Apparatus and method for direct cracking of natural gas to hydrogen and high value carbon

Abstract

The application discloses a device and method for directly cracking natural gas to produce hydrogen and high-value carbon, and the device takes a cracking tank as a core equipment, is divided into three zones of ABC, and is composed of three part tank bodies from top to bottom, the tank body is fully heat-insulated, and the tank wall is composed of fire bricks, heat-insulating materials and steel plates. The cracking tank is provided with a linear motor, high-value carbon transmission equipment, a temperature and pressure transmitter, an industrial television, a cooling air cooling water cooling system and a central control room computer control system. The application further discloses a method for directly cracking natural gas to produce hydrogen and high-value carbon by using the innovative cracking tank device, and the method directly cracks natural gas by taking Cu, Bi alloy or Cu, Sn alloy or Cu, Bi, Sn alloy molten metal as a catalyst; the method is supplemented with a catalyst regeneration system and high-value carbon transmission equipment; and the method adopts a central control room computer control system to control various parameters of a natural gas cracking system, such as temperature fields, flow fields and pressure fields, so as to complete product output. The application reduces the cost and is energy-saving and environment-friendly for industrialized large-scale production of hydrogen and high-value carbon.

Description

Technical Field

[0001] This invention relates to the field of hydrogen production, specifically to an apparatus and method for directly cracking natural gas to produce hydrogen and high-value carbon using a molten metal catalyst. Background Technology

[0002] The technology for producing hydrogen and high-value carbon from molten metal through natural gas cracking, as described in the utility model patent application [202220431346.7] entitled "A High-Temperature Reactor for Direct Hydrogen and High-Value Carbon Production from Methane via Molten Metal Decomposition," has achieved small-scale trials of this technology. However, further scale-up research is needed.

[0003] Chinese invention patent application No. ZL 202010241533.4, entitled "An Apparatus and Method for Hydrogen Production by Catalytic Cracking of Natural Gas or Coalbed Methane," discloses an apparatus and method for hydrogen production by catalytic cracking of natural gas or coalbed methane, wherein the main reaction device 1 is a vertical fluidized bed. The aforementioned vertical fluidized bed is commercially available, for example, it can be purchased from Xi'an Electric Furnace Research Institute Co., Ltd., and its specifications are chemical vapor deposition furnace, Φ2800x3600mm. This invention's main reaction device has certain limitations for large-scale hydrogen production and high-value carbon production.

[0004] Chinese invention patent application No. ZL 202110438154.9, entitled "A System and Method for Producing Hydrogen from Natural Gas Using Liquid Metal Cracking," discloses a system for producing hydrogen from natural gas using liquid metal cracking, comprising a liquid metal melting tank, a liquid metal cracking reactor, and a separator. It also discloses a method for producing hydrogen from natural gas using liquid metal cracking. This invention describes large-scale hydrogen production and carbon black production; however, since carbon black is not a high-value carbon product, the economic benefits of producing hydrogen and carbon black are limited. Furthermore, the cost of large-scale industrial production using this patent, requiring many natural gas-burning enterprises to convert to hydrogen production, is clearly too high. The key to industrial conversion of natural gas into hydrogen lies in simultaneously producing high-value carbon and reducing the cost of hydrogen.

[0005] Chinese invention patent application number ZL 202310248760.3, entitled "A Green Hydrogen Preparation System and Process," describes a process that "achieves a natural gas cracking efficiency of over 98%, produces no carbon dioxide, and yields graphene and carbon black as byproducts; and obtains hydrogen with a purity of over 99.9%." However, this patent suffers from drawbacks, such as overly complex processes and high costs, for industrial furnaces that burn large quantities of hydrogen for large-scale hydrogen production.

[0006] Graphene possesses superior properties in optics, electricity, heat, and mechanics, making it a promising new material with significant application potential and wide applicability to economic and social development. It has already shown promising application prospects in energy equipment, transportation, aerospace, marine equipment, and industrial electronics. Developing the graphene industry is of great practical significance in driving technological progress in related downstream industries, enhancing innovation capabilities, accelerating transformation and upgrading, and stimulating potential consumption. Graphene, with its excellent properties, has become an important component of new materials.

[0007] The present invention provides an apparatus and method for direct cracking of natural gas to produce hydrogen and high-value carbon. This method is a medium-to-large-scale direct cracking method for producing hydrogen and high-value carbon from natural gas. It can solve the problems of catalyst carbon deposition, production continuity and engineering scale-up in the current direct cracking of hydrogen and high-value carbon using molten metal catalysts. It reduces the cost of hydrogen combustion, improves the overall economic benefits of hydrogen production enterprises by producing high-value carbon, and reduces carbon dioxide emissions in industrial combustion.

[0008] In 2019, the building materials industry had 370 flat glass production lines with a capacity of 1.33 billion weight boxes. Assuming a melting furnace energy consumption of 1350 kcal / kg molten glass and an average yield of 88%, the energy required to melt molten glass is: 10² × 10⁻⁶ kcal / kg molten glass. 12 This translates to approximately 14.57 million tons of standard coal equivalent per year. If hydrogen combustion were used instead of natural gas in the melting furnace, carbon dioxide emissions could be reduced by 36.32 million tons per year. This invention is extremely important for reducing hydrogen production costs, especially for large-scale hydrogen combustion to replace natural gas, and for promoting carbon dioxide emission reduction in the glass industry. Summary of the Invention

[0009] This invention primarily addresses the scientific and technological challenges of catalyst coking, production continuity, and scale-up in the direct cracking of natural gas for hydrogen and high-value carbon production. It provides a digitally controlled apparatus and method for the direct cracking of natural gas for hydrogen and high-value carbon production using molten metal catalysts, facilitating large-scale environmentally friendly conversion from natural gas to hydrogen combustion in the glass industry. The technical solution adopted by this invention is as follows: A digitally controlled pyrolysis cell device for direct pyrolysis of natural gas to produce hydrogen and high-value carbon using molten metal catalysts is provided. The device includes: a natural gas pyrolysis cell, molten metal placed inside the pyrolysis cell, a natural gas bubbler cluster distribution device, a regenerated gas bubbler cluster device, a temperature transmitter, an in-cell pressure transmitter, a linear motor, a high-value carbon transfer device, a three-phase silicon carbide rod heating system at the top of the cell, an in-cell cooling water tank, an endoscopic industrial television, a molten metal liquid level control system, an in-cell temperature field detector, and a digitally controlled system.

[0010] The natural gas cracking cell is designed with a lower tank body, an upper cover, and sealing devices in the middle body. The upper and lower tank bodies are supported by steel structures. All parts of the cracking cell are fully insulated, with refractory bricks on the inside and insulating bricks on the outside. The outer shell is made of steel plate.

[0011] The lower tank is made of steel plate as the outer shell and refractory material as the inner layer to form a molten metal tank. The lower tank is divided into three zones: A, B and C. The bottom of zone A is the natural gas inlet, where a natural gas bubbler cluster distribution device is arranged. The bottom of zone B is where a regenerated gas bubbler cluster device is arranged. Zone C is the molten metal catalyst clarification and high-value carbon output zone.

[0012] The bottom of the A, B, and C sections increases in height by 80-100mm in sequence, with the end of section C appropriately narrowed, and the outlet should not be too wide.

[0013] Temperature transmitters are installed in each zone at the bottom of tanks A, B, and C.

[0014] Furthermore, the bubbler distribution cluster adopts the bubbler distribution cluster of the utility model patent "A Bubbling System Applied to Glass Melting Furnace" of Shanghai Jichi Glass Technology Co., Ltd., patent number ZL 201820037546.8.

[0015] The top cover is hoisted by a steel structure. The outer shell of the top cover is made of steel plate, and the inner layer is made of refractory material. The top cover is equipped with a three-phase silicon carbide rod heating system, a temperature transmitter, and a pressure transmitter in the tank. A hydrogen outlet connection device is installed at the tail of area C.

[0016] The intermediate body is divided into fixed seal and movable seal as needed. The outer shell of the intermediate body is made of steel plate, and the inner layer is composed of heat insulation material and refractory material. It is equipped with an endoscopic industrial television, a tank temperature field detector, a tank cooling water tank, a linear motor, and a high-value carbon transmission device.

[0017] Furthermore, the aforementioned endoscopic industrial television adopts the utility model patent of Shanghai Jichi Glass Technology Co., Ltd.: A vertical endoscopic industrial television for float glass tin bath, patent number: ZL 201220391598.8.

[0018] Furthermore, the temperature field detector inside the tank is intended to use a commercially available thermal imaging system, which employs high-performance solid-state infrared imaging technology. It can penetrate the hydrogen gas inside the tank and be clearly visible. The temperature range is sufficient for real-time temperature measurement and analysis of images within the range of 850℃ to 1800℃.

[0019] Furthermore, the linear motor and the high-value carbon transfer device in the tank are manufactured using proprietary technology of Shanghai Jichi Company or customized for the market.

[0020] Furthermore, the high-value carbon outlet of the pyrolysis cell requires a strict seal with high-silica cloth.

[0021] The external devices of the natural gas cracking cell include a supporting steel frame for the natural gas cracking cell, a natural gas control system, a regenerated gas control system, a bottom cooling air device, a circulating water cooling system, a high-value carbon dispensing system, a hydrogen collection and purification system, a high-purity hydrogen storage tank, and a central control room computer system.

[0022] Furthermore, the aforementioned pyrolysis tank support steel structure frame, composed of steel structure, serves to support the lower tank body of the natural gas pyrolysis tank and suspend the top cover of the natural gas pyrolysis tank. The reason for suspending the top cover is to facilitate the installation and maintenance of electric heating elements and the installation of various instruments and equipment related to the pyrolysis tank.

[0023] Furthermore, the aforementioned natural gas control system includes a computer control system for controlling and measuring various valves and parameters such as natural gas supply pressure, supply flow rate, and natural gas on / off states.

[0024] Furthermore, the aforementioned regenerated gas control system includes a computer control system for controlling and measuring various valves and parameters such as regenerated gas supply pressure, supply flow rate, and natural gas on / off status.

[0025] Furthermore, the aforementioned bottom cooling air device serves to ensure a stable and balanced temperature inside the tank, and includes a cooling fan and system integration with computer-controlled temperature control.

[0026] Furthermore, the aforementioned circulating water cooling system is necessary because the temperature in the pyrolysis tank is as high as 800-1200°C. Various instruments and systems require a deionized water circulating cooling system to ensure their normal operation.

[0027] The high-value carbon packaging system further includes packaging, cooling, and transporting the high-value carbon to the finished product warehouse.

[0028] The further hydrogen collection and purification system purifies the hydrogen and delivers it to a hydrogen storage tank or hydrogen utilization system.

[0029] Furthermore, the central control room computer system includes a computer-controlled digital intelligent system for power supply and distribution, as well as reaction temperature, pressure, flow rate, and reaction status at various points during the molten metal catalyst natural gas to hydrogen production and high-value carbon cracking project.

[0030] The method for producing hydrogen and high-value carbon using the aforementioned apparatus for direct cracking of natural gas includes the following: (1) Inspection and acceptance of each system of the natural gas cracking unit: including the natural gas cracking cell and natural gas control system, regenerated gas control system, circulating water cooling system, bottom cooling air device, top three-phase silicon carbide heating system, endoscopic industrial television, temperature field detector inside the cell, cooling water tank inside the cell, linear motor, high-value carbon transmission device, central control room computer system, high-value carbon dispensing system, hydrogen collection and purification system, safety assurance system, etc., which have been inspected and accepted and meet the requirements; (2) After each unit and system has passed inspection and acceptance, it will enter the process of direct cracking of natural gas to produce hydrogen and high-value carbon using molten metal catalyst; (3) Place the designed weight of molten alloy metal in each of zones A, B and C of the natural gas cracking cell, turn on the three-phase silicon carbide heating system at the top of the cell, and the cracking cell heats up according to the given temperature curve. When the temperature of the cracking cell reaches the given temperature of 600-800°C, turn on the nitrogen replacement air system in the cracking cell and replace all the air in the cell with nitrogen. (4) Melt the molten metal in the natural gas cracking tank according to the required melting temperature. When the cracking tank reaches the given temperature of 800-1200°C, turn on the natural gas control system and the computer control system. Input qualified natural gas into the natural gas inlet bubbler cluster distribution device at the bottom of area A, strictly according to the required gas supply pressure of 0.5-1MPa and flow rate and velocity of 0.1-0.25L / M. 2 The system uses a computer control system to precisely control various parameters such as natural gas input pressure, flow rate, bubbling frequency, and bubbling size. (5) The natural gas inlet is a natural gas bubbler cluster distribution device at the bottom of Zone A, including: bubbler cluster, bubbler advance and retreat device, natural gas pressure regulating valve, flow regulating valve, check valve, flow switch, and metal hose connector; (6) Adjust the endoscopic industrial television to observe the bubbling situation and the generation of hydrogen and high-value carbon; (7) Adjust the temperature field detector and computer temperature control system in the tank to maintain the required temperature and temperature gradient in zones A, B and C of the temperature field in the tank. (8) Adjust the hydrogen collection and purification system to ensure normal hydrogen output and a slight positive pressure in the pyrolysis tank; (9) Adjust the linear motor to control the flow of molten metal to ensure that the molten metal flows from A to B to C, so that the high-value carbon can be smoothly output at the high-value carbon transmission device in C of the tank. (10) Adjust the high-value carbon transmission device to ensure a normal gap between it and the tank outlet, and adjust the inlet and outlet circulating cooling water temperature to ensure its normal operation and ensure that the high-value carbon smoothly enters the high-value carbon dispensing system. (11) Adjust the high-value carbon dispensing system to ensure normal output of high-value carbon; (12) Observe the production of hydrogen and high-value carbon by turning on the regeneration gas device. If the production efficiency is found to be low, turn on the regeneration gas bubbling cluster device. The regeneration gas is hydrogen or a mixture of hydrogen and natural gas. The regeneration gas inlet is at the bottom of zone B. The cluster device includes: a regeneration gas bubbler cluster inlet and outlet device, a regeneration gas pressure regulating valve, a flow regulating valve, a check valve, a flow switch, and a metal hose connector. Strictly follow the required gas supply pressure, flow rate, and speed to input qualified regeneration gas. The regeneration gas flow rate, pressure, bubbling frequency, and bubble size are all connected to the operation panel and control computer and can be precisely controlled by the computer system. (13) Adjust the input pressure and flow rate of regenerated gas, and adjust the bubbling frequency and bubbling size by computer; (14) Observe the bubbling of regenerated gas and the changes in the efficiency of hydrogen and high-value carbon production through an endoscopic industrial television. The regenerated gas adjustment is completed when the hydrogen and high-value carbon production efficiency reaches the required level. (15) The direct cracking of hydrogen and high-value carbon from molten metal has been completed and normal production has resumed.

[0031] The beneficial effects of the method for directly pyrolyzing natural gas to produce hydrogen and high-value carbon according to the present invention are as follows: In current patents and literature regarding hydrogen production and high-value carbon production from natural gas pyrolysis, this method is basically in the scientific research stage, undergoing small-scale trials and production. There are three major problems for pilot production: catalyst failure, production continuity, and medium-to-large-scale production. The beneficial effects of the method of directly pyrolyzing natural gas into hydrogen and high-value carbon using molten metal as a catalyst, as described in this invention, are as follows: (1) The steel structure of the natural gas cracking tank of this invention is designed to divide the tank into several zones, A, B, and C, and to have upper, middle and lower shells. The cracking working area is large, which can meet the needs of medium and large-scale production of hydrogen and high-value carbon. (2) The present invention uses a computer control system to control the flow rate, pressure, temperature, size and speed of the bubbles, control the pressure inside the tank, control the temperature at various points inside the tank, control the temperature field of the pyrolysis liquid, control the output speed of high-value carbon and the output speed of hydrogen, so as to ensure the stability of the process system and realize the continuous production of hydrogen and high-value carbon in medium and large batches with high quality. (3) The present invention sets up a molten metal pyrolysis liquid regeneration zone and precisely controls the pressure, flow rate and pressure of the regeneration gas. Through the dynamic action of the regeneration gas bubbling in the pyrolysis liquid, the problem of catalyst failure is effectively solved. (4) Since the present invention realizes computer digital control, it can meet the needs of production of various qualities and quantities or varieties, and can select hydrogen and high-value carbon or hydrogen and graphene, etc., which improves the technical and economic effect of direct cracking of molten metal to produce hydrogen and high-value carbon. (5) This invention expands the application range of hydrogen and high-value carbon directly cracked by natural gas under the action of molten metal as a catalyst. This invention allows large-scale natural gas enterprises to build natural gas cracking tanks on-site to supply hydrogen for combustion, which is low-cost and efficient. In particular, it is of great practical significance for the glass industry, which currently burns a large amount of natural gas, to achieve the "dual carbon" goal, realize the combustion of hydrogen in large-scale natural gas furnaces, reduce carbon dioxide emissions significantly, and achieve green environmental protection. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the equipment and method for direct pyrolysis of hydrogen and high-value carbon from molten metal according to the present invention.

[0033] In the diagram: 1. Natural gas cracking cell; 2. Natural gas bubbler cluster distribution device; 3. Regenerated gas bubbler cluster device; 4. Temperature transmitter; 5. Linear motor; 6. Tank bottom cooling air device; 7. High-value carbon transmission device; 8. High-value carbon dispensing system; 9. Hydrogen collection and purification system; 10. High-purity hydrogen storage tank; 11. Digital intelligent control system; 12. Tank cooling water tank; 13. Tank top three-phase silicon carbide rod heating system; 14. Endoscopic industrial television; 15. Tank temperature field detector; 16. Circulating water cooling system; 17. Natural gas control system; 18. Liquid level control system; 19. Tank pressure transmitter; 20. Regenerated gas control system; 21. Central control room computer system. Detailed Implementation

[0034] The technical solution 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, 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. In the description of the present invention, it should be noted that the directions or positional relationships indicated by terms such as "upper," "lower," "inner," and "outer" are based on the directions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention.

[0035] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected" or "linked" should be interpreted broadly. For example, it can refer to a fixed connection, a detachable connection, or an integral connection; it can refer to a mechanical connection or an electrical connection; it can refer to a direct connection or an indirect connection through an intermediate medium; it can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0036] Example: An apparatus and method for directly cracking natural gas to produce hydrogen and high-value carbon, producing hydrogen, high-value carbon and graphene.

[0037] This invention provides an apparatus and supporting system for the direct cracking of natural gas to produce hydrogen and high-value carbon using a liquid metal catalyst, such as... Figure 1 As shown; An apparatus for directly cracking natural gas to produce hydrogen and high-value carbon is provided, comprising: a natural gas cracking cell 1, a natural gas bubbler cluster distribution device 2, a regenerated gas bubbler cluster device 3, a temperature transmitter 4, a linear motor 5, a high-value carbon transmission device 7, a cooling water tank 12, a three-phase silicon carbide rod heating system at the top of the cell 13, an endoscopic industrial television 14, a temperature field detector inside the cell 15, a liquid level control system 18, and a pressure transmitter inside the cell 19.

[0038] The supporting system for the direct cracking of natural gas to produce hydrogen and high-value carbon further includes: a bottom cooling air device 6, a high-value carbon dispensing system 8, a hydrogen collection and purification device 9, a high-purity hydrogen storage tank 10, a digital control system 11, a circulating water cooling system 16, a natural gas control system 17, a regenerated gas control system 20, and a central control room computer system 21.

[0039] The natural gas cracking tank 1 is a medium-to-large-sized tank design with sealing devices at various points, including a lower tank body, an upper cover, and an intermediate body. The tank body is supported by a steel structure. The outer shell of the lower tank body is made of steel plate, and the inner layer is composed of insulation and refractory materials. The lower tank body is divided into three zones: A, B, and C. Zone A has a natural gas inlet at the bottom and is equipped with a natural gas bubbler cluster distribution device 2. The diameter of a single bubbler hole is 0.8-6 mm, and each bubbler has 1 to 11 holes. Zone B is equipped with a regenerated gas bubbler cluster device 3, with a diameter of a single bubbler hole of 0.8 mm. -6mm, one bubbler has 1 to 11 round holes; Zone C is the molten metal clarification and high-value carbon output zone, the tank is equipped with a molten metal liquid level control system and a high-value carbon transmission device, the liquid level control accuracy is ±0.5 to ±1mm, the bottom of each zone of tanks A, B and C increases by 80-100mm in sequence, which serves as a retaining wall; each zone of the bottom of tanks A, B and C is equipped with a temperature transmitter, one end of the high-purity hydrogen storage tank is connected to the hydrogen collection and purification treatment device, and the other end is connected to the gas bubbler distribution cluster device arranged at the bottom of zone B to regenerate the catalyst, the tank is equipped with a molten metal liquid level control system 18 and a high-value carbon transmission device 7.

[0040] Furthermore, the bottom of the pyrolysis tank, in zones A, B, and C, is raised by 80-100 mm in sequence to serve as a retaining wall and for controlling the liquid flow.

[0041] Furthermore, temperature transmitters 4 are installed in zones A, B, and C at the bottom of the pyrolysis tank.

[0042] The further natural gas bubbler cluster distribution device 2 includes: a bubbler cluster advance and retreat device, a natural gas pressure regulating valve, a flow regulating valve, a check valve, a flow switch, a metal hose connector, etc., and adopts the bubbler distribution cluster of Shanghai Jichi Glass Technology Co., Ltd.'s utility model patent "A Bubbling System Applied to Glass Melting Furnace" patent number ZL 201820037546.8.

[0043] The top cover of the natural gas cracking cell is hoisted by a steel structure. The outer shell of the top cover is made of steel plate, and the inner layer is made of refractory material for hanging. The inner layer is equipped with a three-phase silicon carbide rod heating system 13 on the top of the cell, a temperature transmitter 4, and a pressure transmitter 19 inside the cell. The tail end of the C zone is connected to a hydrogen collection and purification device 9 and a high-purity hydrogen storage tank 10.

[0044] The intermediate part of the pyrolysis tank is divided into a fixed seal and a movable seal as needed. The outer layer is made of steel plate and the inner layer is made of refractory material. It is equipped with an endoscopic industrial television 14, a tank temperature field detector 15, a tank cooling water tank 12, a linear motor 5, and a high-value carbon transmission device 7.

[0045] Furthermore, the endoscopic industrial television 14 adopts the utility model patent of Shanghai Jichi Glass Technology Co., Ltd.: a vertical endoscopic industrial television for float glass tin bath, patent number: ZL 201220391598.8.

[0046] Furthermore, the temperature field detector 15 inside the tank is intended to use a commercially available thermal imaging system that employs high-performance solid-state infrared imaging technology. It can penetrate the hydrogen gas inside the tank and clearly show the temperature of each point of interest. It has a very high practical temperature range and can meet the requirements for real-time temperature measurement and image analysis within a temperature range of 850℃~1800℃.

[0047] Furthermore, the linear motor 5 and the high-value carbon transmission device 7 in the tank are manufactured using proprietary technology of Shanghai Jichi Company or customized for the market. The high-value carbon transmission device has a variable frequency speed adjustment and an adjustable distance from the high-value carbon surface. The high-value carbon transmission device includes a circulating water-cooled transmission roller. The surface of the transmission roller has raised scrapers perpendicular to the direction of high-value carbon travel. The raised scrapers and the edge of the pyrolysis tank outlet form a stable outlet for high-value carbon. The high-value carbon outlet of the pyrolysis tank needs to be strictly sealed with high-silica cloth.

[0048] Furthermore, the high-value carbon outlet in zone C of the aforementioned natural gas cracking cell requires strict sealing with high-silica cloth.

[0049] The external devices of the natural gas cracking cell device 1 include a cracking cell supporting steel structure frame, a bottom cooling air system 6, a high-value carbon dispensing system 8, a hydrogen collection and purification system 9, a high-purity hydrogen storage tank 10, a circulating water cooling system 16, a natural gas control system 17, a regenerated gas control system 20, and a central control room computer system 21.

[0050] Furthermore, the aforementioned natural gas cracking cell supporting steel structure frame, composed of steel structure, serves to support the lower tank body and the top cover of the natural gas cracking cell. The lower tank body is supported to facilitate the installation of the natural gas bubbler cluster distribution device 2, the regenerated gas bubbler cluster device 3, the circulating water cooling system 16, the natural gas control system 17, and the regenerated gas control system 20. The top cover of the cracking cell is suspended to facilitate the manufacture of various equipment components of the upper, middle, and lower parts of the natural gas cracking cell.

[0051] Furthermore, the natural gas control system 17 is a natural gas bubbler cluster distribution device system at the bottom of Zone A that controls the natural gas inlet. It includes a natural gas bubbler cluster inlet / outlet device, a natural gas pressure regulating valve, a flow regulating valve, a check valve, a flow switch, a metal hose connector, natural gas qualified supply pressure, flow control and metering, natural gas on / off, various valves and various computer control sensors.

[0052] The further described regenerated gas control system 20 is a regenerated gas bubbler cluster device system at the bottom of Zone B that controls the regenerated gas inlet. It includes: a regenerated gas bubbler cluster device for inlet and outlet, a regenerated gas pressure regulating valve, a flow regulating valve, a check valve, a flow switch, a metal hose connector, regenerated gas qualified supply pressure, flow control and metering, regenerated gas on / off, various valves and various computer control sensors. This system is connected and integrated with the computer control system.

[0053] The further mentioned bottom cooling air system 6 includes a cooling fan, air ducts and control system, which is responsible for ensuring the temperature stability inside the tank and is connected and integrated with the computer control system.

[0054] Furthermore, the pyrolysis tank circulating water cooling system 16 is designed to ensure the normal operation of various instruments and systems, as the temperature inside the pyrolysis tank is as high as 800-1200°C. This system is connected and integrated with the computer control system.

[0055] Furthermore, the high-value carbon packaging system 8 cools, packages, and transports the high-value carbon to the finished product warehouse.

[0056] The further hydrogen collection and purification system 9 collects and purifies hydrogen to a hydrogen storage tank or a hydrogen utilization system.

[0057] Furthermore, the central control room computer system 21 includes a computer digital intelligent computer control system for power supply and distribution of the entire molten metal catalyst natural gas to hydrogen and high-value carbon cracking project, as well as for controlling the temperature, pressure, flow rate and reaction status of various operating conditions during the cracking process.

[0058] The method for producing hydrogen and high-value carbon using the aforementioned apparatus for direct cracking of natural gas includes the following: (1) The above-mentioned direct cracking of natural gas to produce hydrogen and high-value carbon devices were inspected and accepted, including: linear motor 5, bottom cooling air device 6, high-value carbon transmission device 7, high-value carbon separation device system 8, hydrogen collection and purification system 9, cooling water tank 12, three-phase silicon carbide rod heating system at the top of the tank 13, endoscopic industrial television 14, temperature field detector in the tank 15, circulating water cooling system 16, natural gas control system 17, central control room computer system 21, and various safety protection systems. The inspection and acceptance met the requirements.

[0059] (2) After each device and system has passed inspection and acceptance, it will enter the process of direct cracking of natural gas to produce hydrogen and high-value carbon using natural gas molten metal catalyst.

[0060] (3) Place the corresponding molten alloy metal catalyst liquid of the design weight of the corresponding cracking capacity in each of the A, B and C zones of the natural gas cracking tank 1. The catalyst liquid is Cu-Bi alloy or Cu-Sn alloy or Cu-Bi-Sn alloy. Turn on the three-phase silicon carbide rod heating system 13 at the top of the tank. The cracking tank is heated according to the given temperature curve, and the refractory material is guaranteed not to crack. When the temperature of the cracking tank reaches the given temperature of 600-800°C, turn on the nitrogen replacement air system in the cracking tank and replace the air in the tank with nitrogen.

[0061] (4) Melt the molten metal in the natural gas cracking tank according to the required melting temperature. After the cracking tank reaches the given temperature of 800-1200°C, turn on the natural gas control system 17 and the central control room computer system 21. Strictly control the natural gas bubbling device distribution cluster 2 at the bottom of area A according to the required gas supply pressure (0.5-1MPa), flow rate and velocity (0.1-0.25L / (M)). 2 Input qualified natural gas, and adjust various parameters such as natural gas input pressure, flow rate, bubbling frequency, and bubbling size through computer.

[0062] (5) Adjust the endoscopic industrial television 14 in the natural gas cracking cell to observe the bubbling and high-value carbon generation.

[0063] (6) Adjust the temperature field detector 15 inside the pyrolysis tank so that all points of interest are clearly visible. Adjust the computer system 21 in the central control room according to the given process requirements to maintain the temperature and temperature gradient of the temperature field in zones A, B, and C inside the pyrolysis tank so that the molten metal liquid is in normal working condition.

[0064] (7) Adjust the linear motor 5 to ensure that the high-value carbon in the molten metal flows from A to B to C.

[0065] (8) Adjust the hydrogen collection and purification system 9 to ensure normal hydrogen output and slight positive pressure in the pyrolysis tank.

[0066] (9) Adjust the high-value carbon transfer device 7 in the tank to make it at the normal gap with the tank outlet, so as to ensure that the high-value carbon enters the high-value carbon packaging system 8 smoothly. Adjust the circulating water cooling system 16 to stabilize the process temperature of the pyrolysis tank and ensure its normal operation.

[0067] (10) Adjust the high-value carbon dispensing system 8 to ensure that the high-value carbon is output normally.

[0068] (11) Every hour, the computer records the parameters of the natural gas cracking cell and the normal operation of hydrogen and high-value carbon production.

[0069] (12) If the production efficiency is found to be low, turn on the regenerated gas bubbler cluster device 3: input qualified regenerated gas, which is hydrogen or a mixture of hydrogen and natural gas. Strictly follow the required gas supply pressure, flow rate and speed. All parameters are connected to the operation panel and the central control room computer system 21. The central control room adjusts the regenerated gas input pressure and flow rate, and adjusts the bubbling frequency and bubbling size through the computer system 21.

[0070] (13) Observe the temperature distribution in the tank, observe the bubbling of the regenerated gas and the changes in the hydrogen and high-value carbon production efficiency through the endoscopic industrial television 14 and the temperature field detector 15. Once the hydrogen and high-value carbon production efficiency reaches the required level, the adjustment is completed and normal production begins.

[0071] (14) By formulating production process systems for various products and outputs of hydrogen and high-value carbon, adjusting the input pressure and flow rate of natural gas for direct cracking of natural gas to produce hydrogen and high-value carbon, and adjusting the temperature, pressure and flow rate of each system in the natural gas cracking cell, different varieties of high-value carbon (graphene) and hydrogen can be produced.

[0072] (15) The volume and floor space of direct cracking natural gas to hydrogen and high-value carbon production units differ depending on the production scale required for hydrogen and high-value carbon. The higher the hydrogen production, the larger the volume and floor space of the direct cracking natural gas to hydrogen and high-value carbon production unit system, and the engineering design and process methods should be adjusted according to the specific circumstances.

Claims

1. An apparatus for directly cracking natural gas to produce hydrogen and high-value carbon, characterized in that, This includes a cracking cell for producing hydrogen from natural gas and high-value carbon using molten metal as a catalyst, various process equipment for the cracking cell and its computer digital intelligent control system, hydrogen collection and purification treatment device, high-value carbon packaging system, high-value carbon transmission device and high-purity hydrogen storage tank. The cracking tank for hydrogen production from natural gas and high-value carbon using molten metal as a catalyst is designed as a medium-to-large tank. The cracking tank is divided into a lower tank body, an upper cover and an intermediate body. The intermediate body adopts a fixed seal or a movable seal. The tank body is supported by a steel structure. The lower tank's outer shell is constructed of steel plate, while the interior is made of refractory and insulation materials. The lower tank is characterized by being divided into three zones: A, B, and C, each containing a molten metal catalyst liquid. The catalyst liquid is a Cu-Bi alloy, a Cu-Sn alloy, or a Cu-Bi-Sn alloy. Zone A has a natural gas inlet at its bottom, where a cluster of natural gas bubblers is arranged. Each bubbler has a single orifice diameter of 0.8-6 mm, and each bubbler has 1 to 11 orifices. Zone B has a cluster of regeneration gas bubblers at its bottom, used for catalyst regeneration. Each bubbler has a single orifice diameter of 0.8 mm. -6mm, each bubbler has 1 to 11 round holes. Zone C is the molten metal clarification and high-value carbon output zone. The tank is equipped with a molten metal liquid level control system and a high-value carbon transfer device. The liquid level control accuracy is ±0.5 to ±1mm. The bottom zones of tanks A, B, and C are successively raised by 80-100mm to act as a retaining wall. Temperature transmitters are installed in the bottom zones of tanks A, B, and C. One end of the high-purity hydrogen storage tank is connected to the hydrogen collection and purification treatment device, and the other end is connected to the gas bubbler distribution cluster device arranged at the bottom of zone B to regenerate the catalyst. The top cover is hoisted by a steel structure. The outer shell of the top cover is made of steel plate, and the inside of the top cover is made of refractory material for hanging. The top cover is equipped with a three-phase silicon carbide heating system, a temperature transmitter, and a pressure transmitter in the tank. A hydrogen outlet connection device is installed at the tail of area C, which is connected to the hydrogen collection and purification treatment device. The middle part of the pyrolysis tank has a side wall shell made of steel plate and an interior made of refractory and insulation materials. It is divided into fixed seal and movable seal as needed. The middle part of the pyrolysis tank is equipped with an endoscopic industrial television, a tank temperature field detector, a tank cooling water tank, a linear motor to control the flow of molten metal and high-value carbon to the outlet, and a high-value carbon transmission device. The high-value carbon transmission device has a variable frequency speed control and an adjustable distance from the high-value carbon surface. The high-value carbon transmission device includes a circulating water-cooled transmission roller. The surface of the transmission roller has raised scrapers perpendicular to the direction of high-value carbon travel. The raised scrapers and the edge of the pyrolysis tank outlet form a stable outlet for high-value carbon. The high-value carbon outlet of the pyrolysis tank needs to be strictly sealed with high-silica cloth. The pyrolysis tank outlet is connected to the high-value carbon dispensing system.

2. A method for directly cracking natural gas to produce hydrogen and high-value carbon, characterized in that, The apparatus for direct pyrolysis of natural gas to produce hydrogen and high-value carbon as described in claim 1, and the method for direct pyrolysis of natural gas to produce hydrogen and high-value carbon, include the following steps: (1) Inspection and acceptance of each system of the natural gas cracking unit: including: natural gas cracking cell and natural gas control system, circulating water cooling system, bottom cooling air device, central control room computer system, endoscopic industrial television, temperature field detector inside the cell, cooling water tank inside the cell, linear motor, high value carbon transmission device, high value carbon dispensing system, hydrogen collection and purification system, and each safety assurance system have been inspected and accepted and meet the requirements. (2) After each unit and system has passed inspection and acceptance, it will enter the process of direct cracking of natural gas to produce hydrogen and high-value carbon using molten metal catalyst; (3) Place the designed weight of alloy metal in zones A, B, and C of the natural gas cracking cell, turn on the three-phase silicon carbide rod electric heating system at the top of the cell, and the cracking cell heats up according to the given temperature curve. When the metal in the cracking cell reaches the given temperature of 600-800°C, turn on the nitrogen replacement air system in the cracking cell and replace the air in the cell with nitrogen. (4) Melt the molten metal in the natural gas cracking tank according to the required melting temperature. Once the cracking tank reaches the given temperature of 800-1200°C, turn on the natural gas control system and the central control room computer system. Input qualified natural gas into the natural gas bubbler cluster distribution device at the bottom of Area A, strictly adhering to the required gas supply pressure of 0.3-1MPa and flow rate of 0.1-0.25L / (m³). 2 .s) Natural gas is supplied, and the input pressure, flow rate, bubbling frequency, and bubble size of the natural gas are adjusted by computer. (5) Turn on the endoscopic industrial television to observe the bubbling situation and the generation of hydrogen and high-value carbon. (6) Turn on the temperature field detector in the tank and the computer system in the central control room to maintain the temperature field in the tank, namely the temperature and temperature gradient of zones A, B and C. (7) Start the hydrogen collection and purification system to ensure normal hydrogen output and slight positive pressure in the cracking tank; start the linear motor to ensure that the molten metal liquid flows from area A to area B and then to area C, and flows to the high-value carbon transfer device in area C; start the high-value carbon transfer device in the tank to match the gap of the cracking tank outlet with the high-value carbon production, to ensure that the high-value carbon flows out smoothly to the high-value carbon dispensing system; adjust the circulating cooling water system to ensure that the working temperature of each system is normal. (8) Turn on the high-value carbon dispensing system to enable normal output of high-value carbon; (9) Observe the production of hydrogen and high-value carbon. If the efficiency of the cracking unit system is found to be reduced, turn on the regenerated gas bubbler cluster device. The regenerated gas is hydrogen. Input qualified regenerated gas. Connect all parameters to the operation panel and the computer system in the central control room. Adjust the regenerated gas input pressure, flow rate and bubble frequency and bubble size through the panel. Observe the temperature distribution in the tank through the temperature field detector. Observe the regenerated gas bubbling and hydrogen and high-value carbon generation through the endoscopic industrial television. Monitor the changes in hydrogen and high-value carbon generation efficiency until the hydrogen and high-value carbon production efficiency reaches the requirements. The adjustment is then completed.

3. The method according to claim 2, characterized in that, By installing a liquid level control system, in-tank temperature transmitter, pressure transmitter, endoscopic industrial television, and in-tank temperature field detector inside the natural gas cracking cell, the natural gas cracking conditions can be stabilized, ensuring that the direct cracking of natural gas to produce hydrogen and high-value carbon processes reach production targets.

4. The method according to claim 3, characterized in that, By using a structure with the bottom of the natural gas cracking cell raised by 80-100mm in each of the three zones (A, B, and C) and a linear motor configuration, the flow field of the molten metal catalyst is controlled, as well as the flow direction of the catalyst liquid and high-value carbon, so that the high-value carbon can flow smoothly to the high-value carbon outlet.

Images