CN115285976B - Carbon nano tube and fluidized bed preparation process for carbon nano tube - Google Patents
Carbon nano tube and fluidized bed preparation process for carbon nano tube Download PDFInfo
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- CN115285976B CN115285976B CN202210831351.1A CN202210831351A CN115285976B CN 115285976 B CN115285976 B CN 115285976B CN 202210831351 A CN202210831351 A CN 202210831351A CN 115285976 B CN115285976 B CN 115285976B
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Abstract
The application belongs to the technical field of carbon nanotubes, and particularly relates to a carbon nanotube and a preparation process of a carbon nanotube fluidized bed. Wherein, the preparation process of the carbon nano tube fluidized bed comprises the following steps: adding a carbon nano tube catalyst into an activation unit of a fluidized bed, and performing activation treatment to obtain an activated catalyst; conveying the activated catalyst into a growth unit of a fluidized bed to perform fluidized growth of the carbon nano tube to obtain a crude product; the inner wall of the growth unit is provided with an annular gas distributor; and (3) conveying the crude product to a purification unit for purification treatment to obtain the carbon nano tube. The preparation process of the carbon nano tube fluidized bed combines the fluidized bed production process and the purification process, reduces the production cost, simplifies the production process, is more economical and environment-friendly, has good material fluidization effect and purification effect, and ensures that the prepared carbon nano tube has high purity and good structural integrity.
Description
Technical Field
The application belongs to the technical field of carbon nanotubes, and particularly relates to a carbon nanotube and a preparation process of a carbon nanotube fluidized bed.
Background
Carbon nanotubes are considered as a novel functional material and structural material with excellent performance, and are a hot spot for research in the last twenty years. To date, there are various methods for preparing carbon nanotubes, the most predominant of which include three methods: arc methods, laser ablation methods, and catalytic cracking methods. The catalytic cracking method is a method for growing carbon nanotubes by taking metals such as nanoscale iron, silver and the like as catalysts and taking carbon source gas as raw material gas to perform catalytic cracking reaction at high temperature. The carbon nano tube produced by the method has high purity, controllable specification and easy industrial scale-up, and is considered as the method for preparing the carbon nano tube with the most development prospect.
At present, a chemical vapor deposition method in a catalytic cracking method is mostly adopted in the aspect of carbon nano tube production, and a fluidized bed reactor is adopted in the prior art, and is a common device for batch and continuous production of carbon nano tubes. However, in the actual production of carbon nanotubes by the fluidized bed, there are often the following problems: 1. the gas distribution in the reaction chamber is not uniform enough, resulting in poor fluidization conditions; 2. the internal heating is uneven, so that the temperature difference is difficult to control, the uniformity of the form of the grown carbon nano tube cannot be ensured, and the quality of the carbon nano tube is reduced; 3. the high temperature tail gas produced is not utilized effectively.
Disclosure of Invention
The application aims to provide a carbon nano tube and a preparation process of a carbon nano tube fluidized bed, and aims to solve the problems that the fluidization state is poor and the quality of the carbon nano tube is affected in the existing fluidized bed production process.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a process for preparing a fluidized bed of carbon nanotubes, comprising the steps of:
adding a carbon nano tube catalyst into an activation unit of a fluidized bed, and performing activation treatment to obtain an activated catalyst;
conveying the activated catalyst into a growth unit of a fluidized bed to perform fluidized growth of the carbon nano tube to obtain a crude product; the inner wall of the growth unit is provided with an annular gas distributor;
and (3) conveying the crude product to a purification unit for purification treatment to obtain the carbon nano tube.
Further, the reaction conditions of the activation treatment include: reacting for 10-30 minutes under the conditions that the temperature is 300-400 ℃ and the flow rate of the reducing atmosphere is 80-120L/min.
Further, the reducing atmosphere includes a volume ratio of (1-2): 1 and a shielding gas.
Further, the step of fluidized growth of the carbon nanotubes comprises:
delivering the activated catalyst to the bottom of the growth unit;
after the temperature of the growth unit is increased to a set temperature, introducing carbon source gas and inert atmosphere from the bottom of the growth unit, and simultaneously outputting inert atmosphere along the inside of the growth unit by the annular gas distributor;
the activated catalyst catalyzes and grows carbon nano tubes and moves towards the top of the growth unit along with the airflow;
the top of the growth unit is provided with a gas-solid separation device for separating the crude product and tail gas.
Further, the step of increasing the temperature of the growth unit to a set temperature includes: raising the temperature of the growth unit to a set temperature by a heating assembly;
the growth unit comprises a first heating component arranged at the upper part and a second heating component arranged at the lower part along the height direction of the growth unit, wherein the heating temperature of the first heating component is 550-600 ℃, and the heating temperature of the second heating component is 700-750 ℃.
Further, the flow rate of the carbon source gas is 450-600L/min, and the flow rate of the inert atmosphere is 600-700L/min.
Further, the inert atmosphere comprises at least one of nitrogen, argon and helium.
Further, the gas flow rate of the annular gas distributor is 50-150L/min.
Further, the annular gas distributor is disposed from the bottom of the first heating assembly to the top region of the second heating assembly.
Further, a screen is arranged at the discharge port of the gas-solid separation device and is used for screening the crude product, conveying the crude product with qualified granularity to the purification unit, returning the crude product with unqualified granularity to the growth unit again,
further, the tail gas supplies heat to the growth unit again through the gas-solid separation device.
Further, the purification treatment step includes: and (3) conveying the crude product to the purification unit, spraying concentrated hydrochloric acid to the crude product, enabling the crude product to be in a boiling state, and reacting for 30-90 minutes at the temperature of 1000-1200 ℃ to obtain the carbon nano tube.
Further, the step of bringing the crude product to a boiling state comprises: introducing inert atmosphere with the flow rate of 400-600L/min from the bottom of the purification unit.
In a second aspect, the present application provides a carbon nanotube produced by the above method.
According to the preparation process of the carbon nano tube fluidized bed provided by the first aspect of the application, firstly, the carbon nano tube catalyst is activated in an activating unit, and then the activated catalyst is conveyed into a growing unit of the fluidized bed to catalyze the growth of the carbon nano tube. The annular gas distributor is arranged on the inner wall of the growth unit, so that the uniformity of the reaction temperature and the material concentration in the growth unit is improved, the furnace wall sintering carbon deposition of the growth unit can be effectively prevented, and the fluidization state of the materials can be further regulated. And then conveying the crude product to a purification unit for purification treatment, and removing impurity components in the crude product to obtain the carbon nano tube. The preparation process of the carbon nanotube fluidized bed provided by the application has good material fluidization effect, so that the prepared carbon nanotube has high purity and good structural integrity. And the fluidized bed process and the purification process are combined, so that the production cost is reduced, the production process is simplified, the method is more economical and environment-friendly, and the purification effect is good.
According to the carbon nano tube provided by the second aspect of the application, as the carbon nano tube is prepared by the fluidized bed process, the growth efficiency of the carbon nano tube is improved, so that the carbon nano tube has high purity and good structural integrity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a fluidized bed preparation process for carbon nanotubes according to an embodiment of the present application;
fig. 2 is a schematic structural view of a fluidized bed apparatus according to an embodiment of the present application.
Wherein, each reference sign in the figure:
1-activation unit 2-growth unit 3-purification unit 20-hollow structure
21-first gas inlet 22-first flat gas distributor 23-first heating element
24-second heating assembly 25-annular gas distributor 26-first gas-solid separation device
261-screen 262-tail gas conveying pipeline 263-gas outlet 264-feed inlet
265-discharge port 27-air inlet end 28-air outlet end 29-crude product conveying pipeline
31-second air inlet 32-second plate gas distributor 33-liquid inlet device
331-spray nozzle 34-second gas-solid separator 35-discharge slide valve
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to the specific contents of the respective components but also to the proportional relationship between the weights of the respective components, and thus, it is within the scope of the disclosure of the embodiments of the present application as long as the contents of the relevant components are scaled up or down according to the embodiments of the present application. Specifically, the mass in the embodiments of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
As shown in fig. 1, a first aspect of the embodiment of the present application provides a process for preparing a fluidized bed of carbon nanotubes, which includes the following steps:
s10, adding a carbon nano tube catalyst into an activation unit of a fluidized bed, and performing activation treatment to obtain an activated catalyst;
s20, conveying the activated catalyst into a growth unit of a fluidized bed, and performing fluidized growth on the carbon nano tube to obtain a crude product; the inner wall of the growth unit is provided with an annular gas distributor;
s30, conveying the crude product to a purification unit for purification treatment to obtain the carbon nano tube.
According to the preparation process of the carbon nano tube fluidized bed provided by the first aspect of the embodiment of the application, firstly, the carbon nano tube catalyst is activated in an activation unit, and then the activated catalyst is conveyed into a growth unit of the fluidized bed to catalyze the growth of the carbon nano tube. The inner wall of the growth unit is provided with the annular gas distributor, and gas is conveyed into the growth unit through the annular gas distributor, so that the uniformity of reaction temperature and material concentration in the growth unit is improved, the furnace wall sintering carbon deposition of the growth unit can be effectively prevented, and the fluidization state of the material can be further regulated. And then conveying the crude product to a purification unit for purification treatment, and removing impurity components in the crude product to obtain the carbon nano tube. The preparation process of the carbon nanotube fluidized bed provided by the embodiment of the application has good material fluidization effect, so that the prepared carbon nanotube has high purity and good structural integrity. And the fluidized bed process and the purification process are combined, so that the production cost is reduced, the production process is simplified, the method is more economical and environment-friendly, and the purification effect is good.
In some embodiments, in the step S10, the carbon nanotube catalyst is added to the activation unit of the fluidized bed, and the reaction conditions for performing the activation treatment include: reacting for 10-30 minutes under the conditions that the temperature is 300-400 ℃ and the flow rate of the reducing atmosphere is 80-120L/min. In this case, the carbon nanotube catalyst can be sufficiently activated, and the metal oxide in the carbon nanotube catalyst can be reduced, so that the catalytic activity of the catalyst can be improved, and the reaction efficiency can be ensured.
In some embodiments, the reducing atmosphere comprises a volume ratio of (1-2): 1 and a shielding gas. Under such conditions, the catalyst has better reduction effect on the carbon nano tube. In some embodiments, the inert gas comprises at least one of nitrogen, argon, helium.
In some embodiments, the carbon nanotube catalyst comprises at least one metallic element of iron, molybdenum, cobalt, nickel, titanium, vanadium, chromium, manganese, ruthenium, lead, silver, platinum, gold.
In some embodiments, the activation unit of the fluidized bed is arranged at the top of the growth unit, and the activated carbon nanotube catalyst can directly enter the growth unit from the bottom of the activation unit through the top of the growth unit, so that the production process is simplified. In some embodiments, the communication arrangement may be configured as an openable and closable push-pull door, electric door, etc. as desired during actual use. And opening a door which is communicated with the activating unit to enter the growing unit after the catalyst in the activating unit is activated.
In some embodiments, in step S20, the activated catalyst is conveyed to the fluidized bed growth unit with the assistance of the pulsed air flow, so that the activated catalyst enters the bottom of the growth unit with the assistance of the pulsed air flow, and further, the activated catalyst is fluidized and grown in the growth unit.
In some embodiments, the step of fluidized growth of the carbon nanotubes comprises:
s21, conveying the activated catalyst to the bottom of the growth unit. In some embodiments, the activated catalyst is delivered to the bottom of the growth unit by means of a pulsed gas flow, avoiding adhesion of the activated catalyst to the inside of the growth unit, gas-solid separation devices, etc., ensuring the utilization of the catalyst.
S22, after the temperature of the growth unit is increased to the set temperature, introducing carbon source gas and inert atmosphere from the bottom of the growth unit, and simultaneously outputting the inert atmosphere along the interior of the growth unit by the annular gas distributor. The carbon source gas and the inert atmosphere are introduced from the bottom of the growth unit, so that the catalyst can be fully contacted with the activated catalyst, and the fluidization effect of the activated catalyst can be improved. Meanwhile, the annular gas distributor outputs inert atmosphere along the interior of the growth unit, so that the fluidization state of materials can be further regulated, the uniformity of temperature distribution and concentration distribution in the interior of the growth unit is improved, the gas-solid contact efficiency is improved, and products better enter the separator to be discharged; but also is beneficial to preventing the furnace wall from sintering and depositing carbon. In some embodiments, the surface of the annular gas distributor evenly distributes the gas nozzles through which the gas is evenly and smoothly delivered to the interior of the growth cell.
S23, the activated catalyst catalyzes and grows the carbon nano tube, and moves towards the top of the growth unit along with the airflow; fluidization catalyzes the growth of carbon nanotubes. The more the material moves to the top of the growth unit along with the airflow, the more fully the carbon nano tube catalyzes the growth reaction.
S24, a gas-solid separation device is arranged at the top of the growth unit and used for separating crude products and tail gas. The separated crude product can be conveyed to a purification unit for purification through a pipeline, and the separated tail gas can be directly discharged out of the growth unit through the pipeline or can be reused.
In some embodiments, the step of increasing the temperature of the growth unit to the set temperature comprises: raising the temperature of the growth unit to a set temperature by a heating assembly; the growth unit comprises a first heating component arranged at the upper part and a second heating component arranged at the lower part along the height direction of the growth unit, wherein the heating temperature of the first heating component is 550-600 ℃, and the heating temperature of the second heating component is 700-750 ℃. In this case, two heating elements are disposed in the growth unit, and different temperatures are set, wherein the second heating element near the lower part has a higher heating temperature, so that the activated catalyst at the bottom can be better catalyzed to grow carbon nanotubes, the reaction activity is high, the catalytic effect is good, the temperature of the first heating element disposed at the upper part is relatively low, the catalyst material moves upwards in the fluidized bed along with the airflow, and the heating temperature of the first heating element is enough to enable the catalyst to continue to catalyze the growth of the carbon nanotubes. The energy-saving effect is good.
In some embodiments, the first heating component and the second heating component are both arranged on the outer wall surface of the growth unit, so that the heating component is convenient to disassemble and adjust, and the partition temperature control is easier to realize.
In some embodiments, the flow rate of the carbon source gas is 450 to 600L/min and the flow rate of the inert atmosphere is 600 to 700L/min. Under the condition, the carbon source gas is used as a raw material for the growth of the carbon nanotubes, the carbon source gas is cracked into micromolecular hydrocarbon gas at high temperature, the carbon nanotubes are catalytically grown under the action of the catalyst, the flow speed of the inert atmosphere is slightly higher than that of the carbon source gas, the inert atmosphere can be used as carrier gas, the fluidization effect of materials in the growth unit is ensured, and the oxygen in the growth unit is also prevented from interfering with the catalytic growth efficiency of the carbon nanotubes.
In some embodiments, the carbon source gas includes, but is not limited to, at least one of propylene, ethylene, hexane, acetylene, methane, butane, carbon monoxide, benzene, ethanol. At least one carbon source gas of acetylene, ethylene, hexane, methane, propylene, butane, carbon monoxide, benzene and ethanol adopted by the embodiment of the application can be rapidly and stably cracked into carbon atoms at 660-680 ℃, thereby providing a material foundation for rapid, efficient and stable growth of the subsequent carbon nanotubes. The carbon source gas is preferably propylene, and the reaction is easy to control.
In some embodiments, the inert atmosphere comprises at least one of nitrogen, argon, helium.
In some embodiments, the carbon source gas and inert atmosphere enter from a bottom gas inlet of the growth unit. In some preferred embodiments, a flat gas distributor is provided at the bottom inlet of the growth unit, by which the carbon source gas and inert atmosphere entering the growth unit are more stable, distributed more uniformly, and the flow rate of the gas is advantageously adjusted. The gas distributor according to the embodiment of the application is a device for uniformly distributing the gas entering the fluidized bed over the whole cross section. The embodiment of the application preferably adopts a flat plate type gas distributor.
In some embodiments, the annular gas distributor has a gas flow rate of 50 to 150L/min; under the condition, the gas flow rate of the annular gas distributor can further improve the uniformity of the temperature distribution and the concentration distribution of the region in the growth unit, further adjust the fluidization state of the materials and enable the products to better enter the separator for discharging; but also can avoid the interference of the excessive gas flow rate to the fluidization state of the materials, so that the materials can stably and fully move to the gas-solid separation device for separation.
In some embodiments, an annular gas distributor is disposed from the bottom of the first heating assembly to the top region of the second heating assembly. According to the embodiment of the application, the area from the bottom of the first heating component to the top of the second heating component is considered, the reaction temperature is higher, the growth catalytic activity of the carbon nano tube is higher, the material density is high, and the material is easier to agglomerate in the area, so that the fluidization state of the material can be effectively improved, the risk of material agglomeration is reduced, and meanwhile, the sintering carbon deposition of the furnace wall is prevented.
In some embodiments, the discharge port of the gas-solid separation device is provided with a screen for screening the crude product, conveying the crude product with qualified granularity to the purification unit, and returning the crude product with unqualified granularity to the growth unit again to continue catalytic growth of the carbon nanotubes. The carbon nano tube crude product enters along with the gas flow through a feed inlet of the gas-solid separation device, the gas-solid separation device separates the carbon nano tube crude product from the gas, the carbon nano tube crude product separated by the gas-solid separation device is screened by a screen of a discharge hole, the large carbon nano tube crude product is directly conveyed to a purification unit for purification through a crude product conveying pipeline, and the small crude product can return to a growth unit through the screen again for catalytic growth of the carbon nano tube.
In some embodiments, the tail gas is re-supplied to the growth unit by a gas-solid separation device. Under the condition, the waste heat of the tail gas can be utilized to not only provide heat energy for the growth unit again and promote the catalytic reaction in the growth unit to be carried out, so that the energy is fully utilized, but also reduce the tail gas treatment procedure, and the device is energy-saving and environment-friendly.
In some embodiments, the container wall of the growth unit is a hollow structure, the hollow structure comprises an air inlet end and an air outlet end which are oppositely arranged, a tail gas conveying pipeline of the air-solid separation device is communicated with the air inlet end of the hollow structure, after the tail gas is separated by the air-solid separation device, the tail gas is conveyed to the air inlet end through the tail gas conveying pipeline to enter the hollow structure, and after the waste heat of the tail gas is utilized to provide heat energy for the growth unit, the heat energy is discharged from an air outlet at the air outlet end of the hollow structure. In a further preferred embodiment, the container wall at the lower part of the growth unit is of a hollow structure, and the waste heat of the tail gas is mainly supplied to the lower part of the growth unit in a concentrated mode, so that the catalyst in the growth unit has better catalytic activity.
In some embodiments, in the step S30, the step of purifying includes: and (3) delivering the crude product to a purification unit, spraying concentrated hydrochloric acid to the crude product, enabling the crude product to be in a boiling state, and reacting for 30-90 minutes at the temperature of 1000-1200 ℃ to obtain the carbon nano tube. In this case, carbon impurities in the crude product of carbon nanotubes can react with moisture in hydrochloric acid under high temperature conditions to generate carbon monoxide and hydrogen, and repel carbon impurities in the crude product in gaseous form; meanwhile, under the high temperature environment, metal catalysts such as iron and the like in the crude product of the carbon nano tube can react with hydrochloric acid to generate metal salt and hydrogen, and under the high temperature condition of 1000-1200 ℃, the metal salt can be converted into volatile substances, and the volatile substances are volatilized and removed in the form of tail gas. Therefore, carbon impurities and metal catalyst impurities in the crude product can be removed simultaneously through the purification treatment, the purification efficiency is high, the process is simple, and the purification effect is good.
In some embodiments, a heating unit is provided in the purification unit for providing heat for the purification reaction.
In some embodiments, the step of bringing the crude product to a boiling state comprises: an inert atmosphere with a flow rate of 400-600L/min is introduced from the bottom of the purification unit. In some specific embodiments, in the purification unit, concentrated hydrochloric acid solution is sprayed into the crude product from the upper part, and inert atmosphere such as nitrogen is continuously introduced into the lower part of the purification unit, so that crude product materials are in a tumbling state in the concentrated hydrochloric acid, and the contact and dissolution removal efficiency of the concentrated hydrochloric acid on metal impurities and carbon impurities in the crude product is improved.
In some embodiments, a carbon nanotube fluidized bed preparation process comprises the steps of:
s01, adding a carbon nano tube catalyst into an activation unit of a fluidized bed, and carrying out an activation reaction for 10-30 minutes under the conditions that the temperature is 300-400 ℃ and the flow rate of a reducing atmosphere is 80-120L/min; wherein the reducing atmosphere comprises the following components in volume ratio (1-2): 1 and a shielding gas.
S02, an activation unit is arranged at the top of the growth unit, and an activation catalyst enters the bottom of the growth unit from the bottom of the activation unit through the top of the growth unit under the assistance of pulse gas; setting the heating temperature of the first heating component to 550-600 ℃ and the heating temperature of the second heating component to 700-750 ℃, after the temperature of the growth unit is raised to the set temperature, introducing carbon source gas from a bottom air inlet of the growth unit at a flow rate of 450-600L/min and introducing inert atmosphere at a flow rate of 600-700L/min, and simultaneously outputting the inert atmosphere along the interior of the growth unit at a flow rate of 50-150L/min by an annular gas distributor arranged at the bottom of the first heating component to the top area of the second heating component; the active catalyst catalyzes the growth of the carbon nanotubes and moves toward the top of the growth unit with the gas flow. When the materials move to the top of the growth unit, the materials enter the gas-solid separation device from the feed inlet and are separated into crude products and tail gas. The screen mesh arranged at the discharge port of the gas-solid separation device is used for further screening the crude product, conveying the crude product with qualified granularity to the purification unit, and returning the crude product with unqualified granularity to the growth unit. In addition, the tail gas is conveyed to the hollow structure of the container wall of the growth unit through the tail gas conveying pipeline of the gas-solid separation device, and the waste heat of the tail gas is utilized to provide heat energy for the growth unit and then is discharged from the gas outlet at the gas outlet end of the hollow structure.
S03, after the crude product is conveyed to a purification unit, spraying concentrated hydrochloric acid to the crude product from the top of the purification unit, introducing inert atmosphere with the flow rate of 400-600L/min from the bottom of the purification unit, enabling the crude product to be in a boiling state, and reacting for 30-90 minutes at the temperature of 1000-1200 ℃ to obtain the carbon nano tube.
In some embodiments, the fluidized bed apparatus for preparing carbon nanotubes is shown in fig. 2, and comprises an activation unit 1, a growth unit 2 and a purification unit 3, which are sequentially connected, wherein the activation unit 1 is used for activating a carbon nanotube catalyst, and the activated carbon nanotube catalyst is transferred to the growth unit 2; the bottom of the activation unit 1 is communicated with the top of the growth unit 2. The growth unit 2 is used for catalyzing the growth of the carbon nano tube and comprises a first air inlet 21 arranged at the bottom, a heating component arranged on the wall surface, a first gas-solid separation device 26 arranged at the top and an annular gas distributor 25 arranged around the inner wall of the growth unit 2; wherein the growth unit 2 further comprises a first flat plate gas distributor 22 arranged at the first gas inlet 21. The heating assembly includes a first heating assembly 23 disposed at an upper portion of the growth unit 2 and a second heating assembly 24 disposed at a lower portion thereof in a height direction of the growth unit 2; and the heating temperature of the first heating member 23 is lower than that of the second heating member 24, which is provided on the outer wall surface of the growth unit 2. An annular gas distributor 25 is provided at the bottom of the first heating assembly 23 to the bottom region of the second heating assembly 24. The first gas-solid separation device 26 is used for separating coarse products and tail gas, and comprises a feed inlet 265 and a discharge outlet 264, the coarse products of the carbon nano tubes enter the first gas-solid separation device 26 along with airflow through the feed inlet 265 for gas-solid separation, the discharge outlet 264 is provided with a screen 261, the screen 261 is used for screening the coarse products separated by the first gas-solid separation device 26, the coarse products with qualified granularity are conveyed to the purification unit 3, and the coarse products with unqualified granularity are returned to the growth unit 2 again. The container wall of the growth unit 2 is a hollow structure 20, and the hollow structure 20 comprises an air inlet end 27 and an air outlet end 28 which are oppositely arranged; the tail gas is conveyed to the air inlet end 27 through the tail gas conveying pipeline 262 of the first gas-solid separation device 26, enters the hollow structure 20, and is discharged from the air outlet 263 at the air outlet end 28. The purification unit 3 is used for purifying the crude product, and comprises a second air inlet 31 arranged at the bottom, and a second flat plate gas distributor 32 is further arranged at the second air inlet 31, so that the gas entering the purification unit 3 is more stable and more uniformly distributed through the flat plate gas distributor, and the flow rate of the gas is favorably regulated. A second gas-solid separation device 34 disposed at the top for separating the purified carbon nanotubes and the tail gas; and a liquid inlet device 33 arranged at the top, wherein the liquid inlet device 33 further comprises a plurality of liquid spraying ports 331 arranged at the top of the purifying unit 3. The purification unit 3 is further provided with a discharge slide valve 35 for collecting purified carbon nanotubes. The wall surface of the purification unit 3 is also provided with a heating unit, and a proper reaction temperature is provided for the purification of the crude product of the medium carbon nano tube of the purification unit 3 through the heating unit.
In a second aspect, the present application provides a carbon nanotube, which is manufactured by the above method.
According to the carbon nano tube provided by the second aspect of the embodiment of the application, as the carbon nano tube is prepared by the fluidized bed process, the growth efficiency of the carbon nano tube is improved, so that the purity of the carbon nano tube is high, and the structural integrity is good.
In order that the details and operations of the present application may be clearly understood by those skilled in the art, and that the carbon nanotubes of the embodiments of the present application and the advanced performance of the fluidized bed preparation process of the carbon nanotubes thereof may be significantly embodied, the following examples are given by way of illustration of the above technical solution.
Example 1
A fluidized bed preparation process of carbon nanotubes, the structural schematic diagram of which is shown in figure 2, comprises the following steps:
1. adding the ternary alloy of iron, molybdenum and nickel carried by the catalyst carrier into an activation unit 1, and introducing hydrogen and nitrogen with the volume ratio of 80L/min of 2:1, and reducing for 10min at the reduction temperature of 300 ℃ to obtain an activated catalyst; the activated catalyst is then pulsed in with nitrogen into the furnace of the growth unit 2. The bottom of the activation unit 1 is also mounted on top of the growth unit 2 with a switching channel between them.
2. The heating temperature of the first heating member 23 was 550 c and the heating temperature of the second heating member 24 was 700 c, which were provided in the growth unit 2. After the reaction furnace reached the set temperature, carbon source gas and nitrogen gas were introduced through the first gas inlet 21, and carbon source propylene and nitrogen gas were provided at a gas flow rate of 450L/min and 600L/min in the first flat plate gas distributor 22, and nitrogen gas was provided at a gas flow rate of 50L/min in the annular gas distributor 25. The annular gas distributor 25 surrounds the furnace wall for one circle, and conveys gas inwards to prevent the furnace wall from sintering carbon deposition, and can further adjust the fluidization state of the materials.
3. The materials are reacted from the bottom to the top all the time, and enter the first gas-solid separation device 26 through the feed port 265, wherein the tail gas separated by the first gas-solid separation device 26 is conveyed into the hollow structure 20 at the lower part of the growth unit 2 through the tail gas conveying pipeline 262, and is discharged after supplying heat to the furnace wall at the lower part. In addition, the separated crude product passes through a screen 261 arranged at a discharge port 264 of the first gas-solid separation device 26, large particles are conveyed to the purification unit 3 from the crude product conveying pipeline 29, and small particles enter the growth unit 2 again through the screen 261 for reaction. The time from carbon source entry to final discharge is approximately 40-60 minutes.
4. When the reaction is completed, the crude product is fed to the purification unit 3, and the generated tail gas is discharged from the gas outlet 263 at the gas outlet end 28. Concentrated hydrochloric acid is continuously sprayed from a liquid spraying port 331 of a liquid inlet device 33 at the upper part of the purification unit 3, nitrogen is continuously introduced from a second air inlet 31 at the lower part of the purification unit 3, the speed is regulated to be 500L/min through a second flat gas distributor 32, the materials are in a boiling state, the reaction temperature is set to 1100 ℃, the purification is carried out for 60 minutes, a second gas-solid separation device 34 is arranged at the top of the purification unit 3, the purified products and tail gas are separated, and the purified carbon nanotubes are purged to a small carbon powder tank through a discharge slide valve 35 and collected, so that the purified carbon nanotubes are obtained.
Example 2
A fluidized bed preparation process of carbon nanotubes, the structural schematic diagram of which is shown in figure 2, comprises the following steps:
1. adding the iron, molybdenum and nickel ternary alloy carried by the catalyst carrier into an activation unit 1, and introducing 120L/min of hydrogen and nitrogen with the volume ratio of 2:1, and reducing for 10min at the reduction temperature of 400 ℃ to obtain an activated catalyst; the activated catalyst is then pulsed in with nitrogen into the furnace of the growth unit 2. The bottom of the activation unit 1 is mounted on the top of the growth unit 2 with a switching channel therebetween.
2. The heating temperature of the first heating element 23 is set to 600 c and the heating temperature of the second heating element 24 is set to 750 c in the growth unit 2. After the reaction furnace reached the set temperature, carbon source gas and nitrogen gas were introduced through the first gas inlet 21, and carbon source propylene and nitrogen gas were provided at a gas flow rate of 600L/min and 700L/min in the first flat plate gas distributor 22, and nitrogen gas was provided at a gas flow rate of 150L/min in the annular gas distributor 25. The annular gas distributor 25 surrounds the furnace wall for one circle, and conveys gas inwards to prevent the furnace wall from sintering carbon deposition, and can further adjust the fluidization state of the materials.
3. The materials are reacted from the bottom to the top all the time, and enter the first gas-solid separation device 26 through the feed port 265, wherein the tail gas separated by the first gas-solid separation device 26 is conveyed into the hollow structure 20 at the lower part of the growth unit 2 through the tail gas conveying pipeline 262, and is discharged after supplying heat to the furnace wall at the lower part. In addition, the separated crude product passes through a screen 261 arranged at a discharge port 264 of the first gas-solid separation device 26, large particles are conveyed to the purification unit 3 from the crude product conveying pipeline 29, and small particles enter the growth unit 2 again through the screen 261 for reaction. The time from carbon source entry to final discharge is approximately 40-60 minutes.
4. When the reaction is completed, the crude product is fed to the purification unit 3, and the generated tail gas is discharged from the gas outlet 263 at the gas outlet end 28. Concentrated hydrochloric acid is continuously sprayed from a liquid spraying port 331 of a liquid inlet device 33 at the upper part of the purification unit 3, nitrogen is continuously introduced from a second air inlet 31 at the lower part of the purification unit 3, the speed is regulated to 550L/min through a second flat gas distributor 32, the materials are in a boiling state, the reaction temperature is set to 1150 ℃, the purification is carried out for 56 minutes, a second gas-solid separation device 34 is arranged at the top of the purification unit 3, the purified products and tail gas are separated, and the purified carbon nanotubes are purged to a small carbon powder tank through a discharge slide valve 35 and collected, so that the purified carbon nanotubes are obtained.
Example 3
A fluidized bed preparation process of carbon nanotubes, the structural schematic diagram of which is shown in figure 2, comprises the following steps:
1. adding the iron, molybdenum and nickel ternary alloy carried by the catalyst carrier into an activation unit 1, and introducing hydrogen and nitrogen with the volume ratio of 100L/min of 2:1, and reducing for 10min at the reduction temperature of 350 ℃ to obtain an activated catalyst; the activated catalyst is then pulsed in with nitrogen into the furnace of the growth unit 2. The bottom of the activation unit 1 is also mounted on top of the growth unit 2 with a switching channel between them.
2. The heating temperature of the first heating element 23 was 580c and the heating temperature of the second heating element 24 was 720 c in the growth unit 2. After the reaction furnace reached the set temperature, carbon source gas and nitrogen gas were introduced through the first gas inlet 21, and carbon source propylene and 650L/min nitrogen gas were supplied at a gas flow rate of 500L/min to the first flat plate gas distributor 22, and nitrogen gas was supplied at a gas flow rate of 100L/min to the annular gas distributor 25. The annular gas distributor 25 surrounds the furnace wall for one circle, and conveys gas inwards to prevent the furnace wall from sintering carbon deposition, and can further adjust the fluidization state of the materials.
3. The materials are reacted from the bottom to the top all the time, and enter the first gas-solid separation device 26 through the feed port 265, wherein the tail gas separated by the first gas-solid separation device 26 is conveyed into the hollow structure 20 at the lower part of the growth unit 2 through the tail gas conveying pipeline 262, and is discharged after supplying heat to the furnace wall at the lower part. In addition, the separated crude product passes through a screen 261 arranged at a discharge port 264 of the first gas-solid separation device 26, large particles are conveyed to the purification unit 3 from the crude product conveying pipeline 29, and small particles enter the growth unit 2 again through the screen 261 for reaction. The time from carbon source entry to final discharge is approximately 40-60 minutes.
4. When the reaction is completed, the crude product is fed to the purification unit 3, and the generated tail gas is discharged from the gas outlet 263 at the gas outlet end 28. Concentrated hydrochloric acid is continuously sprayed from a liquid spraying port 331 of a liquid inlet device 33 at the upper part of the purification unit 3, nitrogen is continuously introduced from a second air inlet 31 at the lower part of the purification unit 3, the speed is regulated to 550L/min through a second flat gas distributor 32, the materials are in a boiling state, the reaction temperature is set to 1200 ℃, the purification is carried out for 55 minutes, a second gas-solid separation device 34 is arranged at the top of the purification unit 3, the purified products and tail gas are separated, and the purified carbon nanotubes are purged to a small carbon powder tank through a discharge slide valve 35 and collected, so that the purified carbon nanotubes are obtained.
Comparative example 1
A fluidized bed preparation process of carbon nanotubes, the structural schematic diagram of which is shown in figure 2, comprises the following steps:
the preparation process differs from example 3 in that: the annular gas distributor was closed during the production process and the other steps and operations were the same as in example 3.
Further, in order to verify the progress of the embodiment of the present application, the purity, structural integrity and other properties of the carbon nanotubes prepared in the examples and comparative examples were tested, respectively, and the test results are shown in the following table 1:
TABLE 1
The typical peak for the Raman spectrum of carbon nanotubes appears at 1350cm -1 1580cm -1 Where it is located. Of which 1350cm -1 The peak is called a D peak, and the intensity corresponds to the defect degree of the carbon nano tube; 1580cm -1 The peak is called G peak, and the intensity corresponds to the integrity degree of the carbon nano tube; thus, can pass through I D /I G Characterizing the structural integrity of the carbon nanotubes.
As can be seen from Table 1, the fluidized bed preparation process of examples 1 to 3 of the present application has high purity and good structural integrity. In comparative example 1, since the annular gas distributor was closed, materials were easily agglomerated during the production process, carbon nanotubes were easily agglomerated and grown, the purity of the produced carbon nanotubes was reduced, and I D /I G The value is increased, and defects of the carbon nano tube are increased, so that the purifying effect is also reduced.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (8)
1. The preparation process of the carbon nano tube fluidized bed is characterized by comprising the following steps of:
adding a carbon nano tube catalyst into an activation unit of a fluidized bed, and performing activation treatment to obtain an activated catalyst;
conveying the activated catalyst into a growth unit of a fluidized bed to perform fluidized growth of the carbon nano tube to obtain a crude product; the inner wall of the growth unit is provided with an annular gas distributor;
a first heating assembly disposed at an upper portion and a second heating assembly disposed at a lower portion along a height direction of the growth unit; the annular gas distributor is arranged from the bottom of the first heating component to the top area of the second heating component; the gas flow rate of the annular gas distributor is 50-150L/min;
the step of fluidization growth of the carbon nano tube comprises the following steps: delivering the activated catalyst to the bottom of the growth unit; after the temperature of the growth unit is increased to a set temperature through a heating component, the heating temperature of the first heating component is 550-600 ℃, the heating temperature of the second heating component is 700-750 ℃, carbon source gas and inert atmosphere are introduced from the bottom of the growth unit, and meanwhile, the annular gas distributor outputs inert atmosphere along the interior of the growth unit; the activated catalyst catalyzes and grows carbon nano tubes and moves towards the top of the growth unit along with the airflow;
and (3) conveying the crude product to a purification unit for purification treatment to obtain the carbon nano tube.
2. The process for preparing a fluidized bed of carbon nanotubes according to claim 1, wherein the reaction conditions of the activation treatment include: reacting for 10-30 minutes under the conditions that the temperature is 300-400 ℃ and the flow rate of the reducing atmosphere is 80-120L/min;
and/or, the reducing atmosphere comprises the following components in volume ratio (1-2): 1 and a shielding gas;
and/or the activated catalyst is delivered to the bottom of the growth unit by means of a pulsed jet feed.
3. The fluidized bed preparation process of carbon nanotubes according to claim 1 or 2, wherein the step of fluidized growth of the carbon nanotubes further comprises: the top of the growth unit is provided with a gas-solid separation device for separating the crude product and tail gas.
4. The process for preparing a fluidized bed of carbon nanotubes according to claim 3, wherein the flow rate of the carbon source gas is 450 to 600l/min, and the flow rate of the inert atmosphere is 600 to 700l/min;
and/or the inert atmosphere comprises at least one of nitrogen, argon and helium.
5. The process for preparing a fluidized bed of carbon nanotubes according to claim 4, wherein a screen is arranged in a discharge port of the gas-solid separation device for screening the crude product, conveying the crude product with qualified granularity to the purification unit, and returning the crude product with unqualified granularity to the growth unit;
and/or the tail gas supplies heat for the growth unit again through the gas-solid separation device.
6. The fluidized bed preparation process for carbon nanotubes according to any one of claims 1, 2, 4 to 5, wherein the purification process comprises the steps of: and (3) conveying the crude product to the purification unit, spraying concentrated hydrochloric acid to the crude product, enabling the crude product to be in a boiling state, and reacting for 30-90 minutes at the temperature of 1000-1200 ℃ to obtain the carbon nanotube.
7. The fluidized bed preparation process of carbon nanotubes according to claim 6, wherein the step of bringing the crude product into a boiling state comprises: and introducing inert atmosphere with the flow rate of 400-600L/min from the bottom of the purification unit.
8. A carbon nanotube, wherein the carbon nanotube is produced by the process of any one of claims 1 to 7.
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