CN116675212A

CN116675212A - Method and system for preparing sulfur-nitrogen-containing oil product into carbon material and hydrogen

Info

Publication number: CN116675212A
Application number: CN202310587564.9A
Authority: CN
Inventors: 崔超婕; 骞伟中; 汪剑; 于翔; 焦瑞敬; 李博凡
Original assignee: Tsinghua University
Current assignee: Tsinghua University
Priority date: 2023-05-23
Filing date: 2023-05-23
Publication date: 2023-09-01

Abstract

The invention provides a method and a system for preparing sulfur-nitrogen-containing oil products into carbon materials and hydrogen, wherein the method comprises a descending fluidized bed, an ascending fluidized bed and a purifying and separating device. Introducing the sulfur-nitrogen-containing oil product into a downward fluidized bed to generate hard carbon, hydrogen and light hydrocarbon, and simultaneously changing the organic sulfur-nitrogen component into hydrogen sulfide and ammonia. Solids in the pyrolysis product are trapped at the bottom of the upward fluidized bed under the action of the porous partition plate and the cyclone separator. The gas is treated by a purification and separation device, and pure hydrogen and light hydrocarbon are obtained after the hydrogen sulfide and ammonia in the gas are removed. Light hydrocarbon returns to the upward fluidized bed from the bottom of the device through circulation, and carbon nano tubes are generated under the action of a metal catalyst by utilizing the high-temperature environment provided by hard carbon. The system effectively avoids poisoning influence of sulfur and nitrogen in oil on the metal catalyst, simultaneously utilizes heat generated by high-temperature pyrolysis to prepare energy for the carbon nano tube, has the advantages of short flow, long service life of the catalyst, continuous operation and low cost production of carbon materials and hydrogen.

Description

Method and system for preparing sulfur-nitrogen-containing oil product into carbon material and hydrogen

Technical Field

The invention relates to the technical field of material chemical industry, in particular to a method and a system for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen.

Background

Sulfur-containing and nitrogen-containing oils are often one of the products found in crude oil processing, coal processing, and possibly one of the remaining low value materials for chemical processing. The most common sulfur-containing and nitrogen-containing oils include catalytic diesel, petroleum tar, coal tar, biomass tar, and the like, which are often present in mixtures and often contain a large amount of polycyclic aromatic hydrocarbon compounds. The accumulation amount is huge, and hundreds of millions of tons can be reached each year. It is converted into a high value-added product, so as to meet the requirements of cleanliness and sustainability in the carbon neutralization age. The most common processing method is to convert it to a monocyclic aromatic hydrocarbon or gasoline-like component using hydrocracking technology. However, the yield is low, and a large amount of hydrogen is consumed, and the conditions are severe.

In addition, the preparation of carbon materials and hydrogen by cracking the low-value materials is a double-purpose measure. However, the prior art does not realize efficient utilization of the cracking products.

Disclosure of Invention

The invention provides a method and a system for preparing sulfur-nitrogen-containing oil products into carbon materials and hydrogen, which comprise a descending fluidized bed, an ascending fluidized bed and a purification and separation device, wherein the system can effectively avoid poisoning influence of sulfur nitrogen in the oil products on a metal catalyst, and simultaneously utilizes heat generated by high-temperature thermal pyrolysis to prepare energy for carbon nano tubes. The specific invention comprises the following steps:

In a first aspect, the present invention provides a system for producing sulfur and nitrogen containing oils as carbon material and hydrogen gas, the system comprising: a thermal cracking downstream fluidized bed 1, a catalytic cracking upstream fluidized bed 2 and a purification and separation device 3;

the thermal cracking downstream fluidized bed 1 is provided with a sulfur-nitrogen-containing oil product inlet 8 and a cracking product outlet 9;

a light hydrocarbon gas inlet 12, a catalyst inlet 7, a pyrolysis product inlet 10 communicated with the pyrolysis product outlet 9, a porous distribution plate 11, a cyclone separator 6, a mixed gas outlet 16 and a carbon material outlet 13 are sequentially arranged in the catalytic pyrolysis uplink fluidized bed 2 along the gas flow direction; wherein the light hydrocarbon gas inlet 12 is positioned at the bottom of the catalytic cracking upward fluidized bed 2, the mixed gas outlet 16 is positioned at the top of the catalytic cracking upward fluidized bed 2 and is communicated with the cyclone separator 6, the catalyst inlet 7 is positioned close to the light hydrocarbon gas inlet 12, and the cracking product inlet 10 is positioned above the catalyst inlet 7 so as to avoid contact of hydrogen sulfide and ammonia in the cracking product with the catalyst;

the purification and separation apparatus 3 is provided with a mixed gas inlet 17 communicating with the mixed gas outlet 16, a light hydrocarbon gas outlet 20 communicating with the light hydrocarbon gas inlet 12, and a purified target product hydrogen outlet 25.

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

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 communicated with the mixed gas outlet 16 through a mixed gas inlet 17, the heat exchange device 3-1 is communicated with the light hydrocarbon gas inlet 12 through a light hydrocarbon gas outlet 20, the heat exchange device 3-1 is used for cooling mixed gas entering the mixed gas inlet through the mixed gas inlet 17 and heating light hydrocarbon gas entering the mixed gas inlet through the light hydrocarbon gas inlet 19;

the desulfurization and denitrification device 3-2 is provided with a heat exchange gas inlet 21 and a desulfurization and denitrification gas outlet 22 which are communicated with the heat exchange gas outlet 18; the desulfurization and denitrification device 3-2 is used for removing hydrogen sulfide and ammonia in the mixed gas entering the device through the heat exchange gas inlet 21;

the separation device 3-3 is provided with a desulfurization and denitrification gas inlet 23 communicated with the desulfurization and denitrification gas outlet 22, the hydrogen outlet 25 and a light hydrocarbon gas outlet 24 communicated with the light hydrocarbon gas inlet 19, and the separation device 3-3 is used for separating the light hydrocarbon and hydrogen entering the separation device through the desulfurization and denitrification gas inlet 23.

Optionally, the working temperature of the heat exchange device 3-1 is 300-500 ℃.

In a second aspect, the present invention provides a method for preparing sulfur-nitrogen-containing oil into carbon material and hydrogen, the method being suitable for the system according to the first aspect, the method comprising the steps of:

s1, introducing an oil product containing sulfur and nitrogen into a thermal cracking downstream fluidized bed 1 from a sulfur and nitrogen-containing oil product inlet 8 for thermal cracking reaction to obtain a cracking product containing hard carbon, light hydrocarbon, hydrogen sulfide and ammonia;

s2, introducing the pyrolysis product into a catalytic pyrolysis uplink fluidized bed 2 through a pyrolysis product inlet 10 for gas-solid separation operation so as to intercept hard carbon in the pyrolysis product and output gaseous substances in the pyrolysis product;

s3, enabling the gaseous substances obtained in the step S2 to enter a purification and separation device 3 through a mixed gas inlet 17 so as to remove hydrogen sulfide and ammonia in the gaseous substances and separate light hydrocarbon and hydrogen, wherein the hydrogen is a target product;

s4, introducing the light hydrocarbon obtained in the step S3 into the catalytic cracking ascending fluidized bed 2 from a light hydrocarbon gas inlet 12, and then adding a catalyst through a catalyst inlet 7, wherein the light hydrocarbon is subjected to catalytic cracking reaction, so as to generate a target product carbon nano tube.

Optionally, the purifying and separating device 3 includes a heat exchange device 3-1, a desulfurizing and denitrifying device 3-2 and a separating device 3-3, and the step S3 specifically includes:

s31, introducing the gaseous substance obtained in the step S2 into the heat exchange device 3-1 through the mixed gas inlet 17 for cooling treatment;

s32, introducing the gaseous substances subjected to the temperature reduction treatment into a desulfurization and denitrification device 3-2 through a heat exchange gas inlet 21 so as to remove hydrogen sulfide and ammonia in the gaseous substances and obtain mixed gas consisting of light hydrocarbon and hydrogen;

s33, introducing the mixed gas obtained in the step S32 into a separation device 3-3 through a desulfurization and denitrification gas inlet 23 to separate light hydrocarbon and hydrogen, wherein the hydrogen is a target product.

Optionally, in step S1, the temperature required for the thermal cracking reaction is 800-1100 ℃ for 1-20S.

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

Optionally, in step S32, the desulfurizing and denitrifying apparatus 3-2 removes hydrogen sulfide and ammonia from the gaseous substances by water washing or acid-base neutralization.

Optionally, in step S33, the separation device 3-3 separates the light hydrocarbon and the hydrogen by pressure swing adsorption.

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 which are doped with or not doped with asphalt, the sulfur content of the sulfur-nitrogen-containing oil product is 10-12000mg/kg, and the nitrogen content of the sulfur-nitrogen-containing oil product is 20-5000mg/kg;

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

Compared with the prior art, the invention has the following advantages:

(1) The invention provides a system for preparing sulfur-nitrogen-containing oil products into carbon materials and hydrogen, which combines a high-temperature pyrolysis technology and a medium-temperature catalytic pyrolysis technology to simultaneously produce two products, namely hydrogen and carbon nano tubes, and the added value of the product is improved by 3-10 times compared with that of the product obtained by a pure high-temperature pyrolysis technology. In addition, the high-temperature pyrolysis technology is combined with the medium-temperature catalytic pyrolysis technology to prepare the carbon material and hydrogen, and organic sulfur and organic nitrogen in the sulfur-nitrogen-containing oil product can be converted into hydrogen sulfide and ammonia, so that the desulfurization and denitrification process is simplified, and the hydrogen sulfide and the ammonia can be thoroughly removed only by adopting a water washing or acid-base neutralization mode. And the dosage of the desulfurizing agent and the nitrogen removing agent is small, and the cost is reduced by 30-50%.

(2) According to the system for preparing the sulfur-nitrogen-containing oil into the carbon material and the hydrogen, provided by the invention, through reasonable arrangement of the structure of the catalytic cracking uplink fluidized bed 2, the cracking products entering the system can not be in direct contact with the metal catalyst, so that the poisoning effect of hydrogen sulfide and ammonia on the metal catalyst is avoided, the service life of the catalyst is prolonged by 3-5 times, and the purity of the carbon nanotube product is further improved by 20-40%.

(3) According to the system for preparing the sulfur-nitrogen-containing oil product into the carbon material and the hydrogen, the thermal cracking downstream fluidized bed 1 is connected with the catalytic cracking upstream fluidized bed 2, so that the coupling of two endothermic reactions (the thermal cracking reaction of the sulfur-nitrogen-containing oil product and the catalytic cracking reaction of the light hydrocarbon) is realized, the high-temperature heat energy of the thermal cracking technology is effectively utilized, the catalyst and the light hydrocarbon which subsequently participate in the catalytic cracking reaction are heated by means of the high temperature carried by the thermal cracking product (hard carbon), and the catalytic cracking reaction of the light hydrocarbon is realized under the condition that energy is not additionally provided for the catalytic cracking upstream fluidized bed 2, so that the energy supply cost is reduced by 20-40%.

(4) The method for preparing the sulfur-nitrogen-containing oil product into the carbon material and the hydrogen has wide raw material adaptability, can catalyze diesel oil, coal tar, residual oil, crude oil slurry, biomass tar, petroleum tar and mixtures thereof, and smoothly converts the low-value raw materials under the condition of low energy consumption to obtain high-value materials (carbon nano tubes, hydrogen and hard carbon).

Drawings

In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 shows a schematic diagram of a system for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen gas according to an embodiment of the present invention;

FIG. 2 is a schematic diagram of another system for preparing carbon material and hydrogen from sulfur-nitrogen-containing oil according to an embodiment of the present invention;

fig. 3 shows a flow chart of a method for preparing sulfur-nitrogen-containing oil into carbon material and hydrogen gas according to an embodiment of the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. Any product that is the same as or similar to the present invention, which anyone in the light of the present invention or combines the present invention with other prior art features, falls within the scope of the present invention based on the embodiments of the present invention. And all other embodiments that may be made by those of ordinary skill in the art without undue burden and without departing from the scope of the invention.

Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge. Furthermore, the drawings are merely schematic illustrations of embodiments of the invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus a repetitive description thereof will be omitted. Some of the block diagrams shown in the figures are functional entities and do not necessarily correspond to physically or logically separate entities.

Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate.

In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for defining the components, and are merely for convenience in distinguishing the corresponding components, and the terms are not meant to have any special meaning unless otherwise indicated, so that the scope of the present invention is not to be construed as being limited.

In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.

The first objective of the present invention is to provide a system for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen, specifically referring to fig. 1, fig. 1 shows a schematic structural diagram of a system for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen according to an embodiment of the present invention, as shown in fig. 1, including: a thermal cracking downstream fluidized bed 1, a catalytic cracking upstream fluidized bed 2 and a purification and separation device 3; wherein, the thermal cracking downstream fluidized bed 1 is provided with a sulfur-nitrogen-containing oil product inlet 8 and a cracking product outlet 9. The thermal cracking downstream fluidized bed 1 is used for cracking sulfur-nitrogen-containing oil products entering the fluidized bed through a sulfur-nitrogen-containing oil product inlet 8 to obtain hard carbon, light hydrocarbon, hydrogen sulfide and ammonia; the pyrolysis product passes through the pyrolysis product outlet 9 to exit the pyrolysis downstream fluidized bed 1 and then enters the catalytic pyrolysis upstream fluidized bed 2.

A light hydrocarbon gas inlet 12, a catalyst inlet 7, a pyrolysis product inlet 10 communicated with a pyrolysis product outlet 9, a porous distribution plate 11, a cyclone separator 6, a mixed gas outlet 16 and a carbon material outlet 13 are sequentially arranged in the catalytic pyrolysis uplink fluidized bed 2 along the gas flow direction; wherein, the light hydrocarbon gas inlet 12 is positioned at the bottom of the catalytic cracking upward fluidized bed 2, the mixed gas outlet 16 is positioned at the top of the catalytic cracking upward fluidized bed 2 and is communicated with the cyclone separator 6, the catalyst inlet 7 is arranged close to the light hydrocarbon gas inlet 12, and the cracking product inlet 10 is positioned above the catalyst inlet 7 so as to avoid the contact of hydrogen sulfide and ammonia in the cracking product with the catalyst.

The catalytic pyrolysis up-flow fluidized bed 2 is used for carrying out gas-solid separation on pyrolysis products entering the catalytic pyrolysis up-flow fluidized bed through a pyrolysis product inlet 10; wherein the porous distribution plate 11 is arranged perpendicular to the gas flow direction and is positioned at the waist of the catalytic cracking upstream fluidized bed 2 and used for intercepting solid matters (hard carbon) in the cracking products so as to gather the solid matters at the bottom of the catalytic cracking upstream fluidized bed 2; since the porous distribution plate 11 cannot retain 100% of the solid matter, a trace amount (2-4%) of the solid matter having a small particle diameter is still mixed in the gaseous pyrolysis product, the cyclone separator 6 is used for further solid-gas separation of the pyrolysis product passing through the transverse porous distribution plate 11, and the separated solid matter is conveyed to the bottom of the catalytic pyrolysis upstream fluidized bed 2, and the gaseous pyrolysis product exits the catalytic pyrolysis upstream fluidized bed 2 through the pyrolysis product outlet 9.

The purification and separation apparatus 3 is provided with a mixed gas inlet 17 communicating with the mixed gas outlet 16, a light hydrocarbon gas outlet 20 communicating with the light hydrocarbon gas inlet 12, and a purified target product hydrogen outlet 25. The purification and separation apparatus 3 removes hydrogen sulfide and ammonia from gaseous substances (light hydrocarbon, hydrogen sulfide and ammonia) that enter the mixed gas through the mixed gas inlet 17, and then separates the light hydrocarbon and the hydrogen to obtain target product hydrogen.

Further, the light hydrocarbon separated by the purification and separation device 3 is output through the light hydrocarbon gas outlet 20 and then enters the catalytic cracking ascending fluidized bed 2, and the catalytic cracking ascending fluidized bed 2 is also used for catalytic cracking of the light hydrocarbon entering the device through the light hydrocarbon gas inlet 12, so as to obtain the target product carbon nanotube. The metal catalyst used in the catalytic cracking reaction is added through the catalyst inlet 7, and because the catalyst inlet 7 exists independently from the cracking product inlet 10 and is positioned below the cracking product inlet 10, hydrogen sulfide and ammonia in the cracking product cannot contact with the metal catalyst, and the poisoning effect of the hydrogen sulfide and ammonia on the metal catalyst is avoided. Meanwhile, as the thermal cracking product (hard carbon) exists at the bottom of the catalytic cracking upward fluidized bed 2, the catalyst and the light hydrocarbon which participate in the catalytic cracking reaction are heated by virtue of the high temperature carried by the thermal cracking product (hard carbon), the process of catalyzing the light hydrocarbon by the metal catalyst can be realized without additional heating, the catalytic cracking reaction of the light hydrocarbon is completed under the condition of not providing energy to the catalytic cracking upward fluidized bed 2, and the carbon nano tube of the target product is obtained, and the high-temperature heat energy of the thermal cracking technology is effectively utilized, so that the energy supply cost is reduced by 20-40%. The coupling of two endothermic reactions (thermal cracking reaction of sulfur-nitrogen-containing oil products and catalytic cracking reaction of light hydrocarbon) is realized.

In some embodiments, the purification and separation apparatus 3 comprises: a heat exchange device 3-1, a desulfurization and denitrification device 3-2 and a separation device 3-3; fig. 2 shows a schematic diagram of another system for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen according to an embodiment of the present invention, where as shown in fig. 2, the heat exchange device 3-1 has an operating temperature of 300-500 ℃, and is provided with a heat exchange gas outlet 18 and a light hydrocarbon gas inlet 19, the heat exchange device 3-1 is communicated with the mixed gas outlet 16 through the mixed gas inlet 17, the heat exchange device 3-1 is communicated with the light hydrocarbon gas inlet 12 through the light hydrocarbon gas outlet 20, and the heat exchange device 3-1 is used for cooling the mixed gas entering the mixed gas inlet through the mixed gas inlet 17.

the separation device 3-3 is provided with a desulfurization and denitrification gas inlet 23 communicating with the desulfurization and denitrification gas outlet 22, a hydrogen outlet 25, and a light hydrocarbon gas outlet 24 communicating with the light hydrocarbon gas inlet 19, and the separation device 3-3 is for separating the light hydrocarbon and hydrogen entered therein through the desulfurization and denitrification gas inlet 23.

Further, before the light hydrocarbon separated by the separation device 3-3 returns to the catalytic cracking upstream fluidized bed 2 for catalytic cracking reaction, the light hydrocarbon is introduced into the heat exchange device 3-1 through the light hydrocarbon gas inlet 19, and is heated by the working temperature (300-500 ℃) of the heat exchange device 3-1, so that the light hydrocarbon is heated and then enters the catalytic cracking upstream fluidized bed 2, and the energy required by the catalytic cracking reaction can be further reduced/avoided by the heated light hydrocarbon, so that the energy utilization rate of the system is further improved.

In a second aspect, the present invention provides a method for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen, where the method is applicable to the system of the first aspect, fig. 3 shows a flowchart of a method for preparing a sulfur-nitrogen-containing oil product into a carbon material and hydrogen, and as shown in fig. 3, the method includes the following steps:

in the step, 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 which are mixed with or not mixed with asphalt, the sulfur content of the sulfur-nitrogen-containing oil product is 10-12000mg/kg, and the nitrogen content of the sulfur-nitrogen-containing oil product is 20-5000mg/kg. The temperature of the thermal cracking reaction is 800-1100 ℃, the residence time of the oil product in the thermal cracking downstream fluidized bed 1 under the pressure of 0.1-1MPa is 1-20s, and the obtained light hydrocarbon is specifically C ₁ -C ₁₀ Hydrocarbons.

S2, introducing the pyrolysis product into the catalytic pyrolysis uplink fluidized bed 2 through a pyrolysis product inlet 10 for gas-solid separation operation so as to intercept hard carbon in the pyrolysis product and output gaseous substances in the pyrolysis product.

In this step, 96% to 98% of the solids are retained in the dense solids phase zone 14 by the blockage of the transversely porous distribution plates in the catalytic cracking upward fluidized bed 2. Trace solids enter the solids-lean zone 15 along with gaseous materials. And then goes upward to enter a cyclone separator 6, after gas and solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2, and gaseous substances are output through a mixed gas outlet 16.

S3, the gaseous substances obtained in the step S2 enter the purification and separation device 3 through the mixed gas inlet 17 to remove hydrogen sulfide and ammonia in the gaseous substances, and separate light hydrocarbon and hydrogen, wherein the hydrogen is a target product.

Further, the purification and separation device 3 comprises a heat exchange device 3-1, a desulfurization and denitrification device 3-2 and a separation device 3-3, and the step S3 specifically comprises:

s31, introducing the gaseous substance obtained in the step S2 into the heat exchange device 3-1 through the mixed gas inlet 17 for cooling treatment; the temperature of the gaseous substance obtained by the cooling treatment is 300-500 ℃.

S32, introducing the cooled gaseous substances into a desulfurization and denitrification device 3-2 through a heat exchange gas inlet 21 to remove hydrogen sulfide and ammonia in the gaseous substances, so as to obtain mixed gas consisting of light hydrocarbon and hydrogen; the desulfurization and denitrification device 3-2 removes hydrogen sulfide and ammonia in the gaseous substances by water washing or acid-base neutralization.

S33, introducing the mixed gas obtained in the step S32 into a separation device 3-3 through a desulfurization and denitrification gas inlet 23 to separate light hydrocarbon and hydrogen, wherein the hydrogen is used as a target product; the separation device 3-3 separates light hydrocarbon and hydrogen by pressure swing adsorption.

S4, introducing the light hydrocarbon obtained in the step S3 into the catalytic cracking ascending fluidized bed 2 from a light hydrocarbon gas inlet 12, adding a catalyst through a catalyst inlet 7, and performing catalytic cracking reaction on the light hydrocarbon to generate a target product carbon nano tube.

In the step, the light hydrocarbon entering the catalytic cracking up-flowing fluidized bed 2 is purified light hydrocarbon, hydrogen sulfide and ammonia are not contained, a metal catalyst used in the catalytic cracking reaction is added through a catalyst inlet 7 and contacts with hard carbon at the bottom of the catalytic cracking up-flowing fluidized bed 2, the catalyst and the light hydrocarbon which participate in the medium-temperature catalytic cracking reaction are heated by means of high temperature carried by thermal cracking products (hard carbon), the catalyst and the light hydrocarbon obtain the reaction temperature of 700-850 ℃, the process of catalyzing the light hydrocarbon by the metal catalyst is realized without additional heating, the catalytic cracking reaction of the light hydrocarbon is completed under the condition of not providing energy to the catalytic cracking up-flowing fluidized bed 2, and the carbon nano tube is obtained, so that the high-temperature heat energy of the thermal cracking technology is effectively utilized, and the energy supply cost is reduced. The catalyst is a metal catalyst containing iron, cobalt or nickel; or the catalyst is a metal catalyst and a binary metal catalyst consisting of molybdenum, copper, manganese or tungsten.

In this step, the light hydrocarbon is subjected to the medium-temperature catalytic cracking reaction to generate hydrogen and a small amount of methane, and this gas is mixed with the gas (H) entering the fluidized bed 1 through the cracking product inlet 10 and entering the catalytic cracking ascending fluidized bed 2 ₂ 、H ₂ S、NH ₃ With light hydrocarbon) to dilute H ₂ S and ammonia.

Further, the sulfur-nitrogen-containing oil is continuously introduced into the thermal cracking downstream fluidized bed 1 from the sulfur-nitrogen-containing oil inlet 8, and the catalyst is introduced into the catalytic cracking upstream fluidized bed 2 from the catalyst inlet 7 every 8 hours, so that the process can be continuously operated.

In order that the present invention may be more clearly understood by those skilled in the art, the method of the present invention will now be described in detail by the following examples.

Example 1

The thermal cracking down-flow fluidized bed 1, the catalytic cracking up-flow fluidized bed 2, the heat exchange device 3-1, the desulfurization and denitrification device 3-2 and the separation device 3-3 are sequentially connected as shown in the schematic structure diagram of figure 2.

Introducing sulfur-nitrogen-containing oil products (catalytic diesel oil, sulfur content of 12000mg/kg, nitrogen content of 1000mg/kg and boiling point of 200-400 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the condition of 1100 ℃ and 0.1MPa and controlling the residence time to be 1 s.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plates therein, 96% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 500 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

The separated light hydrocarbon gas is discharged from the separation device 3-3 through the light hydrocarbon gas outlet 24, enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 and is heated to 500 ℃, and is circulated back to the light hydrocarbon gas inlet 12 after discharged from the heat exchange device 3-1 through the light hydrocarbon gas outlet 20, and enters the catalytic cracking up-flowing fluidized bed 2 to be used as fluidizing gas and reaction medium.

A metal-based catalyst (iron-containing catalyst) was fed into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst was mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12 to a temperature of 700 ℃. The contact time of hydrocarbon gas in the catalyst is 0.1min, and the hydrocarbon gas is cracked to produce carbon nanotube and hydrogen or small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 8 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through an outlet 13 to form a carbon material product.

Continuously introducing sulfur-nitrogen-containing oil from a sulfur-nitrogen-containing oil inlet 8 to the thermal cracking downstream fluidized bed 1, and introducing catalyst from a catalyst inlet 7 to the catalytic cracking upstream fluidized bed 2 every 8 hours, so that the process forms continuous operation.

Example 2

Introducing sulfur-nitrogen-containing oil products (coal tar, sulfur containing 7200mg/kg, nitrogen containing 5000mg/kg and boiling point 200-380 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions that the temperature is 920 ℃ and the residence time is controlled to be 20s and 1 MPa.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plates therein, 98% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 300 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

The separated light hydrocarbon gas is discharged from the separation device 3-3 through the light hydrocarbon gas outlet 24, enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 and is heated to 300 ℃, and is circulated back to the light hydrocarbon gas inlet 12 after discharged from the heat exchange device 3-1 through the light hydrocarbon gas outlet 20, and enters the catalytic cracking up-flowing fluidized bed 2 to be used as fluidizing gas and reaction medium.

A metal catalyst (nickel-containing catalyst) was fed into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst was mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12 at a temperature of 850 ℃. The contact time of hydrocarbon gas in the catalyst is 2min, and the hydrocarbon gas is cracked to generate carbon nano tube and hydrogen or a small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 5 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through the outlet 13 to form a carbon material product.

Continuously introducing sulfur-nitrogen-containing oil from a sulfur-nitrogen-containing oil inlet 8 to the thermal cracking downstream fluidized bed 1, and introducing catalyst from a catalyst inlet 7 to the catalytic cracking upstream fluidized bed 2 every 8 hours, so that continuous operation is formed in the process.

Example 3

Introducing sulfur-nitrogen-containing oil products (petroleum tar, sulfur-containing 8500mg/kg, nitrogen-containing 5000mg/kg and boiling point 350-400 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions that the temperature is 920 ℃ and the pressure is 0.5MPa and the residence time is controlled to be 10 s.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 400 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

The separated light hydrocarbon gas is discharged from the separation device 3-3 through the light hydrocarbon gas outlet 24, enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 and is heated to 400 ℃, and is circulated back to the light hydrocarbon gas inlet 12 after discharged from the heat exchange device 3-1 through the light hydrocarbon gas outlet 20, and enters the catalytic cracking up-flowing fluidized bed 2 to be used as fluidizing gas and reaction medium.

A metal catalyst (catalyst containing cobalt and molybdenum) is added into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst is mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12, and the temperature reaches 850 ℃. The contact time of hydrocarbon gas in the catalyst is 2min, and the hydrocarbon gas is cracked to generate carbon nano tube and hydrogen or a small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 10 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through an outlet 13 to form a carbon material product.

Example 4

Introducing sulfur-nitrogen-containing oil products (biomass tar, sulfur content of 10mg/kg, nitrogen content of 20mg/kg and boiling point of 200-300 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the condition that the residence time is controlled to be 5s at 800 ℃ and 0.2 MPa.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plate therein, 97% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 450 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

A metal catalyst (nickel-copper-containing catalyst) was fed into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst was mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12 at a temperature of 750 ℃. The contact time of hydrocarbon gas in the catalyst is 0.6min, and the hydrocarbon gas is cracked to produce carbon nanotube and hydrogen or small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 6 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through the outlet 13 to form a carbon material product.

Example 5

Introducing sulfur-nitrogen-containing oil (residual oil, sulfur content of 500mg/kg, nitrogen content of 5000mg/kg, boiling point of 350-400 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions of 800 ℃ and 0.8MPa and controlling the residence time to be 16 s.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plates therein, 96.5% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 480 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

The separated light hydrocarbon gas is discharged from the separation device 3-3 through the light hydrocarbon gas outlet 24, enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 and is heated to 450 ℃, and is circulated back to the light hydrocarbon gas inlet 12 after discharged from the heat exchange device 3-1 through the light hydrocarbon gas outlet 20, and enters the catalytic cracking up-flowing fluidized bed 2 to be used as fluidizing gas and reaction medium.

A metal catalyst (a catalyst containing nickel and manganese) is added into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst is mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12, and the temperature reaches 780 ℃. The contact time of hydrocarbon gas in the catalyst is 1.2min, and the hydrocarbon gas is cracked to produce carbon nanotube and hydrogen or small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 2 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through the outlet 13 to form a carbon material product.

Example 6

Introducing sulfur-nitrogen-containing oil products (crude oil slurry, sulfur content of 500mg/kg, nitrogen content of 20mg/kg and boiling point of 300-400 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions that the temperature is 850 ℃ and the residence time is controlled to be 12s and 1 MPa.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plate therein, 96.7% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 380 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

The metal catalyst (catalyst containing nickel and tungsten) is added into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7The catalyst was mixed with hard carbon at the bottom and hydrocarbon gas entering through the light hydrocarbon gas inlet 12 at a temperature of 800 ℃. The contact time of hydrocarbon gas in the catalyst is 1.6min, and the hydrocarbon gas is cracked to produce carbon nanotube and hydrogen or small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 14 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through the outlet 13 to form a carbon material product.

Example 7

Introducing sulfur-nitrogen-containing oil products (20% asphalt and 80% catalytic diesel oil, 5500mg/kg sulfur, 2020mg/kg nitrogen, and 300-450 ℃ boiling point) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions of 1050 ℃ and 0.1MPa and controlling the residence time to be 11 s.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plate therein, 97.7% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

A metal catalyst (a catalyst containing iron and molybdenum) is added into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst is mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12, and the temperature reaches 750 ℃. The contact time of hydrocarbon gas in the catalyst is 1.2min, and the hydrocarbon gas is cracked to produce carbon nanotube and hydrogen or small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 3 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through the outlet 13 to form a carbon material product.

Example 8

Introducing sulfur-nitrogen-containing oil products (80% asphalt and 20% biomass diesel oil, sulfur content is 3500mg/kg, nitrogen content is 920mg/kg, boiling point is 250-450 ℃) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions of 1000 ℃ and 0.2MPa, wherein residence time is controlled to be 11 s.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plate therein, 97.6% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 430 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

A metal catalyst (a catalyst containing iron and molybdenum) is added into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst is mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12, and the temperature reaches 780 ℃. The contact time of hydrocarbon gas in the catalyst is 1min, and the hydrocarbon gas is cracked to generate carbon nano tube and hydrogen or a small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. The reaction was controlled for 6 hoursAnd (3) taking the mixture of the generated carbon nano tube and the hard carbon out of the catalytic cracking uplink fluidized bed 2 through an outlet 13 to form a carbon material product.

Example 9

Introducing sulfur-nitrogen-containing oil products (30% coal tar and 70% residual oil, 4500mg/kg of sulfur content, 4200mg/kg of nitrogen content and 280-450 ℃ in boiling point) into a thermal cracking downstream fluidized bed 1 from an inlet 8, and cracking into hard carbon, C1-C10 hydrocarbons, hydrogen sulfide and ammonia under the conditions of 1080 ℃ and 0.5MPa and controlling the residence time to be 11 s.

The gas solid product flows out of the fluidized bed 1 from a pyrolysis product outlet 9 and enters the catalytic pyrolysis upstream fluidized bed 2 through a pyrolysis product inlet 10. Blocked by the transverse porous distribution plate therein, 96.6% of the solids were trapped in the solid dense phase zone 14. A small amount of solids enters the solids-lean zone 15 along with the gas. And then goes upward to enter the cyclone 6. After the gas and the solid are separated, the solid returns to the bottom of the catalytic cracking upward fluidized bed 2.

After the gas is discharged from the mixed gas outlet 16 and catalytically cracked into the upward fluidized bed 2, the gas enters the heat exchange device 3-1 through the mixed gas inlet 17, the temperature is controlled to be 490 ℃, then the gas is discharged from the heat exchange device 3-1 through the heat exchange gas outlet 18, then enters the desulfurization and denitrification device 3-2 through the heat exchange gas inlet 21, all sulfur and nitrogen are removed through the conventional technology (such as water washing, acid-base neutralization and the like), then is discharged from the desulfurization and denitrification gas outlet 22, and finally enters the separation device 3-3 through the desulfurization and denitrification gas inlet 23 to separate hydrogen from hydrocarbon. Pure hydrogen separated by conventional technology (such as pressure swing adsorption and the like) is discharged from the hydrogen outlet 25, and the target product hydrogen is collected.

The separated light hydrocarbon gas is discharged from the separation device 3-3 through the light hydrocarbon gas outlet 24, enters the heat exchange device 3-1 through the light hydrocarbon gas inlet 19 and is heated to 460 ℃, and is circulated back to the light hydrocarbon gas inlet 12 after discharged from the heat exchange device 3-1 through the light hydrocarbon gas outlet 20, and enters the catalytic cracking up-flowing fluidized bed 2 to be used as fluidizing gas and reaction medium.

A metal catalyst (catalyst containing nickel and molybdenum) is added into the catalytic cracking upstream fluidized bed 2 from a catalyst inlet 7, and the catalyst is mixed with hard carbon at the bottom and hydrocarbon gas entering through a light hydrocarbon gas inlet 12, and the temperature reaches 820 ℃. The contact time of hydrocarbon gas in the catalyst is 0.8min, and the hydrocarbon gas is cracked to produce carbon nanotube and hydrogen or small amount of methane. The hydrogen produced will be combined with a small amount of methane with the gas (H) entering through the cleavage product inlet 10 ₂ 、H ₂ S、NH ₃ With hydrocarbons) to dilute H ₂ S and ammonia. And controlling the reaction time for 7 hours, and outputting the generated mixture of the carbon nano tube and the hard carbon from the catalytic cracking uplink fluidized bed 2 through the outlet 13 to form a carbon material product.

In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, one skilled in the art can combine and combine the different embodiments or examples described in this specification.

For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.

The above description of the preparation method of porous carbon and the multistage fluidized bed reactor thereof provided by the invention applies specific examples to illustrate the principle and the implementation of the invention, and the above examples are only used for helping to understand the method and the core idea of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.

Claims

1. A system for producing sulfur and nitrogen containing oils into carbon materials and hydrogen, the system comprising: a thermal cracking downstream fluidized bed, a catalytic cracking upstream fluidized bed and a purifying and separating device;

The thermal cracking downstream fluidized bed is provided with a sulfur-nitrogen-containing oil product inlet and a cracking product outlet;

a light hydrocarbon gas inlet, a catalyst inlet, a pyrolysis product inlet communicated with the pyrolysis product outlet, a porous distribution plate, a cyclone separator, a mixed gas outlet and a carbon material outlet are sequentially arranged in the catalytic pyrolysis uplink fluidized bed along the gas flow direction; the light hydrocarbon gas inlet is positioned at the bottom of the catalytic cracking upward fluidized bed, the mixed gas outlet is positioned at the top of the catalytic cracking upward fluidized bed and is communicated with the cyclone separator, the catalyst inlet is arranged close to the light hydrocarbon gas inlet, and the cracking product inlet is positioned above the catalyst inlet so as to avoid contact of hydrogen sulfide and ammonia in the cracking product with the catalyst;

the purification and separation device is provided with a mixed gas inlet communicated with the mixed gas outlet, a light hydrocarbon gas outlet communicated with the light hydrocarbon gas inlet and a purified target product hydrogen outlet.

2. The system for preparing sulfur and nitrogen containing oil products into carbon material and hydrogen gas according to claim 1, wherein the purification and 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 light hydrocarbon gas inlet, the heat exchange device is communicated with the mixed gas outlet through a mixed gas inlet, the heat exchange device is communicated with the light hydrocarbon gas inlet through the light hydrocarbon gas outlet, and the heat exchange device is used for carrying out cooling treatment on the mixed gas entering the mixed gas through the mixed gas inlet and carrying out heating treatment on the light hydrocarbon gas entering the mixed gas through the light hydrocarbon gas inlet;

the desulfurization and denitrification device is provided with a heat exchange gas inlet and a desulfurization and denitrification gas outlet which are communicated with the heat exchange gas outlet; the desulfurization and denitrification device is used for removing hydrogen sulfide and ammonia in the mixed gas entering the desulfurization and denitrification device 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, a hydrogen outlet and a light hydrocarbon gas outlet communicated with the light hydrocarbon gas inlet, and is used for separating the light hydrocarbon and hydrogen entering the separation device through the desulfurization and denitrification gas inlet.

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

4. A process for preparing sulfur-nitrogen containing oils into carbon materials and hydrogen, said process being suitable for use in the system of any one of claims 1-3, said process comprising the steps of:

s1, introducing an oil product containing sulfur and nitrogen into a thermal cracking downstream fluidized bed from an oil product inlet containing sulfur and nitrogen for thermal cracking reaction to obtain a cracking product containing hard carbon, light hydrocarbon, hydrogen sulfide and ammonia;

s2, introducing the pyrolysis product into a catalytic pyrolysis uplink fluidized bed through a pyrolysis product inlet to perform gas-solid separation operation so as to intercept hard carbon in the pyrolysis product and output gaseous substances in the pyrolysis product;

s3, enabling the gaseous substances obtained in the step S2 to enter a purification and separation device through a mixed gas inlet so as to remove hydrogen sulfide and ammonia in the gaseous substances, and separating light hydrocarbon and hydrogen, wherein the hydrogen is a target product;

s4, introducing the light hydrocarbon obtained in the step S3 into the catalytic cracking upflow fluidized bed from a light hydrocarbon gas inlet of the catalytic cracking upflow fluidized bed, and then adding a catalyst through a catalyst inlet, wherein the light hydrocarbon undergoes a catalytic cracking reaction to generate a target product carbon nano tube.

5. The method for preparing sulfur and nitrogen containing oil products into carbon materials and hydrogen according to claim 4, wherein the purification and separation device comprises a heat exchange device, a desulfurization and denitrification device and a separation device, and the step S3 is specifically as follows:

S31, introducing the gaseous substance obtained in the step S2 into a heat exchange device through a mixed gas inlet for cooling treatment;

s32, introducing the gaseous substances subjected to the temperature reduction treatment into a desulfurization and denitrification device 3-2 through a heat exchange gas inlet so as to remove hydrogen sulfide and ammonia in the gaseous substances and obtain mixed gas consisting of light hydrocarbon and hydrogen;

s33, introducing the mixed gas obtained in the step S32 into a separation device through a desulfurization and denitrification gas inlet to separate light hydrocarbon and hydrogen, wherein the hydrogen is a target product.

6. The method for preparing sulfur and nitrogen containing oil products into carbon materials and hydrogen according to claim 4, wherein in step S1, the temperature required for the thermal cracking reaction is 800-1100 ℃ for 1-20S.

7. The method for preparing sulfur and nitrogen containing oil products into carbon materials and hydrogen according to claim 5, wherein in step S31, the temperature of the gaseous substances obtained by the cooling treatment is 300-500 ℃.

8. The method for preparing sulfur and nitrogen containing oil products into carbon materials and hydrogen according to claim 5, wherein in step S32, the desulfurization and denitrification device removes hydrogen sulfide and ammonia in the gaseous substances by water washing or acid-base neutralization.

9. The method for preparing sulfur and nitrogen containing oil products into carbon material and hydrogen according to claim 5, wherein in step S33, the separation device separates light hydrocarbon and hydrogen by pressure swing adsorption.

10. The method of preparing sulfur-nitrogen-containing oil as carbon material and hydrogen gas according to claim 4, wherein the sulfur-nitrogen-containing oil is at least one of catalytic diesel oil, coal tar, residual oil, crude oil slurry, biomass tar and petroleum tar with/without pitch, the sulfur content of the sulfur-nitrogen-containing oil is 10-12000mg/kg, and the nitrogen content of the sulfur-nitrogen-containing oil is 20-5000mg/kg;