A method and system for producing carbon material and hydrogen gas from sulfur and nitrogen-containing oil

Abstract

The application provides a method and system for preparing sulfur and nitrogen containing oil into carbon material and hydrogen, comprising a down-flow fluidized bed, an up-flow fluidized bed and a purification separation device. The sulfur and nitrogen containing oil is introduced into the down-flow fluidized bed, and hard carbon, hydrogen and light hydrocarbon are generated, and the organic sulfur and nitrogen components are changed into hydrogen sulfide and ammonia. The solid in the cracking product is intercepted at the bottom of the up-flow fluidized bed under the action of a porous partition plate and a cyclone separator. The gas is treated by the purification separation device, and after the hydrogen sulfide and ammonia in the gas are removed, pure hydrogen and light hydrocarbon are separated. The light hydrocarbon is recycled from the bottom of the device to the up-flow fluidized bed, and carbon nanotubes are generated under the action of a metal catalyst in a high-temperature environment provided by the hard carbon. The system effectively avoids the poisoning effect of sulfur and nitrogen in the oil on the metal catalyst, and uses the heat generated by high-temperature pyrolysis to provide energy for the preparation of carbon nanotubes. The system has the advantages of short process, long service life of the catalyst, continuous operation and low-cost production of carbon material and hydrogen.

Description

Technical Field

[0001] This invention relates to the field of materials and chemical engineering, specifically to a method and system for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products. Background Technology

[0002] Sulfur- and nitrogen-containing petroleum products are often byproducts of crude oil and coal processing, and may also be low-value residues from chemical processing. The most common sulfur- and nitrogen-containing petroleum products include catalytic diesel, petroleum tar, coal tar, and biomass tar, often occurring as mixtures and containing large amounts of polycyclic aromatic hydrocarbons (PAHs). Their cumulative amount is enormous, potentially reaching hundreds of millions of tons annually. The most common processing method is hydrocracking, which converts them into monocyclic aromatic hydrocarbons or gasoline-like components. However, this method has low yields, consumes large amounts of hydrogen, and requires stringent conditions.

[0003] Furthermore, producing carbon materials and hydrogen from these low-value materials through pyrolysis is a win-win situation. However, current technologies cannot yet achieve efficient utilization of the pyrolysis products. Summary of the Invention

[0004] To address the aforementioned problems in existing technologies, this invention provides a method and system for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products. The system includes a descending fluidized bed, an ascending fluidized bed, and a purification and separation device. This system effectively avoids the poisoning effect of sulfur and nitrogen in the oil on the metal catalyst, and utilizes the heat generated by high-temperature pyrolysis to power the preparation of carbon nanotubes. It features a short process flow, long catalyst life, continuous operation, and low-cost production of carbon materials and hydrogen. The specific details of the invention are as follows:

[0005] In a first aspect, the present invention provides a system for preparing sulfur- and nitrogen-containing oil products into carbon materials and hydrogen, the system comprising: a thermal cracking downward fluidized bed 1, a catalytic cracking upward fluidized bed 2, and a purification and separation device 3;

[0006] The pyrolysis downflow fluidized bed 1 is provided with a sulfur- and nitrogen-containing oil inlet 8 and a pyrolysis product outlet 9;

[0007] The catalytic cracking upward fluidized bed 2 is provided with, in sequence along the gas flow direction, a light hydrocarbon gas inlet 12, a catalyst inlet 7, a cracking product inlet 10 connected to the cracking product outlet 9, a porous distribution plate 11, a cyclone separator 6, a mixed gas outlet 16, and a carbon material outlet 13; wherein, the light hydrocarbon gas inlet 12 is located at the bottom of the catalytic cracking upward fluidized bed 2, the mixed gas outlet 16 is located at the top of the catalytic cracking upward fluidized bed 2 and connected to the cyclone separator 6, the catalyst inlet 7 is located close to the light hydrocarbon gas inlet 12, and the cracking product inlet 10 is located above the catalyst inlet 7 to avoid contact between hydrogen sulfide and ammonia in the cracking products and the catalyst;

[0008] The purification and separation device 3 is provided with a mixed gas inlet 17 connected to the mixed gas outlet 16, a light hydrocarbon gas outlet 20 connected to the light hydrocarbon gas inlet 12, and a purified target product hydrogen outlet 25.

[0009] Optionally, the purification and separation device 3 includes: a heat exchange device 3-1, a desulfurization and denitrification device 3-2, and a separation device 3-3;

[0010] The heat exchange device 3-1 is provided with a heat exchange gas outlet 18 and a light hydrocarbon gas inlet 19. The heat exchange device 3-1 is connected to the mixed gas outlet 16 through a mixed gas inlet 17 and to the light hydrocarbon gas inlet 12 through the light hydrocarbon gas outlet 20. The heat exchange device 3-1 is used to cool the mixed gas entering through the mixed gas inlet 17 and to heat the light hydrocarbon gas entering through the light hydrocarbon gas inlet 19.

[0011] The desulfurization and denitrification device 3-2 is provided with a heat exchange gas inlet 21 and a desulfurization and denitrification gas outlet 22 connected to the heat exchange gas outlet 18; the desulfurization and denitrification device 3-2 is used to remove hydrogen sulfide and ammonia from the mixed gas that enters it through the heat exchange gas inlet 21.

[0012] The separation device 3-3 is provided with a desulfurization and denitrification gas inlet 23 connected to the desulfurization and denitrification gas outlet 22, a hydrogen outlet 25, and a light hydrocarbon gas outlet 24 connected to the light hydrocarbon gas inlet 19. The separation device 3-3 is used to separate the light hydrocarbons and hydrogen that enter through the desulfurization and denitrification gas inlet 23.

[0013] Optionally, the operating temperature of the heat exchange device 3-1 is 300-500℃.

[0014] In a second aspect, the present invention provides a method for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products, the method being applicable to the system described in the first aspect above, the method comprising the following steps:

[0015] S1. Sulfur-nitrogen-containing oil is fed into the thermal cracking downflow fluidized bed 1 through the sulfur-nitrogen-containing oil inlet 8 to carry out thermal cracking reaction, and obtain cracking products containing hard carbon, light hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0016] S2. The pyrolysis products are fed into the catalytic pyrolysis upward fluidized bed 2 through the pyrolysis product inlet 10 for gas-solid separation, so as to retain the hard carbon in the pyrolysis products and output the gaseous substances in the pyrolysis products.

[0017] S3. The gaseous substance obtained in step S2 enters the purification and separation device 3 through the mixed gas inlet 17 to remove hydrogen sulfide and ammonia from the gaseous substance and separate light hydrocarbons and hydrogen, wherein the hydrogen is the target product.

[0018] S4. The light hydrocarbons obtained in step S3 are introduced into the catalytic cracking upward fluidized bed 2 through the light hydrocarbon gas inlet 12, and then a catalyst is added through the catalyst inlet 7. The light hydrocarbons undergo a catalytic cracking reaction to generate the target product carbon nanotubes.

[0019] Optionally, the purification and separation device 3 includes a heat exchange device 3-1, a desulfurization and denitrification device 3-2, and a separation device 3-3. Step S3 specifically involves:

[0020] S31. The gaseous substance obtained in step S2 is introduced into the heat exchange device 3-1 through the mixed gas inlet 17 for cooling treatment.

[0021] S32. The cooled gaseous substance is introduced into the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21 to remove hydrogen sulfide and ammonia from the gaseous substance and obtain a mixed gas composed of light hydrocarbons and hydrogen.

[0022] S33. The mixed gas obtained in step S32 is introduced into the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate light hydrocarbons and hydrogen, wherein the hydrogen is the target product.

[0023] Optionally, in step S1, the temperature required for the thermal decomposition reaction is 800-1100℃, and the time is 1-20s.

[0024] Optionally, in step S31, the temperature of the gaseous substance obtained by the cooling treatment is 300-500℃.

[0025] Optionally, in step S32, the desulfurization and denitrification device 3-2 removes hydrogen sulfide and ammonia from the gaseous substance by water washing or acid-base neutralization.

[0026] Optionally, in step S33, the separation device 3-3 separates light hydrocarbons and hydrogen by pressure swing adsorption.

[0027] Optionally, the sulfur-nitrogen-containing oil product is at least one of catalytic diesel oil, coal tar, residual oil, crude oil slurry, biomass tar, and petroleum tar with or without asphalt, wherein the sulfur content of the sulfur-nitrogen-containing oil product is 10-12000 mg / kg, and the nitrogen content of the sulfur-nitrogen-containing oil product is 20-5000 mg / kg.

[0028] The catalyst is a metal catalyst containing iron, cobalt, or nickel; or the catalyst is a binary metal catalyst composed of the metal catalyst and molybdenum, copper, manganese, or tungsten.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] (1) This invention provides a system for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products. By combining high-temperature pyrolysis technology with medium-temperature catalytic cracking technology, it simultaneously produces two products: hydrogen and carbon nanotubes, increasing the added value of the products by 3-10 times compared to those obtained by high-temperature pyrolysis technology alone. Furthermore, the combination of high-temperature pyrolysis technology and medium-temperature catalytic cracking technology to prepare carbon materials and hydrogen can convert organic sulfur and organic nitrogen in sulfur- and nitrogen-containing oil products into hydrogen sulfide and ammonia, thereby simplifying the desulfurization and denitrification process. Hydrogen sulfide and ammonia can be completely removed simply by water washing or acid-base neutralization. Moreover, the amount of desulfurizing and denitrifying agents used is small, reducing costs by 30-50%.

[0031] (2) The system provided by the present invention for preparing sulfur-nitrogen-containing oil into carbon materials and hydrogen, through the reasonable setting of the structure of the catalytic cracking upward fluidized bed 2, the cracking products entering it will not come into direct contact with the metal catalyst, thus avoiding the poisoning effect of hydrogen sulfide and ammonia on the metal catalyst, increasing the catalyst life by 3-5 times, thereby increasing the purity of carbon nanotube products by 20-40%.

[0032] (3) The system provided by the present invention for preparing sulfur- and nitrogen-containing oil products into carbon materials and hydrogen is connected to a catalytic cracking upward fluidized bed 2 via a thermal cracking downward fluidized bed 1, thereby achieving the coupling of two endothermic reactions (thermal cracking reaction of sulfur- and nitrogen-containing oil products and catalytic cracking reaction of light hydrocarbons). It effectively utilizes the high-temperature thermal energy of thermal cracking technology, and uses the high temperature carried by the thermal cracking products (hard carbon) to heat the catalyst and light hydrocarbons that participate in the subsequent catalytic cracking reaction. This allows the catalytic cracking reaction of light hydrocarbons to be completed without providing additional energy to the catalytic cracking upward fluidized bed 2, thereby reducing the energy supply cost by 20-40%.

[0033] (4) The method for preparing sulfur-nitrogen-containing oil products into carbon materials and hydrogen provided by the present invention has a wide range of raw material adaptability, including catalytic diesel, coal tar, residual oil, crude oil slurry, biomass tar, petroleum tar and their mixtures, and smoothly converts these low-value raw materials under low energy consumption conditions to obtain high-value materials (carbon nanotubes, hydrogen and hard carbon). Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1A schematic diagram of the system structure for preparing sulfur-nitrogen-containing oil products into carbon materials and hydrogen is shown in an embodiment of the present invention.

[0036] Figure 2 This invention provides a schematic diagram of another system structure for preparing sulfur-nitrogen-containing oil products into carbon materials and hydrogen, according to an embodiment of the present invention.

[0037] Figure 3 A flowchart of a method for preparing carbon materials and hydrogen from sulfur-nitrogen-containing oil products according to an embodiment of the present invention is shown. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. Based on the embodiments of the present invention, any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention. Furthermore, all other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of the present invention.

[0039] Specific experimental steps or conditions are not specified in the embodiments; they can be performed according to the conventional experimental steps or conditions described in the prior art. Reagents and other instruments used, unless otherwise specified, are all commercially available conventional reagent products. Furthermore, the accompanying drawings are merely illustrative diagrams of the embodiments of the present invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and therefore, repeated descriptions of them will be omitted. Some block diagrams shown in the drawings are functional entities and do not necessarily correspond to physically or logically independent entities.

[0040] Techniques, methods, and equipment known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and equipment should be considered part of the specification.

[0041] In the description of this invention, it should be understood that the use of terms such as "first" and "second" to define components is merely for the purpose of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0042] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0043] The primary objective of this invention is to provide a system for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products, as detailed below. Figure 1 , Figure 1 This diagram illustrates the structure of a system for preparing sulfur- and nitrogen-containing oils into carbon materials and hydrogen, as provided in an embodiment of the present invention. Figure 1 As shown, it includes: a thermal cracking downward fluidized bed 1, a catalytic cracking upward fluidized bed 2, and a purification and separation unit 3; wherein, the thermal cracking downward fluidized bed 1 is provided with a sulfur- and nitrogen-containing oil inlet 8 and a cracking product outlet 9. The thermal cracking downward fluidized bed 1 is used to crack the sulfur- and nitrogen-containing oil that enters it through the sulfur- and nitrogen-containing oil inlet 8 to obtain hard carbon, light hydrocarbons, hydrogen, hydrogen sulfide, and ammonia; the cracking products exit the thermal cracking downward fluidized bed 1 through the cracking product outlet 9 and then enter the catalytic cracking upward fluidized bed 2.

[0044] The catalytic cracking upward fluidized bed 2 is provided with the following components arranged sequentially along the gas flow direction: a light hydrocarbon gas inlet 12, a catalyst inlet 7, a cracking product inlet 10 connected to the cracking product outlet 9, a porous distribution plate 11, a cyclone separator 6, a mixed gas outlet 16, and a carbon material outlet 13. The light hydrocarbon gas inlet 12 is located at the bottom of the catalytic cracking upward fluidized bed 2, the mixed gas outlet 16 is located at the top of the catalytic cracking upward fluidized bed 2 and is connected to the cyclone separator 6, the catalyst inlet 7 is located close to the light hydrocarbon gas inlet 12, and the cracking product inlet 10 is located above the catalyst inlet 7 to avoid contact between hydrogen sulfide and ammonia in the cracking products and the catalyst.

[0045] The catalytic cracking upward fluidized bed 2 is used to perform gas-solid separation of the cracking products entering it through the cracking product inlet 10. A porous distribution plate 11 is set perpendicular to the gas flow direction and located at the waist of the catalytic cracking upward fluidized bed 2. It is used to trap solid matter (hard carbon) in the cracking products, causing the solid matter to accumulate at the bottom of the catalytic cracking upward fluidized bed 2. Since the porous distribution plate 11 cannot trap 100% of the solid matter, a trace amount (2-4%) of fine-particle-size solid matter remains mixed in the gaseous cracking products. A cyclone separator 6 is used to further separate the solid and gas of the cracking products passing through the transverse porous distribution plate 11, and to transport the separated solid matter to the bottom of the catalytic cracking upward fluidized bed 2. The gaseous cracking products exit the catalytic cracking upward fluidized bed 2 through the cracking product outlet 9.

[0046] The purification and separation device 3 is equipped with a mixed gas inlet 17 connected to the mixed gas outlet 16, a light hydrocarbon gas outlet 20 connected to the light hydrocarbon gas inlet 12, and a purified target product hydrogen gas outlet 25. The purification and separation device 3 removes hydrogen sulfide and ammonia from the gaseous substances (light hydrocarbons, hydrogen, hydrogen sulfide, and ammonia) entering through the mixed gas inlet 17, and then separates the light hydrocarbons and hydrogen to obtain the target product hydrogen.

[0047] Furthermore, the light hydrocarbons separated by the purification and separation device 3 are output through the light hydrocarbon gas outlet 20 and then enter the catalytic cracking upward fluidized bed 2. The catalytic cracking upward fluidized bed 2 is also used for catalytic cracking of the light hydrocarbons that enter through the light hydrocarbon gas inlet 12 to obtain the target product, carbon nanotubes. The metal catalyst used in the catalytic cracking reaction is added through the catalyst inlet 7. Since the catalyst inlet 7 exists independently of the cracking product inlet 10 and is located below the cracking product inlet 10, the hydrogen sulfide and ammonia in the cracking products will not come into contact with the metal catalyst, thus avoiding the poisoning effect of hydrogen sulfide and ammonia on the metal catalyst. At the same time, since there are thermal cracking products (hard carbon) at the bottom of the catalytic cracking upward fluidized bed 2, the high temperature carried by the thermal cracking products (hard carbon) is used to heat the catalyst and light hydrocarbons participating in the catalytic cracking reaction. This allows the process of catalyzing light hydrocarbons with the metal catalyst to be completed without additional heating, and the catalytic cracking reaction of light hydrocarbons to obtain the target product, carbon nanotubes, is completed without providing additional energy to the catalytic cracking upward fluidized bed 2. This effectively utilizes the high-temperature thermal energy of thermal cracking technology, reducing energy supply costs by 20-40%. It achieves the coupling of two endothermic reactions (the thermal cracking reaction of sulfur and nitrogen-containing oil products and the catalytic cracking reaction of light hydrocarbons).

[0048] In some embodiments, the purification and separation device 3 includes: a heat exchange device 3-1, a desulfurization and denitrification device 3-2, and a separation device 3-3; Figure 2 This invention provides a schematic diagram of another system structure for preparing sulfur- and nitrogen-containing oil products into carbon materials and hydrogen, as shown in an embodiment of the invention. Figure 2 As shown, the heat exchanger 3-1 operates at a temperature of 300-500℃ and is equipped with a heat exchange gas outlet 18 and a light hydrocarbon gas inlet 19. The heat exchanger 3-1 is connected to the mixed gas outlet 16 through the mixed gas inlet 17 and to the light hydrocarbon gas inlet 12 through the light hydrocarbon gas outlet 20. The heat exchanger 3-1 is used to cool the mixed gas that enters through the mixed gas inlet 17.

[0049] The desulfurization and denitrification device 3-2 is provided with a heat exchange gas inlet 21 and a desulfurization and denitrification gas outlet 22 connected to the heat exchange gas outlet 18; the desulfurization and denitrification device 3-2 is used to remove hydrogen sulfide and ammonia from the mixed gas that enters it through the heat exchange gas inlet 21.

[0050] The separation device 3-3 is provided with a desulfurization and denitrification gas inlet 23 connected to the desulfurization and denitrification gas outlet 22, a hydrogen outlet 25, and a light hydrocarbon gas outlet 24 connected to the light hydrocarbon gas inlet 19. The separation device 3-3 is used to separate the light hydrocarbons and hydrogen that enter through the desulfurization and denitrification gas inlet 23.

[0051] Furthermore, before the light hydrocarbons separated by the separation device 3-3 are returned to the catalytic cracking upward fluidized bed 2 for catalytic cracking reaction, they are introduced into the heat exchange device 3-1 through the light hydrocarbon gas inlet 19. The light hydrocarbons are heated by the operating temperature (300-500℃) of the heat exchange device 3-1, so that the light hydrocarbons are heated before entering the catalytic cracking upward fluidized bed 2. The heated light hydrocarbons can further reduce / avoid the additional energy required for the catalytic cracking reaction, and further improve the energy utilization rate of the system.

[0052] Secondly, the present invention provides a method for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products, the method being applicable to the system described in the first aspect above. Figure 3 A flowchart illustrating a method for preparing carbon materials and hydrogen from sulfur- and nitrogen-containing oil products according to an embodiment of the present invention is shown, as follows. Figure 3 As shown, the method includes the following steps:

[0053] S1. Sulfur-nitrogen-containing oil is fed into the thermal cracking downflow fluidized bed 1 through the sulfur-nitrogen-containing oil inlet 8 to carry out thermal cracking reaction, and obtain cracking products containing hard carbon, light hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0054] In this step, the sulfur- and nitrogen-containing oil is at least one of the following: catalytic diesel oil (with or without asphalt), coal tar, residual oil, crude oil slurry, biomass tar, and petroleum tar. The sulfur content of the sulfur- and nitrogen-containing oil is 10-12000 mg / kg, and the nitrogen content is 20-5000 mg / kg. The thermal cracking reaction is carried out at a temperature of 800-1100℃ and a pressure of 0.1-1 MPa. The residence time of the oil in the downward-flowing fluidized bed 1 for thermal cracking is 1-20 s. The obtained light hydrocarbons are specifically C1-C2. 10 Hydrocarbons.

[0055] S2. The pyrolysis products are fed into the catalytic pyrolysis upward fluidized bed 2 through the pyrolysis product inlet 10 for gas-solid separation, so as to retain the hard carbon in the pyrolysis products and output the gaseous substances in the pyrolysis products.

[0056] In this step, due to the obstruction of the transverse porous distribution plate in the upward-flowing fluidized bed 2 of the catalytic cracking, 96% to 98% of the solids are retained in the dense phase zone 14. Trace amounts of solids, along with the gaseous substances, enter the dilute phase zone 15. Continuing upwards, the solids enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the upward-flowing fluidized bed 2 of the catalytic cracking, while the gaseous substances are output through the mixed gas outlet 16.

[0057] S3. The gaseous substances obtained in step S2 enter the purification and separation device 3 through the mixed gas inlet 17 to remove hydrogen sulfide and ammonia from the gaseous substances and separate light hydrocarbons and hydrogen, with hydrogen as the target product.

[0058] Furthermore, the purification and separation device 3 includes a heat exchange device 3-1, a desulfurization and denitrification device 3-2, and a separation device 3-3. Step S3 specifically involves:

[0059] S31. The gaseous substance obtained in step S2 is introduced into the heat exchange device 3-1 through the mixed gas inlet 17 for cooling treatment; the temperature of the gaseous substance obtained after cooling treatment is 300-500℃.

[0060] S32. The cooled gaseous substance is introduced into the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21 to remove hydrogen sulfide and ammonia from the gaseous substance, and a mixed gas composed of light hydrocarbons and hydrogen is obtained. The desulfurization and denitrification device 3-2 removes hydrogen sulfide and ammonia from the gaseous substance by water washing or acid-base neutralization.

[0061] S33. The mixed gas obtained in step S32 is introduced into the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate light hydrocarbons and hydrogen, with hydrogen as the target product; the separation device 3-3 separates light hydrocarbons and hydrogen by pressure swing adsorption.

[0062] S4. The light hydrocarbons obtained in step S3 are introduced into the catalytic cracking upward fluidized bed 2 through the light hydrocarbon gas inlet 12, and then a catalyst is added through the catalyst inlet 7. The light hydrocarbons undergo catalytic cracking reaction to generate the target product carbon nanotubes.

[0063] In this step, the light hydrocarbons entering the upward fluidized bed 2 for catalytic cracking are purified light hydrocarbons, free of hydrogen sulfide and ammonia. The metal catalyst used in the catalytic cracking reaction is added through catalyst inlet 7, contacting the hard carbon at the bottom of the upward fluidized bed 2. The high temperature carried by the thermal cracking products (hard carbon) heats the catalyst and light hydrocarbons participating in the intermediate-temperature catalytic cracking reaction, bringing them to a reaction temperature of 700-850℃. This allows the metal catalyst to catalyze the light hydrocarbons without additional heating, completing the catalytic cracking reaction of light hydrocarbons to obtain carbon nanotubes without providing additional energy to the upward fluidized bed 2. This effectively utilizes the high-temperature thermal energy of thermal cracking technology, reducing energy costs. The catalyst used is a metal catalyst containing iron, cobalt, or nickel; or a binary metal catalyst composed of a metal catalyst and molybdenum, copper, manganese, or tungsten.

[0064] In this step, the light hydrocarbons will also generate hydrogen and a small amount of methane through the medium-temperature catalytic cracking reaction. This part of the gas will be combined with the gas (H2, H2S, NH3 and light hydrocarbons) that enters the fluidized bed 1 through the cracking product inlet 10 and then enters the upward fluidized bed 2 of the catalytic cracking, which will play a role in diluting H2S and ammonia.

[0065] Furthermore, by continuously feeding sulfur- and nitrogen-containing oil into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and by feeding catalyst into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, the above process can be made into continuous operation.

[0066] To enable those skilled in the art to more clearly understand the present invention, the method of the present invention will now be described in detail through the following embodiments.

[0067] Example 1

[0068] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0069] Sulfur- and nitrogen-containing oil (catalytic diesel, sulfur content 12000 mg / kg, nitrogen content 1000 mg / kg, boiling point 200-400℃) is fed into the thermal cracking downward fluidized bed 1 through inlet 8. At 1100℃ and 0.1 MPa, the residence time is controlled to be 1 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0070] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic pyrolysis upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 96% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic pyrolysis upward fluidized bed 2.

[0071] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. After being heated to 500℃, the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18, and then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. Using conventional techniques (such as water washing, acid-base neutralization, etc.), all sulfur and nitrogen are removed. The gas then exits through the desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through the desulfurization and denitrification gas inlet 23 for the separation of hydrogen and hydrocarbons. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption, etc.), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0072] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 500°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0073] A metallic catalyst (containing iron) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 700°C. The hydrocarbon gas contacts the catalyst for 0.1 min, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 8 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0074] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 through the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 through the catalyst inlet 7 every 8 hours, so that the above process is continuous.

[0075] Example 2

[0076] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0077] The sulfur- and nitrogen-containing oil (coal tar, sulfur content 7200 mg / kg, nitrogen content 5000 mg / kg, boiling point 200-380℃) is fed into the thermal cracking downward fluidized bed 1 through inlet 8. At 920℃ and 1MPa, the residence time is controlled at 20s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0078] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 98% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0079] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 300℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0080] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 300°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0081] A metallic catalyst (containing nickel) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 850°C. The hydrocarbon gas contacts the catalyst for 2 minutes, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 5 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0082] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0083] Example 3

[0084] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0085] Sulfur- and nitrogen-containing oil (petroleum tar, sulfur content 8500 mg / kg, nitrogen content 5000 mg / kg, boiling point 350-400℃) is introduced into the thermal cracking downward fluidized bed 1 through inlet 8. At 920℃ and 0.5 MPa, the residence time is controlled at 10 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0086] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 98% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0087] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 400℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0088] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 400°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0089] A metal catalyst (containing cobalt and molybdenum) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 850°C. The hydrocarbon gas contacts the catalyst for 2 minutes, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 10 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0090] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0091] Example 4

[0092] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0093] Sulfur- and nitrogen-containing oil (biomass tar, sulfur content 10 mg / kg, nitrogen content 20 mg / kg, boiling point 200-300℃) is introduced into the thermal cracking downward fluidized bed 1 through inlet 8. At 800℃ and 0.2 MPa, the residence time is controlled at 5 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0094] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 97% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0095] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 450℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0096] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 400°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0097] A metallic catalyst (containing nickel and copper) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, and the temperature reaches 750°C. The hydrocarbon gas has a contact time of 0.6 min with the catalyst, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 6 hours, and the resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13 to form a carbon material product.

[0098] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0099] Example 5

[0100] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0101] Sulfur- and nitrogen-containing oil (residue oil, sulfur content 500 mg / kg, nitrogen content 5000 mg / kg, boiling point 350-400℃) is fed into the thermal cracking downward fluidized bed 1 through inlet 8. At 800℃ and 0.8 MPa, the residence time is controlled at 16 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0102] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 96.5% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0103] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 480℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0104] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 450°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0105] A metallic catalyst (containing nickel and manganese) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 780°C. The hydrocarbon gas contacts the catalyst for 1.2 minutes, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled to 2 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0106] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0107] Example 6

[0108] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0109] Sulfur- and nitrogen-containing oil products (crude oil slurry, sulfur content 500 mg / kg, nitrogen content 20 mg / kg, boiling point 300-400℃) are fed into the thermal cracking downward fluidized bed 1 through inlet 8. At 850℃ and 1 MPa, the residence time is controlled at 12 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0110] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 96.7% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0111] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 380℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0112] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 300°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0113] A metallic catalyst (containing nickel and tungsten) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, and the temperature reaches 800℃. The hydrocarbon gas is in contact with the catalyst for 1.6 min, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 14 hours, and the resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13 to form a carbon material product.

[0114] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0115] Example 7

[0116] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0117] Sulfur- and nitrogen-containing oil products (20% asphalt and 80% catalytic diesel, sulfur content 5500 mg / kg, nitrogen content 2020 mg / kg, boiling point 300-450℃) are introduced into the thermal cracking downward fluidized bed 1 through inlet 8. At 1050℃ and 0.1 MPa, the residence time is controlled at 11s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0118] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 97.7% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0119] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 480℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0120] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 450°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0121] A metallic catalyst (containing iron and molybdenum) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 750°C. The hydrocarbon gas contacts the catalyst for 1.2 minutes, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 3 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0122] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0123] Example 8

[0124] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2 The structural diagrams shown are connected sequentially.

[0125] Sulfur- and nitrogen-containing oil products (80% asphalt and 20% biodiesel, with sulfur content of 3500 mg / kg, nitrogen content of 920 mg / kg, and boiling point of 250-450℃) are introduced into the thermal cracking downward fluidized bed 1 through inlet 8. At 1000℃ and 0.2 MPa, the residence time is controlled at 11 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide, and ammonia.

[0126] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic cracking upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 97.6% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic cracking upward fluidized bed 2.

[0127] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 430℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0128] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 400°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 as a fluidizing gas and reaction medium.

[0129] A metallic catalyst (containing iron and molybdenum) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 780°C. The hydrocarbon gas contacts the catalyst for 1 minute, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 6 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0130] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0131] Example 9

[0132] Thermochemical downward fluidized bed 1, catalytic cracking upward fluidized bed 2, heat exchange device 3-1, desulfurization and denitrification device 3-2, and separation device 3-3 are as follows: Figure 2The structural diagrams shown are connected sequentially.

[0133] Sulfur- and nitrogen-containing oil (30% coal tar and 70% residue oil, sulfur content 4500 mg / kg, nitrogen content 4200 mg / kg, boiling point 280-450℃) is introduced into the thermal cracking downward fluidized bed 1 through inlet 8. At 1080℃ and 0.5 MPa, the residence time is controlled at 11 s, and the oil is cracked into hard carbon, C1-C10 hydrocarbons, hydrogen, hydrogen sulfide and ammonia.

[0134] The aforementioned gaseous and solid products exit the fluidized bed 1 from the pyrolysis product outlet 9 and enter the catalytic pyrolysis upward fluidized bed 2 via the pyrolysis product inlet 10. Due to the obstruction of the transverse porous distribution plate, 96.6% of the solids are retained in the solid dense phase region 14. A small amount of solids enters the solid dilute phase region 15 along with the gas. Continuing upward, they enter the cyclone separator 6. After gas-solid separation, the solids return to the bottom of the catalytic pyrolysis upward fluidized bed 2.

[0135] After exiting the catalytic cracking upward fluidized bed 2 through mixed gas outlet 16, the gas enters the heat exchanger 3-1 through mixed gas inlet 17. The temperature is controlled at 490℃, and the gas exits the heat exchanger 3-1 through heat exchange gas outlet 18. It then enters the desulfurization and denitrification unit 3-2 through heat exchange gas inlet 21. After removing all sulfur and nitrogen using conventional techniques (such as water washing and acid-base neutralization), the gas exits through desulfurization and denitrification gas outlet 22, and then enters the separation unit 3-3 through desulfurization and denitrification gas inlet 23 for hydrogen and hydrocarbon separation. The purified hydrogen, separated using conventional techniques (such as pressure swing adsorption), exits through hydrogen outlet 25, and the target product hydrogen is collected.

[0136] The separated light hydrocarbon gas exits the separation device 3-3 from the light hydrocarbon gas outlet 24, and then enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 to be heated to 460°C. After exiting the heat exchange device 3-1 from the light hydrocarbon gas outlet 20, it is recycled back to the light hydrocarbon gas inlet 12 and enters the catalytic cracking upward fluidized bed 2 to be used as fluidizing gas and reaction medium.

[0137] A metallic catalyst (containing nickel and molybdenum) is added to the catalytic cracking upward fluidized bed 2 through catalyst inlet 7. The catalyst mixes with hard carbon at the bottom and hydrocarbon gas entering through light hydrocarbon gas inlet 12, reaching a temperature of 820°C. The hydrocarbon gas contacts the catalyst for 0.8 minutes, cracking to produce carbon nanotubes and hydrogen or a small amount of methane. The generated hydrogen and a small amount of methane combine with the gases (H2, H2S, NH3, and hydrocarbons) entering through cracking product inlet 10, diluting the H2S and ammonia. The reaction time is controlled at 7 hours. The resulting mixture of carbon nanotubes and hard carbon exits the catalytic cracking upward fluidized bed 2 through outlet 13, forming a carbon material product.

[0138] Sulfur- and nitrogen-containing oil is continuously fed into the thermal cracking downward fluidized bed 1 from the sulfur- and nitrogen-containing oil inlet 8, and catalyst is fed into the catalytic cracking upward fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the above process forms a continuous operation.

[0139] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0140] For the sake of simplicity, the method embodiments are described as a series of actions. However, those skilled in the art should understand that the present invention is not limited to the described order of actions, as some steps can be performed in other orders or simultaneously according to the present invention. Furthermore, those skilled in the art should also understand that the embodiments described in the specification are preferred embodiments, and the actions and components involved are not necessarily essential to the present invention.

[0141] The above provides a detailed description of the method for preparing porous carbon and its multi-stage fluidized bed reactor provided by the present invention. Specific examples have been used to illustrate the principle and implementation of the present invention. The description of the above embodiments is only for the purpose of helping to understand the method and core idea of ​​the present invention. At the same time, for those skilled in the art, there will be changes in the specific implementation and application scope based on the idea of ​​the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A system for producing carbon material and hydrogen gas from a sulfur and nitrogen containing oil product, the system comprising: a reactor vessel; a catalyst; and a hydrogen source. The system comprises a thermal cracking down-flow fluidized bed, a catalytic cracking up-flow fluidized bed and a purification separation device; The thermal cracking down-flow fluidized bed is provided with a sulfur and nitrogen-containing oil product inlet and a cracking product outlet; The catalytic cracking up-flow fluidized bed is sequentially provided with a first light hydrocarbon gas inlet, a catalyst inlet, a cracking product inlet communicated with the cracking product outlet, a porous distribution plate, a cyclone separator, a mixed gas outlet and a carbon material outlet along the gas flow direction; wherein the first light hydrocarbon gas inlet is located at the bottom of the catalytic cracking up-flow fluidized bed, the mixed gas outlet is located at the top of the catalytic cracking up-flow fluidized bed and is communicated with the cyclone separator, the catalyst inlet is arranged close to the first light hydrocarbon gas inlet, and the cracking product inlet is located above the catalyst inlet to avoid the contact between hydrogen sulfide and ammonia in the cracking product and the catalyst; The purification separation device is provided with a mixed gas inlet communicated with the mixed gas outlet, a light hydrocarbon gas outlet communicated with a second light hydrocarbon gas inlet and a purified target product hydrogen gas outlet.

2. The system for producing carbon material and hydrogen gas from sulfur and nitrogen- containing oil according to claim 1, wherein The purification separation device comprises a heat exchange device, a desulfurization and denitrification device and a separation device; The heat exchange device is provided with a heat exchange gas outlet and a second light hydrocarbon gas inlet, the heat exchange device is communicated with the mixed gas outlet through the mixed gas inlet, the heat exchange device is communicated with the first light hydrocarbon gas inlet through the light hydrocarbon gas outlet, the heat exchange device is used for cooling treatment of the mixed gas entering through the mixed gas inlet, and is used for heating treatment of the light hydrocarbon gas entering through the second light hydrocarbon gas inlet; The desulfurization and denitrification device is provided with a heat exchange gas inlet communicated with the heat exchange gas outlet and a desulfurization and denitrification gas outlet; the desulfurization and denitrification device is used for removing hydrogen sulfide and ammonia in the mixed gas entering through the heat exchange gas inlet; The separation device is provided with a desulfurization and denitrification gas inlet communicated with the desulfurization and denitrification gas outlet, the hydrogen gas outlet and the light hydrocarbon gas outlet communicated with the second light hydrocarbon gas inlet, and the separation device is used for separating light hydrocarbon and hydrogen gas entering through the desulfurization and denitrification gas inlet.

3. The system for producing carbon material and hydrogen gas from sulfur and nitrogen- containing oil according to claim 2, wherein The working temperature of the heat exchange device is 300-500 ℃.

4. A method of producing carbon material and hydrogen gas from a sulfur and nitrogen containing oil product, characterized by, The method is suitable for the system of any one of claims 1-3, and the method comprises the following steps: S1, the sulfur and nitrogen-containing oil product is introduced into the thermal cracking down-flow fluidized bed from the sulfur and nitrogen-containing oil product inlet for thermal cracking reaction to obtain a cracking product containing hard carbon, light hydrocarbon, hydrogen, hydrogen sulfide and ammonia; S2, the cracking product is introduced into the catalytic cracking up-flow fluidized bed through the cracking product inlet for gas-solid separation operation to intercept the hard carbon in the cracking product, and the gaseous substances in the cracking product are output; S3, the gaseous substances obtained in step S2 are introduced into the purification separation device through the mixed gas inlet to remove hydrogen sulfide and ammonia in the gaseous substances, and separate light hydrocarbon and hydrogen, and the hydrogen is the target product; S4, the light hydrocarbon obtained in step S3 is introduced into the first light hydrocarbon gas inlet of the catalytic cracking upward fluidized bed, and the catalyst is added through the catalyst inlet, and the light hydrocarbon is subjected to catalytic cracking reaction to generate the target product carbon nanotube.

5. The method of claim 4, wherein the sulfur and nitrogen containing oil is prepared as a carbon material and hydrogen gas. The purification and separation device comprises a heat exchange device, a desulfurization and denitrification device, and a separation device, and step S3 specifically comprises: S31, the gaseous substance obtained in step S2 is introduced into the heat exchange device through the mixed gas inlet for cooling treatment; S32, the gaseous substance after the cooling treatment is introduced into the desulfurization and denitrification device 3-2 through the heat exchange gas inlet to remove hydrogen sulfide and ammonia in the gaseous substance, and a mixed gas composed of light hydrocarbon and hydrogen is obtained; S33, the mixed gas obtained in step S32 is introduced into the separation device through the desulfurization and denitrification gas inlet to separate light hydrocarbon and hydrogen, and the hydrogen is the target product.

6. The method of claim 4, wherein the sulfur and nitrogen containing oil is prepared into carbon material and hydrogen gas. In step S1, the temperature required for the thermal cracking reaction is 800-1100 ℃, and the time is 1-20 s.

7. The method of claim 5, wherein the sulfur and nitrogen containing oil is prepared into carbon material and hydrogen gas. In step S31, the temperature of the gaseous substance obtained by the cooling treatment is 300-500 ℃.

8. The method of claim 5, wherein the sulfur and nitrogen containing oil is prepared into carbon material and hydrogen gas. In step S32, the desulfurization and denitrification device removes hydrogen sulfide and ammonia in the gaseous substance by water washing or acid-base neutralization.

9. The method of claim 5, wherein the sulfur and nitrogen containing oil is prepared into carbon material and hydrogen gas. In step S33, the separation device separates light hydrocarbon and hydrogen by pressure swing adsorption.

10. The method of claim 4, wherein the sulfur and nitrogen containing oil is prepared into carbon material and hydrogen gas. The oil product containing sulfur and nitrogen is at least one of catalytic diesel oil with / without asphalt, coal tar, residual oil, oil slurry, biomass tar and petroleum tar, the sulfur content of the oil product containing sulfur and nitrogen is 10-12000 mg / kg, and the nitrogen content of the oil product containing sulfur and nitrogen is 20-5000 mg / kg; The catalyst is a metal catalyst containing iron, cobalt or nickel; or the catalyst is a dual metal catalyst composed of the metal catalyst and molybdenum, copper, manganese or tungsten.

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