Carbon-containing material pyrolysis method and system in plasma splitting water hydrogen production environment

Abstract

The invention relates to the technical field of carbon-containing material pyrolysis, and discloses a carbon-containing material pyrolysis method and system in a plasma splitting water hydrogen production environment, and the method comprises the following steps: pyrolyzing a carbon-containing material and a high-temperature hydrogen-rich gas in a pyrolysis device to obtain a first pyrolysis product; gas-phase components are introduced into a coupling system composed of a shaft furnace and a plasma device to be subjected to multi-stage coupling treatment, and carbon-containing particles are used for carrying out convective heat exchange on reaction gas to obtain carbon-containing dust and hydrogen-rich synthesis gas; the high-temperature carbon-containing dust is treated with ammonia water, sensible heat of the high-temperature carbon-containing dust is recycled, and ammonia-containing steam is generated; the hydrogen-rich synthesis gas is returned to the first step, and the ammonia-containing steam and the hydrogen-rich synthesis gas are mixed and introduced into the plasma device. According to the invention, the coke production processes of different types of carbon-containing materials are integrated, various carbon-containing materials such as low-tar bituminous coal, high-moisture lignite, oil-rich coal, biomass, organic wastes and oil shale can be treated, and the coke production cost of the various carbon-containing materials is reduced through uniform process flow and equipment configuration.

Description

A method and system for pyrolysis of carbonaceous materials in a plasma-based water splitting hydrogen production environment. Technical Field

[0001] This invention relates to the field of carbon-containing material pyrolysis technology, specifically to a method and system for pyrolysis of carbon-containing materials in a plasma-cracking water hydrogen production environment. Background Technology

[0002] With the transformation of energy structure and increasingly stringent environmental protection requirements, the efficient and clean utilization of carbon-containing materials has become an important research direction in the current energy and chemical industry. Carbon-containing material pyrolysis technology, as an important thermochemical conversion technology, can convert carbon-containing raw materials such as coal and biomass into gaseous, liquid, and solid products, and has broad application prospects in hydrogen production and chemical raw material production.

[0003] Currently, hydrogen production technology through the pyrolysis of carbonaceous materials has received widespread attention and research. Chinese patent CN117819477A discloses a system for producing hydrogen from coal pyrolysis gas via plasma cracking and steam reforming, combining coal pyrolysis with plasma cracking to achieve efficient utilization of wind and solar power and heat recovery and reuse. Chinese patent CN118255323A discloses a method for the synergistic plasma preparation of battery-grade hydrogen from organic solid waste, obtaining hydrogen-rich syngas through plasma cracking and reforming of pyrolyzed oil and gas, establishing a new hydrogen production model with synergistic energy and grade. Chinese patent CN114044490B proposes a device for producing hydrogen-rich gas based on dual-fluidized bed pyrolysis gas conversion, employing a high-temperature tar steam catalytic reforming process, solving the problems of sensible heat waste and low hydrogen content in pyrolysis gas.

[0004] However, existing technologies have the following shortcomings: First, different types of carbonaceous materials (such as low-tar bituminous coal, high-moisture lignite, high-tar bituminous coal, biomass, etc.) have significant differences in their physicochemical properties, requiring different pyrolysis process parameters and equipment configurations for processing, lacking a unified process method and equipment system. Second, existing technologies often design specialized processing techniques for specific types of carbonaceous materials, resulting in low equipment utilization, high production costs, and difficulty in achieving flexible switching and synergistic processing of multiple raw materials. Third, the comprehensive utilization of byproducts generated in traditional pyrolysis processes, such as ammonia water and carbonaceous dust, is not high, and energy recovery efficiency needs to be improved. Finally, the adaptability of existing processes is limited, making it difficult to meet the actual needs of diversified raw materials and flexible processes in industrial production. Summary of the Invention

[0005] This invention addresses the technical problem in existing technologies where different types of carbon-containing materials require different coking processes, resulting in a lack of a unified process method, low equipment utilization, high production costs, and limited process adaptability. It provides a method and system for the pyrolysis of carbon-containing materials in a plasma-cracking water-to-hydrogen environment. The specific technical solution is as follows: A method for the pyrolysis of carbon-containing materials in a plasma-cracking water-to-hydrogen environment includes the following steps: mixing carbon-containing materials with high-temperature hydrogen-rich gas in a pyrolysis device and performing agitated pyrolysis to obtain a first pyrolysis product; selecting... Selectively, the gaseous components of the first pyrolysis product are fed into a coupled system consisting of a vertical shaft furnace and a plasma device for multi-stage coupled processing. The carbon-containing particulate material in the vertical shaft furnace is used to perform convective heat exchange on the reaction gas to obtain carbon-containing dust and hydrogen-rich syngas. The ammonia water generated during the process is used to treat the high-temperature carbon-containing dust, recover its sensible heat and generate ammonia-containing vapor. At least a portion of the hydrogen-rich syngas is returned to step one as a source of high-temperature hydrogen-rich gas, and the ammonia-containing vapor is mixed with a portion of the hydrogen-rich syngas and then fed into the plasma device for reforming, realizing the recycling of hydrogen and oxygen.

[0006] Furthermore, in step one, the carbon-containing materials are low-tar bituminous coal and high-moisture lignite. The first pyrolysis product is separated into a first suspended first pyrolysis material and a first non-suspended first pyrolysis material through gas-solid separation. The first suspended first pyrolysis material includes: water vapor, hydrogen-rich fuel gas, tar gas, light hydrocarbon gas and carbon powder. The first non-suspended first pyrolysis material includes semi-coke and residue. The hydrogen-rich fuel gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

[0007] Preferably, in step two, the carbon-containing particulate material is particulate coal, and the multi-stage coupled processing specifically includes: firstly, the first suspended pyrolysis material is fed into a plasma device for hydrogen production and cracking to obtain hydrogen-rich fuel gas again; then, the hydrogen-rich fuel gas is fed into a vertical shaft furnace to undergo convective pyrolysis with the particulate coal to obtain suspended carbon powder and the first hydrogen-rich syngas, which includes water vapor, hydrogen, carbon monoxide and light hydrocarbon gases.

[0008] Preferably, in step three, the treatment of the high-temperature carbon-containing dust using ammonia water generated during the process specifically involves: heating the carbon powder to 1100°C, and indirectly exchanging heat between the ammonia water from the evaporative cooling device and the high-temperature carbon powder in the evaporative cooling device to generate ammonia-containing vapor.

[0009] Preferably, in step four, the ammonia-containing vapor is mixed with a portion of the first hydrogen-rich syngas and then introduced into a plasma device for reforming. Specifically, the ammonia-containing vapor is mixed with the first hydrogen-rich syngas and introduced into a plasma device to undergo a cracking and reforming reaction, generating hydrogen-rich gas after hydrogenation. The hydrogen-rich gas is then introduced into a gas holder to be heated and returned to step S1 to become high-temperature hydrogen-rich gas.

[0010] Preferably, in step one, the carbon-containing material is high-tar bituminous coal or high-tar lignite, and the first pyrolysis product is separated into a second suspended first pyrolysis material and a second non-suspended first pyrolysis material through gas-solid separation; the second suspended first pyrolysis material includes: water vapor, hydrogen-rich fuel gas, tar gas, light hydrocarbon gas and carbon powder, and the second non-suspended first pyrolysis material includes semi-coke and residue, and the hydrogen-rich fuel gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

[0011] Preferably, in step two, the carbon-containing particulate material is particulate coal, and the multi-stage coupled processing specifically includes: firstly, the second-stage suspended first pyrolysis material is introduced into the medium-temperature section of the vertical shaft furnace and pyrolyzed with the lump coal in the medium-temperature section to obtain the second-stage suspended second pyrolysis material; the second-stage suspended second pyrolysis material is introduced into a plasma device for water splitting and wet reforming reaction to obtain the second-stage hydrogen-rich syngas; finally, the second-stage hydrogen-rich syngas is introduced into the high-temperature section of the vertical shaft furnace and pyrolyzed with the particulate coal in the high-temperature section to obtain suspended carbon powder and the third-stage hydrogen-rich syngas; both the second-stage and third-stage hydrogen-rich syngas contain water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0012] Preferably, in step one, the carbon-containing materials are low-tar bituminous coal and high-moisture lignite. The first pyrolysis product is separated into a fourth suspended first pyrolysis material and a fourth non-suspended first pyrolysis material through gas-solid separation. The fourth suspended first pyrolysis material includes: water vapor, hydrogen-rich fuel gas, tar gas, light hydrocarbon gas and carbon powder. The fourth non-suspended first pyrolysis material includes semi-coke and residue. The hydrogen-rich fuel gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

[0013] Preferably, in step two, the carbon-containing particulate material is low-ash coal, low-ash lump coal, and biomass particles. The multi-stage coupling process specifically includes: first, the fourth-path suspended first pyrolysis material is fed into a plasma device for hydrogen production and cracking to obtain hydrogen-rich fuel gas; then, the hydrogen-rich fuel gas is fed into a vertical shaft furnace and convectively pyrolyzed with the carbon-containing particulate material to obtain suspended carbon powder and the fourth-path hydrogen-rich syngas, which includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0014] Preferably, in step three, the treatment of carbon-containing dust at high temperature using ammonia water generated during the process includes passing ammonia water and carbon powder into a steam activation device to perform steam activation treatment on the carbon powder to obtain activated carbon or activated coke.

[0015] Preferably, in step one, the carbon-containing material is biomass powder and wood vinegar, and the first pyrolysis product is separated into a fifth suspended first pyrolysis material and a fifth non-suspended first pyrolysis material through gas-solid separation; the fifth suspended first pyrolysis material includes: water vapor, combustible gas, tar gas and biochar powder, the fifth non-suspended first pyrolysis material includes biochar, and the combustible gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

[0016] Preferably, in step two, the carbon-containing particle material is biomass particles, and the multi-stage coupling treatment specifically includes: first, the fifth-path suspended first pyrolysis material is introduced into the medium-temperature section of the vertical shaft furnace to undergo pyrolysis with the biomass particles in the medium-temperature section to obtain the fifth-path suspended second pyrolysis material; the fifth-path suspended second pyrolysis material is introduced into a plasma device for water splitting and wet reforming reactions to obtain combustible gas again; finally, the combustible gas is introduced into the high-temperature section of the vertical shaft furnace to undergo high-temperature pyrolysis with the biomass particles in the high-temperature section to obtain suspended biochar powder and the fifth-path hydrogen-rich syngas; the fifth-path hydrogen-rich syngas includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0017] A system for pyrolysis of carbonaceous materials, comprising: a pyrolysis unit including a rotary kiln and a fluidized bed; a vertical shaft furnace having a 650°C intermediate temperature section and a 950°C high temperature section sequentially formed from top to bottom; a plasma device for cracking water through a high-temperature plasma jet to induce a wet reforming reaction; a gas holder for storing gases; an evaporative cooling device for cooling and condensing ammonia-containing vapors; an activation furnace for steam activation treatment; a screw discharge device with steam-protected coke quenching; and an electromagnetic induction heating device for heating the materials.

[0018] As can be seen from the above technical solution, the present invention has the following beneficial effects: Compared with the prior art, the present invention integrates the coking processes of different types of carbon-containing materials, significantly improving the adaptability of the same coking process, and can process a variety of carbon-containing materials such as low-tar bituminous coal, high-moisture lignite, oil-rich coal, biomass, organic waste, and oil shale; through a unified process flow and equipment configuration, the coking cost of various carbon-containing materials is effectively reduced, and the technical effect of one process producing multiple products is achieved. Attached Figure Description

[0019] Figure 1 is a schematic diagram of the system used in the pyrolysis of low-tar bituminous coal and high-moisture lignite containing carbonaceous materials in the pyrolysis unit; Figure 2 is a schematic diagram of the system used in the pyrolysis of low-ash briquettes, low-ash lump coal and biomass pellets containing carbonaceous granular materials in the vertical furnace.

[0020] In the diagram: 1. Pyrolysis unit; 11. Rotary kiln; 12. Fluidized bed; 2. Vertical shaft furnace; 3. Plasma unit; 4. Gas holder; 5. Evaporation and cooling unit; 6. Activation furnace; 7. Spiral discharge unit; 8. Electromagnetic induction heating unit. Detailed Implementation

[0021] 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. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] In the description of the embodiments of the present invention, it should be noted that the terms "inner", "outer", "upper", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship in which the product of the invention is usually placed when 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. Therefore, they should not be construed as limiting the present invention.

[0023] As shown in Figures 1 and 2, this invention provides a method for pyrolysis of carbon-containing materials in a plasma-cracking water hydrogen production environment. This method achieves multi-stage processing through a coupling system between the plasma device 3 and the vertical furnace 2, processing various carbon-containing materials and carbon-containing particulate materials, and using ammonia water for heat recovery to achieve the recycling of hydrogen and oxygen. The arrows in the figures indicate the direction of material flow. In Figure 1, the carbon-containing material placed in pyrolysis unit 1 is low-tar bituminous coal or high-moisture lignite, and the carbon-containing granular material in vertical furnace 2 is granular coal, or the carbon-containing material is low-tar bituminous coal or high-moisture low-tar lignite, and the carbon-containing granular material is briquettes; in Figure 2, the carbon-containing material is high-tar bituminous coal or high-tar lignite, and the carbon-containing granular material is lump coal placed in the medium-temperature section of vertical furnace 2 and granular coal placed in the high-temperature section of vertical furnace 2, or the carbon-containing material is biomass powder and wood vinegar, and the carbon-containing granular material is biomass pellets, or the carbon-containing material is biomass powder, organic waste and wood vinegar, and the carbon-containing granular material is a mixture of organic waste and biomass pellets, or the carbon-containing material is oil shale powder, and the carbon-containing granular material is oil shale pellets; secondly, the carbon-containing material is low-tar bituminous coal or high-moisture lignite, and the carbon-containing granular material is a mixture of low-ash briquettes, low-ash lump coal and biomass pellets.

[0024] Step 1: The carbon-containing material is mixed with high-temperature hydrogen-rich gas in pyrolysis device 1 and subjected to agitation and pyrolysis to obtain the first pyrolysis product. Pyrolysis device 1 includes a rotary kiln 11 and a fluidized bed 12. The carbon-containing material is fed into the rotary kiln 11 and the fluidized bed 12 respectively, and the rotary kiln 11 and the fluidized bed 12 are heated to 950°C by an electromagnetic induction heating device 8. The carbon-containing material enters the rotary kiln 11 and the fluidized bed 12 through a feeding mechanism and is mixed with the high-temperature hydrogen-rich gas. The high-temperature hydrogen-rich gas is heated to 950°C by the electromagnetic induction heating device 8 and then enters the rotary kiln 11 and the fluidized bed 12. The carbon-containing material undergoes rapid pyrolysis in a hydrogen-rich environment. The finer fraction is rapidly pyrolyzed by the hot hydrogen-rich gas, releasing a large amount of water vapor, hydrogen, carbon monoxide, light hydrocarbon gases, tar gas, and a small amount of other component gases, forming the first pyrolysis product in suspension. The coarser fraction is in an unsuspended state. The suspended and unsuspended fractions are obtained through gas-solid separation.

[0025] The pyrolysis process varies depending on the type of carbon-containing material. When the carbon-containing material is low-tar bituminous coal and high-moisture lignite, or low-tar bituminous coal and high-moisture low-tar lignite, the temperature of the rotary kiln 11 and fluidized bed 12 is set to 950℃. The first pyrolysis product is separated into a first suspended first pyrolysis material and a first non-suspended first pyrolysis material through gas-solid separation. The first suspended first pyrolysis material includes steam, hydrogen-rich fuel gas, tar gas, and carbon powder. The first non-suspended first pyrolysis material includes semi-coke and residue. The hydrogen-rich fuel gas includes hydrogen, carbon monoxide, and a small amount of carbon dioxide.

[0026] When the carbonaceous material is high-tar bituminous coal or high-tar lignite, the temperature of rotary kiln 11 and fluidized bed 12 is adjusted to 650℃. The first pyrolysis product is separated into a second suspended first pyrolysis material and a second non-suspended first pyrolysis material through gas-solid separation. The second suspended first pyrolysis material includes steam, hydrogen-rich fuel gas, tar gas, and carbon powder, while the second non-suspended first pyrolysis material includes semi-coke and residue.

[0027] When the carbon-containing material is biomass powder and wood vinegar, or biomass powder, organic waste and wood vinegar, or oil shale powder, the first pyrolysis product is separated into a fifth suspended first pyrolysis material and a fifth non-suspended first pyrolysis material through gas-solid separation. The fifth suspended first pyrolysis material includes water vapor, combustible gas, tar gas, and biochar powder; the fifth non-suspended first pyrolysis material includes biochar; and the combustible gas includes hydrogen, carbon monoxide, and a small amount of carbon dioxide.

[0028] Step Two: Depending on the type of carbon-containing material, the gaseous components of the first pyrolysis product are selectively introduced into a multi-stage coupled system consisting of a vertical shaft furnace 2 and a plasma device 3 for processing. The carbon-containing particles in the vertical shaft furnace 2 are used to convectively heat the reaction gas, yielding carbon-containing dust and hydrogen-rich syngas. The vertical shaft furnace 2 consists of a 650°C mesotemperature section and a 950°C high-temperature section from top to bottom. The plasma device 3 uses a high-temperature plasma jet to split water, initiating a wet reforming reaction.

[0029] For the processing of low-tar bituminous coal and high-moisture lignite, the carbonaceous particulate material is granular coal. The multi-stage coupled processing includes: firstly, the first suspended pyrolysis material is introduced into plasma device 3 for hydrogen production and cracking. The plasma torch generates high-temperature hydrogen ions and oxygen ions at 1100℃, which react with carbon powder, light hydrocarbon gases, tar, and other hydrocarbons entering the wet reforming reactor for rapid wet reforming. Oxygen ions react with carbon powder to generate carbon monoxide, and water vapor and fine carbon powder undergo gasification to generate hydrogen and carbon monoxide, yielding hydrogen-rich fuel gas. Then, the hydrogen-rich fuel gas is introduced into shaft furnace 2 for convective pyrolysis with the granular coal, while simultaneously heating the lump coal to 1100℃, yielding suspended carbon powder and the first hydrogen-rich syngas, which includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0030] For the processing of high-tar bituminous coal and high-tar lignite, the carbonaceous granular material is granular coal. The multi-stage coupled processing includes: first, the second-stage suspended first pyrolysis material is fed into the intermediate temperature section (intermediate temperature refers to 650℃) of the vertical shaft furnace 2, where it undergoes pyrolysis with the lump coal in the intermediate temperature section to obtain the second-stage suspended second pyrolysis material; the second-stage suspended second pyrolysis material is then fed into the plasma device 3 for water cracking and wet reforming reactions, where the plasma torch cracks the water vapor to generate high-temperature hydrogen ions and oxygen ions at 1100℃, obtaining the second-stage hydrogen-rich syngas; finally, the second-stage hydrogen-rich syngas is fed into the high-temperature section (high temperature refers to 950℃) of the vertical shaft furnace 2, where it undergoes high-temperature pyrolysis with the granular coal in the high-temperature section to obtain suspended carbon powder and the third-stage hydrogen-rich syngas. Both the second-stage and third-stage hydrogen-rich syngas contain water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0031] In a preferred embodiment, when the carbon-containing material is low-tar bituminous coal and high-moisture lignite, the carbon-containing particulate material can be low-ash briquettes, low-ash lump coal, and biomass pellets. The multi-stage coupled processing includes: first, the fourth-path suspended first pyrolysis material is introduced into the plasma device 3 for hydrogen production and cracking to obtain hydrogen-rich fuel gas; then, the hydrogen-rich fuel gas is introduced into the vertical furnace 2 and convectively pyrolyzed with the carbon-containing particulate material to obtain suspended carbon powder and the fourth-path hydrogen-rich syngas, which includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0032] In another preferred embodiment, when the carbon-containing material is biomass powder and wood vinegar, the carbon-containing granular material is biomass granules; or when the carbon-containing material is biomass powder, organic waste, and wood vinegar, the carbon-containing granular material is a mixture of organic waste and biomass granules; or when the carbon-containing material is oil shale powder and the carbon-containing granular material is oil shale granules, the multi-stage coupling process includes: first, the fifth-path suspended first pyrolysis material is introduced into the medium-temperature section of the vertical furnace 2 to undergo pyrolysis with the biomass granules in the medium-temperature section to obtain the fifth-path suspended second pyrolysis material; the fifth-path suspended second pyrolysis material is introduced into the plasma device 3 for water splitting and wet reforming reactions to obtain combustible gas again; finally, the combustible gas is introduced into the high-temperature section of the vertical furnace 2 to undergo high-temperature pyrolysis with the biomass granules in the high-temperature section to obtain suspended biochar powder and the fifth-path hydrogen-rich syngas; the fifth-path hydrogen-rich syngas includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

[0033] Step 3: The ammonia water generated during the process is used to treat the high-temperature carbon-containing dust, recovering its sensible heat and generating ammonia-containing vapor. The fine carbon powder and residue from the wet reforming reactor, captured by the lump coal particle layer filter, are heated to 1100°C and then enter the evaporative cooling device 5. The carbon powder is heated to 1100°C, and the ammonia water from the evaporative cooling device 5 indirectly exchanges heat with the high-temperature carbon powder. After the carbon powder is cooled to 120°C, it is discharged into the spiral discharge device 7 equipped with steam protection for coke quenching for further cooling and discharge, generating ammonia-containing vapor.

[0034] In a preferred embodiment, when the carbon-containing material is low-tar bituminous coal and high-moisture lignite, and the carbon-containing granular material can be low-ash briquettes, low-ash lump coal and biomass pellets, the treatment of the carbon-containing dust at high temperature using ammonia water generated during the process specifically refers to: passing ammonia water and carbon powder into a steam activation device to perform steam activation treatment on the carbon powder to obtain activated carbon or activated coke.

[0035] Step 4: At least a portion of the hydrogen-rich syngas is returned to Step 1 as a source of high-temperature hydrogen-rich gas. Ammonia-containing vapor is mixed with a portion of the hydrogen-rich syngas and then introduced into plasma device 3 for reforming, achieving hydrogen and oxygen recycling. Specifically: Ammonia-containing vapor is mixed with the first stream of hydrogen-rich syngas and introduced into plasma device 3 for cracking and reforming, generating hydrogen-rich gas. This hydrogen-rich gas is first cooled and washed in evaporative cooling device 5, then introduced into gas holder 4. After being heated by electromagnetic induction heating device 8, it is returned to Step 1 as high-temperature hydrogen-rich gas. Simultaneously, the generated steam and the hot semi-coke discharged from the two electromagnetic induction heated rotary kilns 11 and fluidized bed 12 enter evaporative cooling device 5. Together with the steam generated from the indirect heat exchange of the remaining ammonia water and a small portion of the recycled syngas, it enters the plasma torch for cracking and reforming. Furthermore, the cracking water in plasma device 3 generates high-temperature hydrogen-rich reducing gas at 1100℃, providing a heat source for vertical furnace 2 and improving energy utilization.

[0036] Throughout the process, the hydrogen-rich syngas cooled to 120°C, along with hydrogen, carbon monoxide, light hydrocarbon gases, tar gas, and other minor pyrolysis gas components produced by the pyrolysis of lump coal in the vertical furnace 2, are introduced into the evaporative cooling unit 5 by a blower. After separating out the tar, tar residue, and condensate, the syngas is sent to the gas holder 4. Most of the recycled syngas is supplied to gas-fired power plants or chemical plants.

[0037] This method achieves efficient pyrolysis of carbon-containing materials and recycling of hydrogen by coupling plasma device 3 with vertical furnace 2. It not only improves energy utilization efficiency, but also realizes effective recovery of ammonia waste heat, forming a complete recycling system.

[0038] Example 2: This system includes the following main components: pyrolysis device 1, plasma device 3, gas holder 4, evaporation and cooling device 5, activation furnace 6, and spiral discharge device 7.

[0039] The pyrolysis unit 1 includes a rotary kiln 11 and a fluidized bed 12, used for preliminary pyrolysis treatment of raw materials. The rotary kiln 11 and fluidized bed 12 employ electromagnetic induction heating, capable of controlling the temperature at 650℃ or 950℃, adjustable according to the characteristics of different raw materials. The fluidized bed 12 works in conjunction with the rotary kiln 11 to ensure sufficient heat transfer and reaction of the raw materials during the pyrolysis process.

[0040] Shaft furnace 2 is the core reaction equipment of the system, consisting of a 650℃ intermediate temperature section and a 950℃ high temperature section from top to bottom. The intermediate temperature section is mainly used to process bituminous coal or lignite with high tar content, undergoing preliminary pyrolysis at 650℃ to release components such as water vapor, hydrogen, carbon monoxide, light hydrocarbon gases, and tar gas. The high temperature section reaches 950℃ for further pyrolysis, allowing unreacted materials to undergo convective heat exchange with the granular coal from the top of shaft furnace 2, while simultaneously heating the lump coal to 1100℃. The lump coal granular layer inside shaft furnace 2 also has a filtration function, capable of capturing unreacted fine carbon powder and residue from the wet reforming reactor.

[0041] Plasma device 3 uses a high-temperature plasma jet to split water, initiating a wet reforming reaction. The plasma torch generates a temperature of 1100°C, splitting water vapor to produce hydrogen and oxygen ions. These high-temperature ions react rapidly with pyrolysis gases from rotary kiln 11 and fluidized bed 12 within the wet reforming chamber. Oxygen ions react with carbon produced from the cracking of carbon powder, light hydrocarbon gases, tar, and other hydrocarbon compounds entering the wet reforming reactor, generating carbon monoxide. Water vapor reacts with fine carbon powder particles to produce hydrogen and carbon monoxide. The plasma device 3 generates a high-temperature, hydrogen-rich reducing gas at 1100°C from the water splitting process, providing the necessary reducing atmosphere and heat source for subsequent reactions, thus improving energy efficiency. Furthermore, the energy source for plasma device 3 is clean energy, reducing environmental pollution.

[0042] Gas holder 4 is used to store gas and receive syngas processed by evaporative cooling device 5. Part of the hydrogen-rich syngas stored in gas holder 4 is heated by electromagnetic induction heating device 8 and then recycled back into the system to participate in the reaction, while the other part is supplied to gas-fired power plants or chemical plants. The gas that needs to be introduced into gas holder 4 must first be cooled and washed by evaporative cooling device 5 before being introduced into gas holder 4 for storage.

[0043] Evaporative cooling unit 5 is used to cool and condense ammonia-containing vapors. High-temperature hydrogen-rich syngas from vertical furnace 2 and various gaseous components generated from pyrolysis are introduced into it via a blower. During the condensation process, the system can separate byproducts such as tar, tar residue, and condensate. The treated gas is then sent to gas holder 4 for storage.

[0044] Activation furnace 6 is used for steam activation treatment, mainly for the production of activated carbon or activated coke. When the system is used to produce activated carbon products, the material in vertical furnace 2 is changed to low-ash coal briquettes, low-ash lump coal, biomass pellets, etc. The high-temperature carbon material is steam activated by the steam activation device, transforming it into activated carbon or activated coke products with high specific surface area and rich pore structure.

[0045] The spiral discharge device 7, equipped with steam-protected coke quenching function, is located at the end of the system. The material processed by the evaporative cooling device 5 is indirectly cooled to 120°C through heat exchange with the residual ammonia water from the evaporative cooling device 5, and then discharged into the spiral discharge device 7 with steam-protected coke quenching function for further cooling before discharge. The steam protection function prevents the high-temperature char from burning during the discharge process, ensuring product quality and operational safety.

[0046] The electromagnetic induction heating device 8 drives the eddy current heating structure, which heats the material through eddy current heating.

[0047] The system operates as follows: raw materials undergo preliminary pyrolysis via a rotary kiln 11 and fluidized bed 12. The resulting gas and unreacted materials enter the wet reforming chamber of the plasma device 3, where they undergo a wet reforming reaction with high-temperature ions generated by the plasma torch. The reaction products are further processed in different temperature zones of the vertical shaft furnace 2, and finally, various products are separated by an evaporative cooling device 5. Hydrogen-rich gas is stored in a gas holder 4. Through steam circulation and heat recovery, the system achieves efficient energy utilization and the combined production of multiple products.

[0048] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0049] The technologies, shapes, and structures not described in detail in this invention are all known technologies.

Claims

1. A method for pyrolysis of carbonaceous materials in a plasma-driven water splitting hydrogen production environment, characterized in that, The process includes the following steps: S1: Mixing carbon-containing materials with high-temperature hydrogen-rich gas in a pyrolysis device (1) and stirring and pyrolyzing to obtain a first pyrolysis product; S2: Selectively introducing the gaseous components of the first pyrolysis product into a coupling system consisting of a vertical furnace (2) and a plasma device (3) for multi-stage coupling processing according to the type of carbon-containing materials, and using the carbon-containing particles in the vertical furnace (2) to perform convective heat exchange on the reaction gas to obtain carbon-containing dust and hydrogen-rich synthesis gas; S3: Using ammonia water generated during the process to treat the high-temperature carbon-containing dust, recovering its sensible heat and generating ammonia vapor; S4: Returning at least a portion of the hydrogen-rich synthesis gas to step S1 as the gas source of the high-temperature hydrogen-rich gas, and mixing the ammonia vapor with a portion of the hydrogen-rich synthesis gas before introducing it into the plasma device (3) for reforming to achieve hydrogen and oxygen recycling.

2. The method for pyrolysis of carbon-containing materials according to claim 1, characterized in that, In step one, the carbon-containing materials are low-tar bituminous coal and high-moisture lignite, and the first pyrolysis product is separated into a first suspended first pyrolysis material and a first non-suspended first pyrolysis material through gas-solid separation. The first suspended pyrolysis material includes: water vapor, hydrogen-rich fuel gas, tar gas, light hydrocarbon gas and carbon powder; the first non-suspended pyrolysis material includes semi-coke and residue; and the hydrogen-rich fuel gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

3. The method for pyrolysis of carbon-containing materials according to claim 2, characterized in that, In step two, the carbon-containing particulate material is particulate coal. The multi-stage coupling process specifically includes: first, the first suspended pyrolysis material is fed into the plasma device (3) for hydrogen production and cracking to obtain the hydrogen-rich gas again; then, the hydrogen-rich gas is fed into the vertical furnace (2) and convectively pyrolyzed with the particulate coal to obtain the suspended carbon powder and the first hydrogen-rich syngas, wherein the first hydrogen-rich syngas includes water vapor, hydrogen, carbon monoxide and light hydrocarbon gases.

4. The pyrolysis method for carbon-containing materials according to claim 3, characterized in that, In step three, the process of using ammonia water generated during the process to treat the carbon dust at high temperature is specifically as follows: the carbon powder is heated to 1100°C, and the ammonia water from the evaporative cooling device (5) is used to indirectly exchange heat with the high-temperature carbon powder in the evaporative cooling device (5) to generate the ammonia vapor.

5. The method for pyrolysis of carbon-containing materials according to claim 4, characterized in that, In step four, the mixing of ammonia vapor with a portion of the first hydrogen-rich synthesis gas and then passing it into the plasma device (3) for reforming specifically involves mixing the ammonia vapor with the first hydrogen-rich synthesis gas and passing it into the plasma device (3) to undergo a cracking and reforming reaction, generating hydrogen-rich gas after hydrogenation. The hydrogen-rich gas is then passed into the gas holder (4) and heated before returning to step S1 to become the high-temperature hydrogen-rich gas.

6. The method for pyrolysis of carbon-containing materials according to claim 1, characterized in that, In step one, the carbon-containing material is high-tar bituminous coal or high-tar lignite, and the first pyrolysis product is separated into a second suspended first pyrolysis material and a second non-suspended first pyrolysis material through gas-solid separation. The second suspended first pyrolysis material includes: water vapor, hydrogen-rich fuel gas, tar gas, light hydrocarbon gas and carbon powder; the second non-suspended first pyrolysis material includes semi-coke and residue; and the hydrogen-rich fuel gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

7. The pyrolysis method for carbon-containing materials according to claim 6, characterized in that, In step two, the carbon-containing granular material is granular coal. The multi-stage coupling process specifically includes: first, the second-path suspended first pyrolysis material is introduced into the medium-temperature section of the vertical furnace (2) and pyrolyzed with the lump coal in the medium-temperature section to obtain the second-path suspended second pyrolysis material; the second-path suspended second pyrolysis material is introduced into the plasma device (3) for water cracking and wet reforming reaction to obtain the second-path hydrogen-rich syngas; finally, the second-path hydrogen-rich syngas is introduced into the high-temperature section of the vertical furnace (2) and pyrolyzed with the granular coal in the high-temperature section to obtain the suspended carbon powder and the third-path hydrogen-rich syngas; the second-path hydrogen-rich syngas and the third-path hydrogen-rich syngas both include water vapor, hydrogen, carbon monoxide and light hydrocarbon gases.

8. The method for pyrolysis of carbon-containing materials according to claim 1, characterized in that, In step one, the carbon-containing materials are low-tar bituminous coal and high-moisture lignite, and the first pyrolysis product is separated into a fourth suspended first pyrolysis material and a fourth non-suspended first pyrolysis material through gas-solid separation. The fourth suspended first pyrolysis material includes: water vapor, hydrogen-rich fuel gas, tar gas, light hydrocarbon gas and carbon powder; the fourth non-suspended first pyrolysis material includes semi-coke and residue; and the hydrogen-rich fuel gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

9. The method for pyrolysis of carbon-containing materials according to claim 8, characterized in that, In step two, the carbon-containing particulate material is low-ash coal, low-ash lump coal, and biomass particles. The multi-stage coupling process specifically includes: first, the fourth-path suspended first pyrolysis material is introduced into the plasma device (3) for hydrogen production and cracking to obtain the hydrogen-rich gas; then, the hydrogen-rich gas is introduced into the vertical furnace (2) and convectively pyrolyzed with the carbon-containing particulate material to obtain suspended carbon powder and the fourth-path hydrogen-rich synthesis gas, wherein the fourth-path hydrogen-rich synthesis gas includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

10. The method for pyrolysis of carbon-containing materials according to claim 9, characterized in that, In step three, the process of using ammonia water generated during the process to treat the carbon-containing dust at high temperature includes passing the ammonia water and the carbon powder into a steam activation device to perform steam activation treatment on the carbon powder to obtain activated carbon or activated coke.

11. The method for pyrolysis of carbon-containing materials according to claim 1, characterized in that, In step one, the carbon-containing material is biomass powder and wood vinegar. The first pyrolysis product is separated into a fifth suspended first pyrolysis material and a fifth non-suspended first pyrolysis material through gas-solid separation. The fifth suspension-state first pyrolysis material includes: water vapor, combustible gas, tar gas and biochar powder; the fifth non-suspension-state first pyrolysis material includes biochar; and the combustible gas includes hydrogen, carbon monoxide and a small amount of carbon dioxide.

12. The method for pyrolysis of carbon-containing materials according to claim 11, characterized in that, In step two, the carbon-containing granular material is biomass granules. The multi-stage coupling treatment specifically includes: first, the fifth-path suspended first pyrolysis material is introduced into the medium-temperature section of the vertical furnace (2) and pyrolyzed with the biomass granules in the medium-temperature section to obtain the fifth-path suspended second pyrolysis material; the fifth-path suspended second pyrolysis material is introduced into the plasma device (3) for water splitting and wet reforming reaction to obtain the combustible gas again; finally, the combustible gas is introduced into the high-temperature section of the vertical furnace (2) and pyrolyzed with the biomass granules in the high-temperature section to obtain the suspended biochar powder and the fifth-path hydrogen-rich synthesis gas; the fifth-path hydrogen-rich synthesis gas includes water vapor, hydrogen, carbon monoxide, and light hydrocarbon gases.

13. A system based on the pyrolysis method for carbonaceous materials according to any one of claims 1 to 12, characterized in that, The system includes: a pyrolysis device (1), which includes a rotary kiln (11) and a fluidized bed (12); a vertical furnace (2), which has a medium-temperature section of 650°C and a high-temperature section of 950°C from top to bottom; a plasma device (3), which splits water through a high-temperature plasma jet to produce a wet reforming reaction; a gas holder (4) for storing gas; an evaporative cooling device (5) for cooling and condensing the ammonia-containing vapor; an activation furnace (6) for steam activation treatment; a spiral discharge device (7) with steam protection for coke quenching; and an electromagnetic induction heating device (8) for heating materials.

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