CN115285976A - Carbon nano tube and carbon nano tube fluidized bed preparation process - Google Patents
Carbon nano tube and carbon nano tube fluidized bed preparation process Download PDFInfo
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- CN115285976A CN115285976A CN202210831351.1A CN202210831351A CN115285976A CN 115285976 A CN115285976 A CN 115285976A CN 202210831351 A CN202210831351 A CN 202210831351A CN 115285976 A CN115285976 A CN 115285976A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C01B32/164—Preparation involving continuous processes
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
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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. 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 to a growth unit of a fluidized bed for 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 conveying the crude product to a purification unit for purification treatment to obtain the carbon nano tube. The preparation process of the carbon nanotube fluidized bed combines the production process of the fluidized bed and the purification process, reduces the production cost, simplifies the production process, is more economic and environment-friendly, and has good material fluidization effect and good purification effect, so that the prepared carbon nanotube 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 to be a novel functional material and structural material with excellent performance, and have been the focus of research in the last two decades. There are several methods for preparing carbon nanotubes so far, and the most predominant methods include three: arc, laser ablation, and catalytic cracking. The catalytic cracking method is a method for growing carbon nanotubes by taking a catalytic cracking reaction at a high temperature by taking nano-scale metals such as iron, silver and the like as a catalyst and taking a carbon source gas as a raw material gas. The carbon nano tube produced by the method has high purity, controllable specification and easy industrial amplification, and is considered to be the method for preparing the carbon nano tube with the greatest development prospect.
At present, the chemical vapor deposition method in the catalytic cracking method, which is frequently used in the production of carbon nanotubes, adopts a fluidized bed reactor in the prior art, and the fluidized bed reactor is a common device for mass and continuous production of carbon nanotubes. However, in the actual production of carbon nanotubes by fluidized bed, the following problems often occur: 1. the gas distribution in the reaction chamber is not uniform enough, resulting in poor fluidization state; 2. the internal heating is uneven, so that the temperature difference is difficult to control, the form of the grown carbon nano tube cannot be consistent, and the quality of the carbon nano tube is reduced; 3. the generated high-temperature tail gas is not effectively utilized.
Disclosure of Invention
The application aims to provide a carbon nanotube and a preparation process of a carbon nanotube fluidized bed, and aims to solve the problem that the quality of the carbon nanotube is affected due to the fact that the fluidized state is not good in the process of producing the carbon nanotube by using the existing fluidized bed to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a fluidized bed process for preparing 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 to a growth unit of a fluidized bed for 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 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 comprises a mixture of (1-2): 1 hydrogen and a shielding gas.
Further, the step of fluidized growth of carbon nanotubes comprises:
transporting the activated catalyst to the bottom of the growth unit;
after the temperature of the growth unit is raised to a 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 activated catalyst catalyzes and grows the carbon nano tube and moves to the top of the growth unit along with the airflow;
and a gas-solid separation device is arranged at the top of the growth unit and used for separating the crude product and the tail gas.
Further, the step of raising 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 assembly arranged at the upper part and a second heating assembly arranged at the lower part along the height direction of the growth unit, the heating temperature of the first heating assembly is 550-600 ℃, and the heating temperature of the second heating assembly 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, helium.
Further, the gas flow rate of the annular gas distributor is 50-150L/min.
Further, the annular gas distributor is disposed from a bottom of the first heating assembly to a top region of the second heating assembly.
Furthermore, a discharge port of the gas-solid separation device is provided with a screen mesh for screening the crude product, the crude product with qualified granularity is conveyed to the purification unit, the crude product with unqualified granularity returns to the growth unit again,
further, the tail gas supplies heat to the growth unit again through the gas-solid separation device.
Further, the step of purifying treatment comprises: and after conveying the crude product to the purification unit, spraying concentrated hydrochloric acid on 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 boiling comprises: and 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, which is produced by the above method.
In the preparation process of the carbon nanotube fluidized bed provided by the first aspect of the present application, the carbon nanotube catalyst is activated in the activation unit, and then the activated catalyst is transported in the growth unit of the fluidized bed to catalyze the growth of the carbon nanotube. The inner wall of the growth unit is provided with the annular gas distributor, so that the uniformity of the reaction temperature and the material concentration in the growth unit is favorably improved, the sintering carbon deposition on the furnace wall of the growth unit can be effectively prevented, and the fluidization state of the material can be further adjusted. 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 has the advantages that the material fluidization effect is good, and 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 economic and environment-friendly, and the purification effect is good.
The carbon nanotube provided by the second aspect of the present application is prepared by the fluidized bed process, so that the growth efficiency of the carbon nanotube is improved, the purity of the carbon nanotube is high, and the structural integrity is good.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow chart of a fluidized bed preparation process of carbon nanotubes provided in the examples of the present application;
FIG. 2 is a schematic structural diagram of a fluidized bed apparatus provided in an embodiment of the present application.
Wherein, in the figures, the various reference numbers:
1-activating unit 2-growing unit 3-purifying unit 20-hollow structure
21 first inlet 22 first plate 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-inlet end 28-outlet end 29-crude product conveying pipeline
31-second inlet 32-second flat gas distributor 33-liquid inlet device
331-liquid spray port 34-second gas-solid separation device 35-discharge slide valve
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) 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, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, 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 function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of 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 weight of the related components mentioned in the embodiments of the present specification may not only refer to the specific content of each component, but also represent the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the embodiments of the present specification is within the scope disclosed in the embodiments of the present specification. Specifically, the mass in the examples of the present application may be in units of mass known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. 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 present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a fluidized bed preparation process of carbon nanotubes, including 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 to a growth unit of a fluidized bed for 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 S30, conveying the crude product to a purification unit, and performing purification treatment to obtain the carbon nano tube.
In the preparation process of the carbon nanotube fluidized bed provided in the first aspect of the embodiment of the present application, the carbon nanotube catalyst is activated in the activation unit, and then the activated catalyst is transported in the growth unit of the fluidized bed to catalyze the growth of the carbon nanotube. 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 the reaction temperature and the material concentration in the growth unit is favorably improved, the sintering carbon deposition on the furnace wall of the growth unit can be effectively prevented, and the fluidization state of the material can be further adjusted. 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 the advantages that the material fluidization effect is good, and 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 economic 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 to reduce the metal oxide in the carbon nanotube catalyst, thereby improving the catalytic activity of the catalyst and ensuring the reaction efficiency.
In some embodiments, the reducing atmosphere comprises a volume ratio of (1-2): 1 hydrogen and a shielding gas. Under the condition, the carbon nano tube catalyst has better reduction effect. 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 metal element selected from the group consisting of iron, molybdenum, cobalt, nickel, titanium, vanadium, chromium, manganese, ruthenium, lead, silver, platinum, and gold.
In some embodiments, the activation unit of the fluidized bed is arranged at the top of the growth unit, and the carbon nanotube catalyst after activation treatment 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 device can be a push-pull door, a power door, etc. which can be opened or closed according to the requirement during the actual use. And after the catalyst in the activation unit is activated, opening a door arranged in a communicating manner to enter the growth unit.
In some embodiments, in the step S20, the activated catalyst is delivered to the fluidized bed growth unit with the aid of the pulse gas flow, and the activated catalyst is advantageously introduced into the bottom of the growth unit and is more advantageously fluidized and grown in the growth unit with the aid of the pulse gas flow.
In some embodiments, the step of fluidized growth of carbon nanotubes comprises:
and S21, conveying the activated catalyst to the bottom of the growth unit. In some embodiments, the activated catalyst is conveyed to the bottom of the growth unit by means of the pulse airflow, so that the activated catalyst is prevented from being adhered to the inside of the growth unit, a gas-solid separation device and the like, and the utilization rate of the catalyst is ensured.
And S22, after the temperature of the growth unit is raised to a set temperature, introducing a carbon source gas and an inert atmosphere from the bottom of the growth unit, and simultaneously outputting the inert atmosphere along the inside 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 carbon source gas and the inert atmosphere can be fully contacted with the activated catalyst, and the fluidization effect of the activated catalyst is improved. Meanwhile, the annular gas distributor outputs inert atmosphere along the inside of the growth unit, so that the fluidization state of the material can be further adjusted, the uniformity of the temperature distribution and the concentration distribution of the area in the growth unit is improved, the gas-solid contact efficiency is improved, and the product can better enter a separator for discharging; but also is beneficial to preventing the sintering carbon deposition of the furnace wall. In some embodiments, the surface of the annular gas distributor is uniformly distributed with gas nozzles through which gas is uniformly and smoothly delivered to the interior of the growth unit.
S23, activating a catalyst to catalyze and grow the carbon nano tube, and moving the carbon nano tube to the top of the growth unit along with airflow; fluidization catalyzes the carbon nanotube growth. The more the material moves to the top of the growth unit along with the airflow, the more the carbon nano tube has full catalytic growth reaction.
And S24, arranging a gas-solid separation device at the top of the growth unit, and separating the crude product from the tail gas. The separated crude product can be transported to a purification unit through a pipeline for purification, and the separated tail gas can be directly discharged out of the growth unit through a pipeline or can be reused.
In some embodiments, the step of raising 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 assembly arranged at the upper part and a second heating assembly arranged at the lower part along the height direction of the growth unit, the heating temperature of the first heating assembly is 550-600 ℃, and the heating temperature of the second heating assembly is 700-750 ℃. Under the condition, two heating assemblies are arranged in the growth unit, different temperatures are set, wherein the second heating assembly close to the lower part has higher heating temperature, the activated catalyst at the bottom can be better catalyzed to grow the carbon nano tubes, the reaction activity is high, the catalysis effect is good, the temperature of the first heating assembly arranged at the upper part is relatively lower, the catalyst material moves upwards in the fluidized bed along with the air flow, and the heating temperature of the first heating assembly is enough to enable the catalyst to continuously catalyze the growth of the carbon nano tubes. The energy-saving effect is good.
In some embodiments, the first heating assembly and the second heating assembly are arranged on the outer wall surface of the growth unit, so that the heating assemblies can be detached and adjusted conveniently, and the partitioned temperature control can be realized more easily.
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 nano tube, the carbon source gas is pyrolyzed into small molecular hydrocarbon gas at high temperature, the carbon nano tube is catalytically grown under the action of the catalyst, and the flow rate of the inert atmosphere is slightly higher than that of the carbon source gas, so that the inert atmosphere can serve as a carrier gas, the fluidization effect of the material in the growth unit is ensured, and the catalytic growth efficiency of the carbon nano tube is favorably prevented from being interfered by oxygen in the growth unit.
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 selected from acetylene, ethylene, hexane, methane, propylene, butane, carbon monoxide, benzene and ethanol adopted in the embodiment of the application can be rapidly and stably cracked into carbon atoms under the condition that the temperature is 660-680 ℃, so that a material basis is provided for rapid, efficient and stable growth of subsequent carbon nanotubes. Propylene is preferably used as the carbon source gas, 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 the inert atmosphere enter from a bottom gas inlet of the growth unit. In some preferred embodiments, a flat gas distributor is arranged at the gas inlet at the bottom of the growth unit, and the gas distributor can be used for enabling the carbon source gas and the inert atmosphere entering the growth unit to be smoother and more uniform, and is beneficial to regulating the flow rate of the gas. The gas distributor of the embodiment of the present application is a device for uniformly distributing the gas entering the fluidized bed over the entire cross section. The embodiments of the present application preferably employ a flat plate gas distributor.
In some embodiments, the annular gas distributor has a gas flow rate of 50 to 150L/min; in this case, the gas flow velocity of the annular gas distributor can further improve the uniformity of the regional temperature distribution and the concentration distribution in the growth unit, and further adjust the fluidization state of the material, so that the product can better enter the separator for discharging; and the problem that the fluidization state of the material is interfered by overlarge gas flow velocity can be avoided, so that the material can stably and fully move to a gas-solid separation device for separation.
In some embodiments, an annular gas distributor is disposed from a bottom of the first heating assembly to a top region of the second heating assembly. The bottom of first heating element is considered to the top region of second heating element in this application embodiment, and reaction temperature is higher, and carbon nanotube growth catalytic activity is higher, and material density is high, and the material is agglomerated more easily in this region, therefore sets up the fluidization state that annular gas distributor can effectively improve the material in this region, reduces the risk that the material is agglomerated, prevents the oven sintering carbon deposit simultaneously.
In some embodiments, the discharge port of the gas-solid separation device is provided with a screen mesh for screening the coarse product, the coarse product with qualified particle size is conveyed to the purification unit, and the coarse product with unqualified particle size returns to the growth unit again to continue the catalytic growth of the carbon nano tube. The carbon nano tube crude product enters along with the air 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 obtained by the separation of the gas-solid separation device is screened through a screen of a discharge port, the large carbon nano tube crude product is directly conveyed to a purification unit through a crude product conveying pipeline for purification, and the small carbon nano tube crude product can pass through the screen and return to the growth unit again for catalytic growth of the carbon nano tube.
In some embodiments, the tail gas is passed through a gas-solid separation device to re-supply heat to the growth unit. Under the condition, the waste heat of the tail gas is 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 the tail gas treatment process is reduced, and the energy is saved and the environment is protected.
In some embodiments, the container wall of the growth unit is a hollow structure, the hollow structure includes an air inlet end and an air outlet end which are arranged oppositely, a tail gas conveying pipeline of the gas-solid separation device is communicated with the air inlet end of the hollow structure, the tail gas is separated by the gas-solid separation device, conveyed to the air inlet end through the tail gas conveying pipeline to enter the hollow structure, and is discharged from an air outlet at the air outlet end of the hollow structure after providing heat energy for the growth unit by using the waste heat of the tail gas. In a further preferred embodiment, the container wall of the lower part of the growth unit is of a hollow structure, and the waste heat of the tail gas is mainly and intensively supplied to the lower part of the growth unit, 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) conveying the crude product to a purification unit, spraying concentrated hydrochloric acid on 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, the carbon impurities in the carbon nanotube crude product can react with the moisture in the hydrochloric acid to generate carbon monoxide and hydrogen under high temperature conditions, and the carbon impurities in the crude product are rejected in a gaseous state; meanwhile, under the high-temperature environment, the metal catalyst such as iron in the carbon nano tube crude product 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 volatilized and removed in the form of tail gas. Therefore, the purification treatment can simultaneously remove carbon impurities and metal catalyst impurities in the crude product, and has the advantages of high purification efficiency, simple process and good purification effect.
In some embodiments, a heating unit is disposed in the purification unit to provide heat for the purification reaction.
In some embodiments, the step of bringing the crude product to boiling comprises: and introducing inert atmosphere with the flow rate of 400-600L/min from the bottom of the purification unit. In some 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 the crude product material is in a boiling 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 includes 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 a volume ratio of (1-2): 1 hydrogen and a shielding gas.
S02, arranging an activation unit at the top of a growth unit, and enabling an activated catalyst to enter 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 assembly to be 550-600 ℃, the heating temperature of the second heating assembly to be 700-750 ℃, after the temperature of the growth unit is raised to a set temperature, introducing carbon source gas at a flow rate of 450-600L/min and inert atmosphere at a flow rate of 600-700L/min from a bottom gas inlet of the growth unit, and simultaneously outputting the inert atmosphere at a flow rate of 50-150L/min along the inside of the growth unit by an annular gas distributor arranged from the bottom of the first heating assembly to the top area of the second heating assembly; the active catalyst catalyzes the growth of the carbon nanotubes and moves along with the gas flow to the top of the growth unit. When the material moves to the top of the growth unit, the material enters the gas-solid separation device from the feed inlet and is separated into a crude product and tail gas. And the screen mesh arranged at the discharge port of the gas-solid separation device further screens the coarse products, the coarse products with qualified granularity are conveyed to the purification unit, and the coarse products with unqualified granularity return to the growth unit again. In addition, tail gas is conveyed to the gas inlet end through a tail gas conveying pipeline of the gas-solid separation device to enter the hollow structure of the container wall of the growth unit, and is discharged from the gas outlet at the gas outlet end of the hollow structure after heat energy is provided for the growth unit by utilizing the waste heat of the tail gas.
S03, conveying the crude product to a purification unit, spraying concentrated hydrochloric acid to the crude product from the top of the purification unit, introducing an 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, as shown in fig. 2, includes an activation unit 1, a growth unit 2, and a purification unit 3, which are connected in sequence, wherein the activation unit 1 is used to activate 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 arranged to communicate with the top of the growth unit 2. The growth unit 2 is used for catalyzing the growth of carbon nanotubes and comprises a first gas inlet 21 arranged at the bottom, a heating assembly 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 plate gas distributor 22 disposed 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 unit 23 is lower than that of the second heating unit 24, and the heating units are disposed on the outer wall surface of the growth unit 2. An annular gas distributor 25 is provided from 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 a crude product and tail gas, and comprises a feed port 265 and a discharge port 264, the crude product of the carbon nano tube enters the first gas-solid separation device 26 through the feed port 265 along with the gas flow to perform gas-solid separation, the discharge port 264 is provided with a screen 261, the screen 261 is used for screening the crude product separated by the first gas-solid separation device 26, the crude product with qualified granularity is conveyed to the purification unit 3, and the crude product with unqualified granularity returns 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 transported to the gas inlet end 27 through the tail gas transport pipe 262 of the first gas-solid separation device 26, enters the hollow structure 20, and is discharged from the gas outlet 263 at the gas outlet end 28. Purification unit 3 is used for purifying the crude product, including setting up the second air inlet 31 in the bottom, second air inlet 31 department still is provided with second flat gas distributor 32, makes the gas that gets into purification unit 3 more steady through this flat gas distributor, and the distribution is more even, and is favorable to adjusting gaseous velocity of flow. A second gas-solid separation device 34 arranged at the top for separating the purified carbon nanotubes and the tail gas; and a liquid inlet means 33 provided at the top, the liquid inlet means 33 further comprising a plurality of liquid ejection ports 331 provided at the top of the purification unit 3. The purification unit 3 is further provided with a discharge slide valve 35 for collecting the purified carbon nanotubes. The wall surface of the purification unit 3 is further provided with a heating unit, and the heating unit provides a suitable reaction temperature for the purification of the crude product of the carbon nanotubes in the purification unit 3.
In a second aspect, embodiments of the present application provide a carbon nanotube, which is prepared by the above method.
In the carbon nanotube provided by the second aspect of the embodiment of the present application, since the carbon nanotube is prepared by the fluidized bed process, the growth efficiency of the carbon nanotube is improved, so that the carbon nanotube has high purity and good structural integrity.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the progress of the carbon nanotubes and the fluidized bed preparation process of the carbon nanotubes in the examples of the present application obviously evident, the above technical solutions are illustrated by a plurality of examples.
Example 1
A fluidized bed preparation process of carbon nanotubes, the structure schematic diagram of the fluidized bed equipment is shown as the attached figure 2, and the process comprises the following steps:
1. adding the ternary alloy of iron, molybdenum and nickel carried by a catalyst carrier into an activation unit 1, introducing 80L/min of hydrogen and nitrogen with the volume ratio of 2; the activated catalyst is then pulsed with nitrogen into the furnace conveying the growth unit 2. The bottom of the activation unit 1 is also mounted on the top of the growth unit 2 with a switch channel disposed therebetween.
2. The growth unit 2 was set to have a heating temperature of 550 ℃ for the first heating unit 23 and 700 ℃ for the second heating unit 24. After the temperature in the reaction furnace reaches the set temperature, carbon source gas and nitrogen gas are introduced through the first gas inlet 21, carbon source propylene with the gas flow rate of 450L/min and nitrogen gas with the gas flow rate of 600L/min are arranged in the first flat gas distributor 22, and nitrogen gas with the gas flow rate of 50L/min is arranged in the annular gas distributor 25. The annular gas distributor 25 surrounds the furnace wall for one circle, and conveys gas inwards to prevent carbon deposition in the furnace wall, and can further adjust the fluidization state of materials.
3. The material is reacted from the bottom to the top and enters the first gas-solid separation device 26 through the feed inlet 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 pipe 262 to supply heat to the furnace wall at the lower part and then is discharged. 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 the entry of the carbon source to the final discharge is approximately 40-60min.
4. When the reaction is completed, the crude product is introduced into the purification unit 3, and the generated tail gas is discharged from the gas outlet 263 at the gas outlet end 28. Continuously spraying concentrated hydrochloric acid from a liquid spraying port 331 of a liquid inlet device 33 at the upper part of the purification unit 3, continuously introducing nitrogen from a second air inlet 31 at the lower part of the purification unit 3, adjusting the speed to be 500L/min by a second flat gas distributor 32, keeping the materials in a boiling state, setting the reaction temperature to be 1100 ℃, purifying for 60 minutes, arranging a second gas-solid separation device 34 at the top of the purification unit 3, separating and purifying products and tail gas, and blowing the purified carbon nano tubes to a small carbon powder tank through a discharge slide valve 35 for collection to obtain the purified carbon nano tubes.
Example 2
A fluidized bed preparation process of carbon nanotubes, the structure schematic diagram of the fluidized bed equipment is shown as the attached figure 2, and the process comprises the following steps:
1. adding the ternary alloy of iron, molybdenum and nickel carried by a catalyst carrier into an activation unit 1, introducing 120L/min of hydrogen and nitrogen with the volume ratio of 2; the activated catalyst is then pulsed with nitrogen into the furnace that delivers the growth unit 2. The bottom of the activation unit 1 is mounted on the top of the growth unit 2, and a switch channel is arranged between the activation unit and the growth unit.
2. The first heating unit 23 and the second heating unit 24 were set in the growth unit 2 at 600 ℃ and 750 ℃. After the temperature in the reaction furnace reaches the set temperature, carbon source gas and nitrogen gas are introduced through the first gas inlet 21, carbon source propylene with the gas flow rate of 600L/min and nitrogen gas with the gas flow rate of 700L/min are arranged in the first flat gas distributor 22, and nitrogen gas with the gas flow rate of 150L/min is arranged in the annular gas distributor 25. The annular gas distributor 25 surrounds the furnace wall for one circle, and conveys gas inwards to prevent sintering and carbon deposition on the furnace wall and further adjust the fluidization state of the materials.
3. The material is reacted from the bottom to the top and enters the first gas-solid separation device 26 through the feed inlet 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 pipe 262 to supply heat to the furnace wall at the lower part and then is discharged. 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 the carbon source entry to the final discharge is approximately 40-60min.
4. When the reaction is completed, the crude product enters the purification unit 3, and the generated tail gas is discharged from the gas outlet 263 at the gas outlet end 28. Continuously spraying concentrated hydrochloric acid from a liquid spraying port 331 of a liquid inlet device 33 at the upper part of the purification unit 3, continuously introducing nitrogen from a second air inlet 31 at the lower part of the purification unit 3, adjusting the speed to 550L/min by a second flat gas distributor 32, keeping the materials in a boiling state, setting the reaction temperature to 1150 ℃, purifying for 56 minutes, arranging a second gas-solid separation device 34 at the top of the purification unit 3, separating a purified product and tail gas, and blowing the purified carbon nano tube to a small carbon powder tank through a discharge slide valve 35 for collection to obtain the purified carbon nano tube.
Example 3
A fluidized bed preparation process of carbon nanotubes, the structure schematic diagram of the fluidized bed equipment is shown as the attached figure 2, and the process comprises the following steps:
1. adding the ternary alloy of iron, molybdenum and nickel carried by a catalyst carrier into an activation unit 1, introducing 100L/min of hydrogen and nitrogen with the volume ratio of 2 to 1, and reducing for 10min at the reduction temperature of 350 ℃ to obtain an activated catalyst; the activated catalyst is then pulsed with nitrogen into the furnace that delivers the growth unit 2. The bottom of the activation unit 1 is also mounted on the top of the growth unit 2 with a switch channel disposed therebetween.
2. The heating temperature of the first heating unit 23 is 580 deg.C and the heating temperature of the second heating unit 24 is 720 deg.C in the growth unit 2. After the temperature in the reaction furnace reaches the set temperature, carbon source gas and nitrogen gas are introduced through the first gas inlet 21, carbon source propylene with the gas flow rate of 500L/min and nitrogen gas with the gas flow rate of 650L/min are arranged in the first flat gas distributor 22, and nitrogen gas with the gas flow rate of 100L/min is arranged in the annular gas distributor 25. The annular gas distributor 25 surrounds the furnace wall for one circle, and conveys gas inwards to prevent carbon deposition in the furnace wall, and can further adjust the fluidization state of materials.
3. The material is reacted from the bottom to the top and enters the first gas-solid separation device 26 through the feeding 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 to supply heat to the furnace wall at the lower part and then is discharged. 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 the carbon source entry to the final discharge is approximately 40-60min.
4. When the reaction is completed, the crude product enters the purification unit 3, and the generated tail gas is discharged from the gas outlet 263 at the gas outlet end 28. Continuously spraying concentrated hydrochloric acid from a liquid spraying port 331 of a liquid inlet device 33 at the upper part of the purification unit 3, continuously introducing nitrogen from a second air inlet 31 at the lower part of the purification unit 3, adjusting the speed to 550L/min by a second flat gas distributor 32, keeping the materials in a boiling state, setting the reaction temperature to 1200 ℃, purifying for 55 minutes, arranging a second gas-solid separation device 34 at the top of the purification unit 3, separating a purified product and tail gas, and blowing the purified carbon nano tube to a small carbon powder tank through a discharge slide valve 35 for collection to obtain the purified carbon nano tube.
Comparative example 1
A fluidized bed preparation process of carbon nanotubes, the structure schematic diagram of the fluidized bed equipment is shown as the attached figure 2, and the process comprises the following steps:
compared with the preparation process of the embodiment 3, the preparation process is characterized in that: the annular gas distributor was closed during the production, and the other steps and operation were the same as in example 3.
Further, in order to verify the improvement of the examples of the present application, the purity, structural integrity and other properties of the carbon nanotubes prepared in the examples and the comparative examples were respectively tested, and the test results are shown in table 1 below:
TABLE 1
For Raman spectrum of carbon nanotube, its typical peak appears at 1350cm -1 And 1580cm -1 To (3). Wherein the length of the groove is 1350cm -1 The peak is called D peak, and the intensity of the peak corresponds to the defect degree of the carbon nano tube; 1580cm -1 The peak is called G peak, and the intensity of the peak 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, examples 1 to 3 of the present applicationThe carbon nano tube obtained by the fluidized bed preparation process has high purity and good structural integrity. In comparative example 1, the annular gas distributor was closed, the material was easily agglomerated during the production process, the carbon nanotubes were easily agglomerated and grown, the purity of the carbon nanotubes was reduced, and I D /I G The value is increased, the defects of the carbon nano tube are increased, and therefore, the purification effect is also reduced.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation process of a carbon nano tube fluidized bed is characterized by comprising 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 to a growth unit of a fluidized bed for 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 conveying the crude product to a purification unit for purification treatment to obtain the carbon nano tube.
2. The fluidized bed preparation process of carbon nanotubes according to claim 1, wherein the reaction conditions of the activation treatment comprise: 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 a volume ratio of (1-2): 1 hydrogen and a shielding gas;
and/or the activated catalyst is delivered to the bottom of the growth unit by means of a pulse jet feed.
3. The carbon nanotube fluidized bed preparation process of claim 1 or 2, wherein the step of fluidized growth of carbon nanotubes comprises:
transporting the activated catalyst to the bottom of the growth unit;
after the temperature of the growth unit is raised to a 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 activated catalyst catalyzes and grows the carbon nano tube and moves to the top of the growth unit along with the airflow;
and a gas-solid separation device is arranged at the top of the growth unit and used for separating the crude product and the tail gas.
4. The fluidized bed carbon nanotube production process of claim 3, wherein the step of raising the temperature of the growth unit to a 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 assembly arranged at the upper part and a second heating assembly arranged at the lower part along the height direction of the growth unit, the heating temperature of the first heating assembly is 550-600 ℃, and the heating temperature of the second heating assembly is 700-750 ℃.
5. The fluidized bed preparation process of carbon nanotubes according to claim 4, 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.
6. The fluidized bed preparation process of carbon nanotubes according to claim 4 or 5, wherein the gas flow rate of the annular gas distributor is 50 to 150L/min;
and/or the annular gas distributor is arranged from the bottom of the first heating assembly to the top area of the second heating assembly.
7. The carbon nanotube fluidized bed preparation process of claim 6, wherein a screen is disposed in a discharge port of the gas-solid separation device for screening the coarse product, conveying the coarse product with qualified particle size to the purification unit, and returning the coarse product with unqualified particle size to the growth unit again;
and/or the tail gas supplies heat to the growth unit again through the gas-solid separation device.
8. The fluidized bed preparation process of carbon nanotubes according to any one of claims 1, 2, 4 to 5 or 7, wherein the purification treatment step comprises: and after conveying the crude product to the purification unit, spraying concentrated hydrochloric acid on 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.
9. The fluidized bed preparation process of carbon nanotubes according to claim 8, wherein the step of bringing the crude product to a boiling state comprises: and introducing inert atmosphere with the flow rate of 400-600L/min from the bottom of the purification unit.
10. A carbon nanotube produced by the method according to any one of claims 1 to 9.
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