detection and distribution device, and the gas detection and distribution device is respectively connected to the thermal conversion reactor and the hydrogen separator, and the generated hydrogen-rich gas enters the hydrogen storage tank for storage; The plasma enhanced catalytic reactor is connected to a plasma power source, which can catalyze the removal of solid particles from biomass pyrolysis volatiles and water vapor to perform a reforming reaction to generate hydrogen-rich gas, while reducing greenhouse gas emissions through carbon capture, and promoting dry reforming reactions to enhance hydrogen production during the catalyst regeneration stage. Two sets of plasma enhanced catalytic units are connected in parallel; The gas detection and distribution device is respectively connected to the thermal conversion reactor or the hydrogen separator and the hydrogen storage tank, and 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.

[0007] In some embodiments, the biomass raw material screw feeder can break up the biomass raw material and ensure continuous feeding into the thermal conversion reactor, and the energetic waste batch feeder can feed the energetic waste into the thermal conversion reactor in batches.

[0008] 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 back-end reactor.

[0009] In some embodiments, the plasma enhanced catalytic reactor is two sets of parallel dielectric barrier discharge plasma enhanced catalytic reactors, and the two systems operate alternately.

[0010] 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 water vapor (reforming mode). During this process, the plasma can promote the reforming reaction and catalyze the reforming and cracking of tar molecules into small molecule products on the one hand, and on the other hand, it can promote the adsorption of carbon dioxide by the multifunctional catalyst to enhance hydrogen production and reduce greenhouse gas emissions. After the catalyst is saturated with carbon dioxide adsorption, it is switched to the regeneration mode, and the carbon dioxide is desorbed under the assistance of plasma and dry reformed with the introduced methane gas 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.

[0011] 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 the middle area to promote hydrogen production and carbon capture conversion.

[0012] In some embodiments, the plasma-enhanced catalytic reactor is filled with a multifunctional catalyst that can simultaneously cooperate with plasma to catalyze the pyrolysis of biomass volatiles and steam reforming to produce hydrogen, the adsorption of carbon dioxide during the reaction, and the desorption of carbon dioxide from the catalyst during the regeneration stage and the dry reforming reaction.

[0013] In some embodiments, each of the individual longitudinal plasma reactors in the plasma enhanced catalytic reactor is coated with an insulating heat-insulating layer, which can ensure mutual insulation between each plasma reactor and maintain the temperature of the reaction gas therein to achieve energy saving.

[0014] In some embodiments, the plasma power supply can generate a plasma discharge region in the reforming reactor and control the discharge power of the reaction zone by controlling the applied voltage. The high voltage electrode and the ground electrode in each plasma reactor are connected to the positive and negative electrodes of the plasma power supply.

[0015] 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 converted to regeneration mode, methane gas is switched to dry reforming reaction with desorbed carbon dioxide to enhance hydrogen production.

[0016] In some embodiments, the intelligent control device is capable of controlling the feed rate of raw materials, gas flow rate, fluidized bed reaction residence time, reaction temperature, plasma reactor power and the alternating operation time of two sets of plasma enhanced catalytic reforming reactors.

[0017] Another aspect of the present application is to provide a method for producing hydrogen by thermal conversion of biomass and energetic waste by carbon capture conversion and plasma enhancement, using the above system, including the following steps: S1, after pre-treatment such as crushing and splitting, the biomass raw materials are transported to the thermal conversion reactor by the biomass raw material screw feeder, and the energetic waste is added into the thermal conversion reactor in batches by the energetic waste batch feeder, and water vapor is introduced at the same time; S2, the volatile components of the reaction products after dust removal by a cyclone dust collector and water vapor enter the plasma enhanced catalytic reactor in working state; S3, Carbon capture and plasma-enhanced catalytic hydrogen production from biomass and energetic waste volatiles and water vapor in a plasma-enhanced catalytic reactor under the action of a multifunctional catalyst bed and plasma discharge; S4, after the multifunctional catalyst bed is saturated with carbon dioxide adsorption, the reactor switches to regeneration mode, and carbon dioxide is desorbed under the assistance of plasma and dry reformed with the introduced methane gas to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass and energetic waste volatiles. The two sets of plasma-enhanced catalytic reactors are used alternately to ensure continuous operation of the system; S5, a small amount of macromolecular liquid products remaining in the volatile components after the catalytic reaction are cooled and condensed by a condensing device and separated and collected in a liquid product collector, a gas detection and distribution device detects the composition of the gas products and distributes the gas according to the hydrogen content of the gas products and feeds back a signal to control the plasma enhanced catalytic reactor to switch to a regeneration state, 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.

[0018] In some embodiments, in step S1, the temperature of the thermal conversion reactor is maintained at 650° C.-850° C., and the steam flow rate is 3-5 ml / h / g material.

[0019] In some embodiments, in steps S3 and S4, the multifunctional catalyst bed is filled with a multifunctional catalyst having catalytic reforming activity, carbon capture and conversion activity, and synergistic effect with plasma, wherein the multifunctional catalyst is one or more of 40-60 mesh particles, 0.5-1.0 mm diameter pellets, or monolithic catalysts, and the multifunctional catalyst comprises a carrier, a catalytically active component, a carbon dioxide capture agent, and a promoter, wherein the carrier 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, and the promoter is one or two of cerium and lanthanum, and the total content of the catalytically active component, the carbon dioxide capture agent, and the promoter is 1-40 wt%, based on the mass of the catalyst carrier.

[0020] 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. The carrier gas is cut off in the plasma enhanced catalytic reactor entering the regeneration stage, and 15% CH4 / N2 or 15% CH4 / Ar is introduced as the regeneration atmosphere to carry out dry reforming reaction with the desorbed carbon dioxide.

[0021] The present invention provides a carbon capture conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production method, which can not only enhance hydrogen production efficiency and reduce tar generation by catalytic reforming of biomass pyrolysis volatiles through the synergistic effect of plasma and catalyst, but also achieve greenhouse gas emission reduction and catalyst regeneration through the catalyst carbon capture conversion cycle, and at the same time can flexibly use various types of new energy to generate electricity to power the plasma reactor, thereby improving biomass energy conversion efficiency while saving energy and reducing emissions, and achieving efficient and clean treatment of solid waste and resource utilization.

[0022] Compared with the prior art, the carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system and method of the present invention has the following advantages: (1) Improve gasification efficiency and hydrogen purity: Through the synergistic effect of plasma and catalyst, the pyrolysis volatile matter of biomass is catalyzed and reformed, which can enhance the hydrogen production efficiency and reduce tar generation. At the same time, the hydrogen-rich synthesis gas produced in the reforming process can be separated to obtain high-purity hydrogen.

[0023] (2) Reduction of by-products: The system design can effectively reduce common by-products 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.

[0024] (3) Environmental benefits: Greenhouse gas emissions are reduced through carbon capture technology, and dry reforming reaction is used to enhance hydrogen production during the catalyst regeneration stage, thereby achieving the recycling of carbon dioxide and reducing the environmental burden.

[0025] (4) Flexible application of new energy: 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.

[0026] (5) Continuous operation capability: By setting up two sets of plasma-enhanced catalytic reforming units running 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.

[0027] (6) Application of multifunctional catalysts: The use of catalysts with multiple activities can not only improve the selectivity and efficiency of the reforming reaction, but also promote the adsorption and desorption of carbon dioxide, achieve self-regeneration of the catalyst, and reduce the cost of long-term operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 Schematic diagram of a carbon capture conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production system in an embodiment of the present application Figure 2 Schematic diagram of the structure of the plasma enhanced catalytic reactor in the embodiment of the present application: front view (top); top view (bottom) Figure 3 This is a flow chart of a method for producing hydrogen by thermal conversion of biomass and energetic waste by carbon capture conversion and plasma enhancement in an embodiment of the present application; Reference numerals: 1-Biomass raw material 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-Inner electrode (high voltage electrode); 13-Catalyst bed; 14-Thermal insulation cover; 15-Condensation device; 16-Liquid product collector; 17-Gas detection and distribution device; 18-Hydrogen separator; 19-Hydrogen storage tank. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0031] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0033] In the description of the embodiments of the present invention, it should be noted that if the terms "upper", "lower", "horizontal", "inner", etc. indicate an orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship in which the product of the invention is usually placed when in use, it is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. In addition, the terms "first", "second", etc. are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.

[0034] In addition, if the term "horizontal" appears, it does not mean that the component must be absolutely horizontal, but can be slightly tilted. For example, "horizontal" only means that its direction is more horizontal than "vertical", which does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0035] In the description of the embodiments of the present invention, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "set", "install", "connect", and "connect" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal connection of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0036] The present invention is further described in detail below in conjunction with the accompanying drawings: like Figure 1 As shown, the embodiment of the present application proposes a carbon capture conversion and plasma-enhanced biomass gasification hydrogen production system, including a biomass raw material 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 outer electrode (ground electrode) 11, an inner electrode (high-voltage electrode) 12, a catalyst bed 13, a thermal insulation sleeve 14, a condensing 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 biomass raw material screw feeder 1 can crush the biomass raw material and ensure continuous feeding to the thermal conversion reactor 5. The energetic waste batch feeder 2 can feed the energetic waste into the thermal conversion reactor 5 in batches. The plunger metering pump 3 and the steam generator 4 are connected to the thermal conversion reactor 5 to generate water vapor for use in the pyrolysis and subsequent reforming reaction stages and to control the water vapor flow rate. The thermal conversion reactor 5 is connected to a cyclone dust collector 7 and an ash collector 8 to separate and collect solid particles in the product gas phase flow. The cyclone dust collector 7 is connected to two sets of parallel plasma enhanced catalytic reactors 10. The pyrolysis volatiles of biomass and energetic waste enter the plasma enhanced catalytic reactor 10 for enhanced catalytic hydrogen production after particle separation. In this process, the plasma and the multifunctional catalyst bed 13 work synergistically to pyrolyze the volatiles. The two plasma power supplies 9 are respectively connected to two sets of plasma enhanced catalytic reforming reactors 10 for generating plasma in the discharge area between the outer electrode 11 and the inner electrode 12 and controlling the corresponding discharge power. The plasma enhanced catalytic reforming reactor 10 is connected to the condensing device 15 and the 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 components of the gas products 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. The hydrogen-poor gas enters the burner and is burned to supply heat energy to the aforementioned thermal conversion reactor 5.

[0037] 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.

[0038] In some specific embodiments, the shells of the thermal conversion reactor 5 and the plasma enhanced catalytic reactor 10 are filled with a thermal insulation layer, which acts as an insulating layer between the individual plasma reactors in the plasma enhanced catalytic reactor 10 to insulate the individual reactors from each other.

[0039] Preferably, the thermal insulation layer is ceramic fiber. Due to the excellent thermal insulation performance and extremely low heat capacity of ceramic fiber, the energy consumption and surface temperature of the equipment can be greatly reduced, and a significant energy-saving effect is achieved.

[0040] In some specific embodiments, a single dielectric barrier discharge plasma reactor in the plasma enhanced catalytic reactor 10 may be made of high temperature resistant quartz or corundum, and the outer electrode or ground electrode material may be made of stainless steel or copper.

[0041] In some specific embodiments, a temperature measuring device is installed in the thermal conversion reactor 5 and the plasma enhanced catalytic reactor 10 to monitor the temperature in the reactor and feed back to the intelligent controller 6 .

[0042] System electrical and control system description: This system uses a 380V power supply except for the plasma enhanced catalytic reforming unit, and is connected to the main power distribution cabinet through the intelligent control front to distribute to each power-consuming part of the system. The plasma enhanced catalytic reforming unit is powered by a separate 380V power supply, and is connected to the reactor to generate plasma through the plasma power supply. In order to facilitate the start and stop control of each device in the system and adjust the operating parameters, this test control is completed on the on-site control cabinet, which integrates the control of each system equipment and the numerical display of each instrument.

[0043] On the other hand, the present application embodiment provides a method for producing hydrogen by thermal conversion of biomass and energetic waste by carbon capture and conversion and plasma enhancement, using the above-mentioned carbon capture and conversion and plasma enhancement biomass and energetic waste thermal conversion hydrogen production system, such as Figure 3 As shown, the following steps are included: S1, after pre-treatment such as crushing and splitting, the biomass raw materials are transported to the thermal conversion reactor by the biomass raw material screw feeder, and the energetic waste is added into the thermal conversion reactor in batches by the energetic waste batch feeder, and water vapor is introduced at the same time; S2, the volatile components of the reaction products after dust removal by a cyclone dust collector and water vapor enter the plasma enhanced catalytic reactor in working state; S3, Carbon capture and plasma-enhanced catalytic hydrogen production from biomass and energetic waste volatiles and water vapor in a plasma-enhanced catalytic reactor under the action of a multifunctional catalyst bed and plasma discharge; S4, after the multifunctional catalyst bed is saturated with carbon dioxide adsorption, the reactor switches to regeneration mode, and carbon dioxide is desorbed under the assistance of plasma and dry reformed with the introduced methane gas to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass and energetic waste volatiles. The two sets of plasma-enhanced catalytic reactors are used alternately to ensure continuous operation of the system; S5, a small amount of macromolecular liquid products remaining in the volatile components after the catalytic reaction are cooled and condensed by a condensing device and separated and collected in a liquid product collector, a gas detection and distribution device detects the composition of the gas products and distributes the gas according to the hydrogen content of the gas products and feeds back a signal to control the plasma enhanced catalytic reactor to switch to a regeneration state, 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.

[0044] The present invention provides a carbon capture conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production method, which can not only enhance hydrogen production efficiency and reduce tar generation by catalytic reforming of biomass pyrolysis volatiles through the synergistic effect of plasma and catalyst, but also achieve greenhouse gas emission reduction and catalyst regeneration through the catalyst carbon capture conversion cycle, and at the same time can flexibly use various types of new energy to generate electricity to power the plasma reactor, thereby improving biomass energy conversion efficiency while saving energy and reducing emissions, and achieving efficient and clean treatment of solid waste and resource utilization.

[0045] The present invention is further described below through specific examples. Example

[0046] like Figure 1 As shown, the embodiment of the present application proposes a carbon capture conversion and plasma-enhanced biomass and energetic waste thermal conversion hydrogen production method, including a biomass raw material 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 outer electrode (ground electrode) 11, an inner electrode (high-voltage electrode) 12, a catalyst bed 13, a thermal insulation sleeve 14, a condensing 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 biomass raw material screw feeder 1 can crush the biomass raw material and ensure continuous feeding to the thermal conversion reactor 5. The energetic waste batch feeder 2 can feed the energetic waste into the thermal conversion reactor 5 in batches. The plunger metering pump 3 and the steam generator 4 are connected to the thermal conversion reactor 5 to generate water vapor for use in the pyrolysis and subsequent reforming reaction stages and to control the water vapor flow rate. The thermal conversion reactor 5 is connected to a cyclone dust collector 7 and an ash collector 8 to separate and collect solid particles in the product gas phase flow. The cyclone dust collector 7 is connected to two sets of parallel plasma enhanced catalytic reactors 10. The pyrolysis volatiles of biomass and energetic waste enter the plasma enhanced catalytic reactor 10 for enhanced catalytic hydrogen production after particle separation. In this process, the plasma and the multifunctional catalyst bed 13 act synergistically on the pyrolysis volatiles. The catalytic reforming and in-situ carbon capture are simultaneously performed to enhance hydrogen production. Two plasma power supplies 9 are respectively connected to two sets of plasma enhanced catalytic reactors 10 to generate plasma in the discharge area between the outer electrode 11 and the inner electrode 12 and control the corresponding discharge power. The plasma enhanced catalytic reforming reactor 10 is connected to the condensing device 15 and the 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 components of the gas products and distributes the gas according to the hydrogen content of the gas products and feedbacks 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. The hydrogen-poor gas enters the burner and is burned to supply heat energy to the aforementioned thermal conversion reactor 5.

[0047] 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.

[0048] 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 acts as an insulating layer between the individual plasma reactors in the plasma enhanced catalytic reactor 10 to insulate the individual reactors from each other.

[0049] In this embodiment, the heat insulation layer is ceramic fiber. Due to the excellent heat insulation performance and extremely low heat capacity of ceramic fiber, the energy consumption and surface temperature of the equipment can be greatly reduced, and a significant energy-saving effect is achieved.

[0050] In this embodiment, a single dielectric barrier discharge plasma reactor in the plasma enhanced catalytic reactor 10 can be made of high temperature resistant quartz, and the outer electrode or ground electrode material is made of stainless steel.

[0051] 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 in the reactor and feed back to the intelligent controller 6 .

[0052] In this embodiment, the temperature of the thermal conversion reactor 5 and the plasma enhanced catalytic reactor 10 is 650°C, and the steam flow rate is 3 ml / h / g 物料 .

[0053] In this embodiment, the multifunctional catalyst is selected as 40-60 mesh NiCaCe / Al2O3 particles, and the contents of Ni, Ca and Ce are 10%, 30% and 5% respectively based on the mass of the catalyst carrier.

[0054] 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. The carrier gas is cut off in the plasma enhanced catalytic reactor entering the regeneration stage, and 15% CH4 / Ar is introduced as the regeneration atmosphere to carry out dry reforming reaction with the desorbed carbon dioxide.

[0055] System electrical and control system description: This system uses a 380V power supply except for the plasma enhanced catalytic reforming unit, and is connected to the main power distribution cabinet through the intelligent control front to distribute to each power-consuming part of the system. The plasma enhanced catalytic reforming unit is powered by a separate 380V power supply, and is connected to the reactor to generate plasma through the plasma power supply. In order to facilitate the start and stop control of each device in the system and adjust the operating parameters, this test control is completed on the on-site control cabinet, which integrates the control of each system equipment and the numerical display of each instrument.

[0056] like Figure 3 As shown, a carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production method, using the above carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system, includes the following steps: S1, the granular biomass raw material with a moisture content of less than 15 wt% and a size of 60 mesh after pretreatment is crushed and split, and then transported to the thermal conversion reactor by a feeder for pyrolysis, and the energetic waste is fed into the thermal conversion reactor in batches by an energetic waste batch feeder, and water vapor is introduced; The main reactions occurring in the thermal conversion reactor 5 are: Pyrolysis reaction: biomass + energetic waste + H2O → CO + CO2 + H2 + CH4 + other hydrocarbons Water-gas shift reaction: C + H2O → CO + H2 CO + H2O → CO2 + H2 Methanation reaction: CO + 3H2 → CH4 + H2O CO2 + 4H2 → CH4 + 2H2O S2, the reaction products (mainly H2, CO, CH4, CO2 and a small amount of hydrocarbons) are treated by cyclone dust collector and then enter the working plasma enhanced catalytic reactor together with water vapor; S3, carbon capture and plasma-enhanced co-pyrolysis of energetic biomass waste volatiles and steam catalytic reforming to produce hydrogen under the synergistic effect of multifunctional catalyst bed (40-60 mesh NiCaCe / Al2O3 particles) and plasma discharge; The main reactions occurring in the plasma enhanced catalytic reactor 10 (reforming stage) are: H2O + e → H + OH + e Ar + e → Ar* + e Ar* + H2O → Ar + OH + H H + H → H2 CO + H2O → CO2 + H2 H2O + e → H2O- C + H2O → CO + H2 C + CO2 →2CO CH4 + H2O → CO + 3H2 CaO + CO2 → CaCO3 S4, after the multifunctional catalyst bed is saturated with carbon dioxide adsorption, the reactor switches to regeneration mode, and carbon dioxide is desorbed under the assistance of plasma and dry reformed with the introduced methane gas to enhance hydrogen production. At the same time, another set of equipment performs catalytic reforming of biomass and energetic waste volatiles. The two sets of plasma-enhanced catalytic reactors are used alternately to ensure continuous operation of the system; The main reactions occurring in the plasma enhanced catalytic reactor 10 (regeneration phase) are: CaCO3 → CaO + CO2 CO2 + CH4 → 2CO + 2H2 (under the synergistic effect of plasma and multifunctional catalyst) S5, a small amount of macromolecular liquid products remaining in the volatile components after the catalytic reaction are cooled and condensed by a condensing device and separated and collected in a liquid product collector, a gas detection and distribution device detects the composition of the gas products and distributes the gas according to the hydrogen content of the gas products and feeds back a signal to control the plasma enhanced catalytic reactor to switch to a regeneration state, 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.

[0057] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system, characterized in that: It comprises a biomass raw material 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 outer electrode (ground electrode) (11), an inner electrode (high voltage electrode) (12), a catalyst bed (13), a thermal insulation sleeve (14), a condensing 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 flows 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), and the particle 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 condensing device (15). The liquid generated after the gas is condensed is collected by the liquid product collector (16); the gas outlet of the condensing device (15) is connected to the gas detection and distribution device (17), and the gas detection and distribution device (17) is respectively connected to the thermal conversion reactor (5) and the hydrogen separator (18), and 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), and is capable of catalyzing the removal of solid particles from biomass pyrolysis volatiles and water vapor to undergo a reforming reaction to generate hydrogen-rich gas, while reducing greenhouse gas emissions through carbon capture, and promoting dry reforming reactions during the catalyst regeneration phase to enhance hydrogen production. Two sets of plasma enhanced catalytic units are connected in parallel; The gas detection and distribution device (17) is respectively connected to the thermal conversion reactor (5) or the hydrogen separator (18) and the hydrogen storage tank (19), and is capable of detecting the gas product components and distributing 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. A carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 1, characterized in that: The biomass raw material screw feeder (1) is capable of crushing the biomass raw material and ensuring continuous feeding to the thermal conversion reactor (5), and the energetic waste batch feeder (2) is capable of feeding the energetic waste into the thermal conversion reactor (5) in batches and intervals; The thermal conversion reactor (5) is connected to a carrier gas supply, and the carrier gas supply can control the gas flow rate and ensure the pyrolysis atmosphere of the rear reactor; the plasma enhanced catalytic reactor (10) is two sets of parallel dielectric barrier discharge plasma enhanced catalytic reactors, and the two systems operate alternately.

3. A carbon capture 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 performs carbon capture and plasma enhanced catalytic reforming of biomass volatiles and water vapor (reforming mode). During this process, the plasma can promote the reforming reaction and catalyze the reforming and cracking of tar molecules into small molecular 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 is switched to the regeneration mode, and carbon dioxide is desorbed under the assistance of plasma and a dry reforming reaction is carried out with the introduced methane gas to enhance hydrogen production. At the same time, the other set of equipment performs catalytic reforming of biomass volatiles to ensure continuous operation of the system.

4. A carbon capture 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 composed of a plurality of longitudinal tubular plasma reactors connected in parallel, each plasma reactor having an outer electrode (ground electrode) (11) and an inner electrode (high voltage electrode) (12), wherein plasma discharge can be generated in the middle region thereof to promote hydrogen production and carbon capture conversion. The plasma enhanced catalytic reactor (10) is filled with a multifunctional catalyst (13), which can simultaneously cooperate with plasma to catalyze the pyrolysis of biomass volatiles and steam reforming to produce hydrogen, the adsorption of carbon dioxide during the reaction process, and the desorption of carbon dioxide from the catalyst during the regeneration stage and the dry reforming reaction.

5. The carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 2, characterized in that: Each of the individual longitudinal plasma reactors in the plasma enhanced catalytic reactor (10) is coated with an insulating heat-insulating layer (14), and the insulating heat-insulating layer (14) can ensure that each plasma reactor is insulated from each other and can maintain the temperature of the reaction gas therein to achieve 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, and the high-voltage electrode and the ground electrode in each plasma reactor are connected to the positive and negative electrodes of the plasma power supply.

6. A carbon capture 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 the regeneration mode, the methane gas is switched to a dry reforming reaction with desorbed carbon dioxide to enhance hydrogen production.

7. The carbon capture conversion and plasma enhanced biomass and energetic waste thermal conversion hydrogen production system according to claim 1, characterized in that: The entire system is connected to an intelligent controller (6), which is capable of controlling the raw material feed rate, gas flow rate, fluidized bed reaction residence time, reaction temperature, plasma reactor power, and the alternating operation time of the two sets of plasma enhanced catalytic reactors (10).

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

9. A method for producing hydrogen by thermal conversion of biomass and energetic waste with carbon capture conversion and plasma enhancement according to claim 8, characterized in that: In step S1, the temperature of the thermal conversion reactor (5) is maintained at 650°C-850°C, and the steam flow rate is 3-5 ml / h / g 物料 ; In the steps S3 and S4, the multifunctional catalyst bed (13) is filled with a multifunctional catalyst having catalytic reforming activity, carbon capture and conversion activity, and synergistic effect with plasma, wherein the multifunctional catalyst is one or more of 40-60 mesh particles, 0.5-1.0 mm diameter pellets, or monolithic catalysts, and the multifunctional catalyst comprises a carrier, a catalytically active component, a carbon dioxide capture agent, and a co-catalyst, wherein the carrier 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, and the co-catalyst is one or two of cerium and lanthanum, and the total content of the catalytically active component, the carbon dioxide capture agent, and the co-catalyst is 1-40 wt%, based on the mass of the catalyst carrier.

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

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