CN112250060A - Device and method for continuously preparing single-walled carbon nanotubes - Google Patents
Device and method for continuously preparing single-walled carbon nanotubes Download PDFInfo
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Abstract
The invention provides a device and a method for continuously preparing single-walled carbon nanotubes, which comprises a carbon nanotube precursor solution injector, a reaction cavity, a collection chamber and a carbon nanotube gas collector communicated with the reaction cavity and the collection chamber; the method comprises the steps of uniformly mixing a liquid carbon source, a composite catalyst and a catalytic assistant to prepare a carbon nano tube precursor solution, injecting the carbon nano tube precursor solution into a reaction cavity through a precursor solution injector to grow a single-walled carbon nano tube, connecting the reaction cavity and a collection chamber through a carbon nano tube gas collector, and conveying the generated single-walled carbon nano tube to the collection chamber to realize continuous collection of products. Compared with the prior art, the device has the advantages of simple structure, no moving part of the carbon nano tube gas collector collecting device, low noise, small volume and high safety, is used for continuously collecting the single-walled carbon nano tube aerogel, and has great significance for boosting the industrial production of the single-walled carbon nano tube.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and relates to a device and a method for continuously preparing single-walled carbon nanotubes.
Background
As a novel nano material, the carbon nano tube has excellent electrical property, mechanical property, thermal property, electromagnetic property and the like due to the unique geometric structure and electronic energy band structure, and has wide application prospect in the aspects of light weight, high strength and high conductivity preparation.
The current methods for preparing carbon nanotubes mainly comprise: arc method, laser evaporation method, chemical vapor deposition method. The three methods can prepare the high-quality carbon nano tube with single wall and few walls. The chemical vapor deposition method has attracted extensive attention because of the simple equipment and the most possible realization of the industrial preparation technology of the single-walled carbon nanotube aerogel.
At present, a method for growing high-quality carbon nanotubes by adopting a chemical vapor deposition method is adopted, a catalyst prepared by iron-cobalt elements is fluidized in a reactor, a gaseous carbon source is introduced at high temperature for growing, most of the prepared carbon nanotubes are few-wall tubes, the graphitization degree is low, and the yield is low. The other method adopts a liquid-phase carbon source such as ethanol or toluene and the like, adds a catalyst such as ferrocene and the like, and leads the reaction stock solution into a high-temperature tubular furnace under the condition of containing reductive carrier gas, and the carbon nanotube macroscopic body is synthesized by high-temperature catalytic cracking growth (Li et al. science 2004 and US Patent 2005/006801-A1).
The single-walled carbon nanotubes can be prepared by the above report, but the graphitization degree and the catalyst utilization efficiency are not high, and the carbon nanotube aerogel is difficult to realize continuous collection.
Disclosure of Invention
In order to solve the problems, the invention improves the graphitization degree of the prepared single-walled carbon nanotube and the utilization efficiency of the catalyst through the prepared carbon nanotube precursor solution, and realizes continuous collection of the grown single-walled carbon nanotube aerogel through the advantages of no electric motor, no moving parts, low noise, small volume and high safety of a carbon nanotube gas collector, so that the large-scale preparation of the single-walled carbon nanotube becomes possible.
The technical scheme of the invention is as follows: an apparatus for continuously preparing single-walled carbon nanotubes, comprising: the carbon nano tube precursor solution injector comprises a reaction cavity and a collection chamber, and a product is continuously collected by connecting the reaction cavity with a collection device through a carbon nano tube gas collector;
wherein the carbon nanotube precursor solution injector comprises:
a carbon nano tube precursor solution injection pump, a driver and an atomizing head;
the carbon nano tube precursor solution delivery pipe is connected with the injection pump and the atomizing head;
the atomizing head extends into the reaction cavity;
and the injection pump injects atomized carbon nano tube precursor solution into the reaction cavity through the delivery pipe and the atomizing head.
And a carrier gas injection port is also arranged between the carbon nano tube precursor solution injector and the main reaction cavity.
The reaction cavity is made of corundum tubes, quartz tubes or mullite tubes.
As a further improvement of the invention, the reaction cavity is connected with the reaction cavity and the collection chamber through a carbon nano tube gas collector.
As a further improvement of the invention, the carbon nanotube gas collector is made of 304S, 316S, 309S or 310S.
As a further improvement of the invention, the carbon nano tube precursor solution composite catalyst, the liquid carbon source and the catalytic assistant are uniformly stirred at a certain temperature.
The liquid carbon source comprises absolute ethyl alcohol, acetone and toluene.
As a further improvement of the invention, the composite catalyst is formed by compounding a catalyst A and a catalyst B, ferrocene is used as the catalyst A, and the catalyst B comprises one or more of rare metal organic compounds of lanthanum tricarbazole, cerium tricarbazole, praseodymium tricarbazole, neodymium tricarbazole, samarium tricarbazole or metallocene complex cyclopentadienyl tungsten tricarbonyl dimer, cyclopentadienyl molybdenum tricarbonyl dimer, cyclopentadienyl chromium tricarbonyl dimer, zirconocene dichloride or metallocene derivative ferrocenecarboxaldehyde, and 1,1' -bis (diphenylphosphine) ferrocene.
As a further improvement of the invention, the catalytic promoter is one or a mixture of two of thiophene, carbon disulfide and sulfur powder.
As a further improvement of the invention, the mass percent of the liquid carbon source is 96-99%, the mass percent of the composite catalyst is 0.5-4%, the mass percent of the catalyst A is 0.6-2.5%, the mass percent of the catalyst B is 0.1-1.5%, and the mass percent of the catalytic assistant is 0.05-0.5%.
Another object of the present invention is to provide a method for preparing the above apparatus for continuously preparing single-walled carbon nanotubes, the method comprising the steps of:
s1, injecting inert gas into the reaction cavity through the carrier gas injection port, raising the temperature of the reaction cavity to 1100-1600 ℃, and keeping the temperature constant.
S2, conveying and injecting the reducing gas into the reaction cavity through the carrier gas;
s3, uniformly injecting the carbon nanotube precursor solution into an atomizing head through a carbon source injection pump, driving the atomizing head to atomize the carbon nanotube precursor solution through a driver, and generating single-walled carbon nanotube aerogel in a reaction cavity;
s4, introducing inert gas with certain pressure and flow into the carbon nanotube gas collector, connecting the carbon nanotube gas collector with the reaction cavity, forming negative pressure suction at the upper end, and forming positive pressure blowing at the lower end to transport the single-wall carbon nanotube aerogel into the collection chamber;
as a further improvement of the present invention, the inert gas comprises: argon, nitrogen, helium, and the like; the reducing gas includes: hydrogen, carbon monoxide and carbon dioxide; the total flow of the carrier gas is 2-20L/min, the volume of the reducing gas accounts for 40-90%, and the volume percentage of the inert gas is 10-60%.
As a further improvement of the invention, the speed of injecting the carbon nano tube precursor solution into the reaction cavity is 3-120 ml/h.
As a further improvement of the invention, the pressure of the carbon nano tube gas collector is 0.6-1.5 MPa, and the inert gas flow of the carbon nano tube gas collector is 3-50L/min.
As a further improvement of the invention, the outlet end of the sprayer is positioned in the reaction cavity at the temperature of 150-400 ℃;
as a further improvement of the invention, the collection chamber is liquid-sealed with water to prevent air from being sucked back.
The invention provides a device and a method for continuously preparing single-walled carbon nanotubes, the device has simple structure, effective method and high graphitization degree, and can be applied to the aspects of conductive additives, electromagnetic shielding, transparent antistatic films, inductive switches, heat dissipation coatings and the like.
The invention has the following beneficial effects:
the invention uses the composite catalyst to prepare the carbon nano tube precursor solution, and the composite catalyst can improve the catalytic efficiency and simultaneously improve the graphitization degree of the product.
The invention realizes the collection of the carbon nano tube aerogel by using the carbon nano tube gas collector, takes inert gas as a driving gas source, one end of the inert gas generates negative pressure suction, the other end of the inert gas generates positive pressure blowing force, and the grown carbon nano aerogel is conveyed into a collection chamber through a pipeline along with high-speed airflow. The device has the advantages of no electric motor, no electric interference, no moving parts, low noise, small volume and high safety, and is used for collecting the single-walled carbon nanotube aerogel.
The carrier gas brings the carbon nanotube precursor solution into the high-temperature reaction zone to grow the carbon nanotubes with high graphitization degree, meanwhile, the negative pressure suction at the lower end shortens the time of the catalyst reaching the high-temperature zone, reduces the agglomeration of catalyst particles, is easy to form the carbon nanotubes with high graphitization degree, enables the generated carbon nanotube aerogel to be rapidly transported into the collection chamber, and simultaneously reserves a reaction space for the continuous growth of new products, thereby being beneficial to improving the yield of the high-quality carbon nanotubes.
The device and the method for continuously preparing the single-walled carbon nanotube have the advantages of simple structure, effective method, high graphitization degree, high crystallinity, good electrical conductivity, thermal conductivity, strength and biocompatibility, and can be obviously applied in a large number. The material of the invention can be applied to the aspects of primary batteries, secondary batteries, semiconductors, capacitors, electric automobiles, cables, biomedical equipment, engineering materials, electromagnetic interference shielding, tires and the like, conductive additives, electromagnetic shielding, composite material reinforcement, permanent antistatic, inductive switches, heat dissipation coatings and the like.
The material of the invention can be applied to medical appliances, household appliances, electronic products, communication equipment, electric vehicles, electromagnetic shielding and the like, and has wide application prospect.
The material has high graphitization degree, high crystallinity, high G/D ratio of 120 and specific surface area of 970m2/g。
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for continuously preparing single-walled carbon nanotubes according to the present invention.
Fig. 2 is a schematic cross-sectional view of a carbon nanotube gas collector of an apparatus for continuously preparing single-walled carbon nanotubes according to the present invention.
FIG. 3 is a scanning electron micrograph of the single-walled carbon nanotube prepared in example 3.
FIG. 4 is a scanning electron micrograph of the single-walled carbon nanotube prepared in comparative example 3.
FIG. 5 is a thermogravimetric characterization of single-walled carbon nanotubes prepared using the apparatus of the present invention.
FIG. 6 is a thermogravimetric characterization of single-walled carbon nanotubes prepared using the apparatus of the present invention.
FIG. 7 is a Raman spectrum of a continuous preparation of single-walled carbon nanotubes according to the present invention.
FIG. 8 is a transmission electron micrograph of a single-walled carbon nanotube according to the present invention.
In the figure:
220. the device comprises a precursor solution injector, 222, a driver, 224, an injection pump, 225, a precursor solution delivery pipe, 226, an ultrasonic atomizing head, 228, a carrier gas injection port, 230, a reaction chamber, 232, a heating body, 234, a heating body, 240, a carbon nano tube gas collector, 242, a gas inlet, 244, an annular high-pressure chamber, 246, a nozzle, 248 negative pressure suction, 249, positive pressure blowing force and 250, a collection chamber.
Detailed Description
The invention is further illustrated by the following specific examples:
the raw materials used in the following examples are all commercially available products, the parts are by weight, and the examples are further illustrative of the present invention and do not limit the scope of the present invention; variations in structure, method, or function that may be apparent to those of ordinary skill in the art upon reading the foregoing description are intended to be within the scope of the present invention.
The Raman spectrum characterization and the thermal gravimetric analysis test standard of the high-quality carbon nanotube sample are disclosed in GB/T32871-2016 and GB/T24490-2009.
The present invention will be described in detail below with reference to embodiments shown in the drawings. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.
As shown in fig. 1, an apparatus for continuously preparing single-walled carbon nanotubes according to the present invention includes a precursor solution injector 220, a reaction chamber 230, a carbon nanotube gas collector 240, a collection chamber 250;
a carbon nanotube precursor solution injector 220 for inputting the carbon nanotube precursor solution into the reaction chamber 230 and uniformly spraying the solution in an atomized form;
a reaction chamber 230 for forming a constant temperature region and cracking a carbon source to grow the single-walled carbon nanotube;
a carbon nanotube gas collector 240 for collecting single-walled carbon nanotubes by forming a negative pressure space at an upper end of the interior of the reaction chamber 230 using a gas flow, and simultaneously blowing the collected single-walled carbon nanotubes to the collection chamber 250 by forming a positive pressure blowing force at a lower end of the interior of the reaction chamber 230;
a collection chamber 250 for storing single-walled carbon nanotubes.
Wherein, the carbon nanotube precursor solution delivery pipe 225 is connected with the injection pump 224 and the atomizing head 226; the atomizing head extends into the reaction cavity from the top of the reaction cavity, and a carrier gas injection port 228 is further arranged between the carbon nanotube precursor solution injector and the reaction cavity;
the collecting chamber 250 is disposed at the bottom of the reaction chamber 230 and connected to the reaction chamber, and the carbon nanotube gas collector 240 is disposed at the connection.
The reaction chamber 230 is used for generating single-walled carbon nanotubes, and the heating bodies 232 and 234 supply heat to the reaction chamber 230, and the reaction chamber continuously grows the generated single-walled carbon nanotubes. The carbon nanotube gas collector 240 connects the reaction chamber 230 and the collection chamber 250.
As shown in fig. 2, in the carbon nanotube gas collector, after the inert gas flows into the annular high-pressure chamber 244 through the gas inlet 242, the inert gas flows through the nozzle 246 at a high speed, the high-speed gas flow generates vacuum negative pressure at the inlet 248, so that the inlet product is sucked into the pipeline, when the product reaches the nozzle 246, the product is blown again by the high-pressure gas flow, and finally the product is conveyed to the designated position 249 through the pipeline.
A method for preparing single-walled carbon nanotubes by using the device for continuously preparing single-walled carbon nanotubes comprises the following steps:
s1) injecting inert gas into the reaction cavity through the carrier gas injection port 228, raising the temperature of the reaction cavity 230 to 1100-1600 ℃, and keeping the temperature constant;
s2) injecting 228 the reducing gas into the reaction chamber 230 by the carrier gas;
s3) injecting the carbon nanotube precursor solution uniformly into the atomizing head 226 through the carbon source injection pump 224, driving the atomizing head 226 to atomize the carbon nanotube precursor solution through the driver 222, and generating single-walled carbon nanotube aerogel in the reaction chamber;
s4) introducing inert gas with a certain pressure and flow rate through the gas inlet 242 of the carbon nanotube gas collector, forming a negative pressure suction 248 at the upper end connected with the reaction chamber, and forming a positive pressure blowing at the lower end to transport the single-walled carbon nanotube aerogel into the collection chamber 250.
The carbon nanotube precursor solution in S3) comprises a composite catalyst, a liquid carbon source and a catalytic assistant;
the mass percent of the liquid carbon source is 96-99%, the mass percent of the composite catalyst is 0.5-4%, and the mass percent of the catalytic assistant is 0.05-0.5%.
The composite catalyst comprises a catalyst A and a catalyst B, wherein the mass percent of the catalyst A is 0.6-2.5%, and the mass percent of the catalyst B is 0.1-1.5%.
The catalyst A is ferrocene;
the catalyst B is one or more of rare metal organic compounds of lanthanum cyclopentadienyl, cerium cyclopentadienyl, praseodymium cyclopentadienyl, neodymium cyclopentadienyl, samarium cyclopentadienyl or metallocene complex cyclopentadienyl tungsten tricarbonyl dimer, cyclopentadienyl molybdenum tricarbonyl dimer, cyclopentadienyl chromium tricarbonyl dimer, zirconocene dichloride or metallocene derivative ferrocene formaldehyde and 1,1' -bis (diphenylphosphine) ferrocene.
The total flow of carrier gas in the S2) is 2-20L/min, the volume of reducing gas accounts for 40-90%, and the volume percentage of inert gas is 10-60%;
the inert gas is argon, nitrogen or helium;
the reducing gas is a mixed gas of hydrogen and carbon dioxide, wherein the hydrogen accounts for 98.5-99.9% of the volume of the carbon dioxide accounts for 0.02-1.5%;
carbon monoxide can also be added into the reducing gas; the addition amount of the carbon monoxide accounts for 0.02-5% of the mixed gas ratio of the hydrogen and the carbon dioxide.
The speed of injecting the carbon nanotube precursor solution into the reaction cavity 230 is 3-120 ml/h;
the pressure of the carbon nanotube gas collector 240 is 0.6-1.5 MPa, and the inert gas flow of the carbon nanotube gas collector 240 is 3-50L/min.
The liquid carbon source comprises absolute ethyl alcohol, acetone and toluene.
The catalytic assistant is one or two mixtures of thiophene, carbon disulfide and sulfur powder.
Example 1
Introducing 1L/min argon gas, heating the reaction furnace to 1100 ℃, then introducing 1L/min hydrogen gas and 0.02L carbon dioxide, injecting the carbon nanotube precursor solution into an atomizing head through an injection pump at a speed of 6ml/h, driving the atomizing head to atomize the carbon nanotube precursor solution through a driver, and generating single-walled carbon nanotube aerogel in a reaction cavity;
the carbon nanotube gas collector 240 is driven by nitrogen gas at a pressure of 5L/min under 0.6MPa to collect the generated single-walled carbon nanotube aerogel and transport it into the collection chamber 250.
The carbon nano tube precursor solution is prepared according to the following scheme:
adding 1.2% of ferrocene into a liquid carbon source absolute ethyl alcohol, heating to 30 ℃, stirring for 15min, then adding 0.3% of lanthanum cyclopentadienyl, stirring for 15min under the condition of keeping the temperature at 30 ℃, finally cooling to 20 ℃, adding 0.1% of thiophene solution, and stirring for 30min to obtain the carbon nano tube precursor solution.
Example 2
Introducing 2.5L/min argon gas, heating the reaction furnace to 1300 ℃, then introducing 5L/min hydrogen and 0.2L carbon dioxide, injecting the carbon nanotube precursor solution into the atomizing head 226 through the injection pump 224 at the speed of 30ml/h, driving the atomizing head to atomize the carbon nanotube precursor solution through the driver 222, and generating single-walled carbon nanotube aerogel in the reaction chamber;
the carbon nanotube gas collector 240 is driven by nitrogen gas at 25L/min under a pressure of 0.8MPa as a driving gas to collect the generated single-walled carbon nanotube aerogel and transport it into the collection chamber 250.
The carbon nano tube precursor solution is prepared according to the following scheme:
adding 1.5% of ferrocene into a liquid carbon source absolute ethyl alcohol, heating to 35 ℃, stirring for 15min, then adding 0.5% of tricresyl praseodymium, stirring for 20min under the condition of keeping the temperature at 35 ℃, finally cooling to 20 ℃, adding 0.2% of sulfur powder solution, and stirring for 30min to obtain the carbon nano tube precursor solution.
Example 3
Introducing helium gas of 8L/min, heating the reaction furnace to 1600 ℃, then introducing hydrogen of 12L/min and carbon dioxide of 0.5L/min, injecting the carbon nanotube precursor solution into the atomizing head 226 through the injection pump at a speed of 90ml/h, driving the atomizing head to atomize the carbon nanotube precursor solution through the driver, and generating single-walled carbon nanotube aerogel in the reaction chamber 230;
the carbon nanotube gas collector 240 is driven by nitrogen gas at a pressure of 50L/min under 1.0MPa as a driving gas to collect the generated single-walled carbon nanotube aerogel and transport it into a collection chamber.
The carbon nano tube precursor solution is prepared according to the following scheme:
adding 1.9% of ferrocene into a liquid carbon source toluene, heating to 35 ℃, stirring for 15min, then adding 0.6% of praseodymium triscene, keeping the temperature at 35 ℃, stirring for 20min, finally cooling to 25 ℃, adding 0.2% of thiophene and 0.1 of sulfur powder solution, and stirring for 30min to obtain the carbon nano tube precursor solution.
The Raman characterization of the obtained sample is shown in FIG. 7, the characteristic peak RBM of the single-walled carbon nanotube is obvious, the G/D ratio of the sample is shown as 120 in Table 1, and the specific surface area of the sample is up to 970m2The/g is the high-crystallinity single-wall carbon nano tube; the thermogravimetric characterization shown in fig. 5 shows that the residual mass of the product is 11.3%, and the scanning electron micrograph characterization of the product is shown in fig. 3, which shows that the surface impurities of the sample are less, and the purity of the obtained sample is higher; the transmission electron micrograph of the obtained sample is shown in figure 8, and the sample is determined to be a single-wall carbon nanotube and has less defects.
Example 4
Firstly introducing 3L/min helium, heating the reaction furnace to 1400 ℃, then introducing 5L/min hydrogen and 0.2L/min carbon dioxide, injecting the carbon nanotube precursor solution into the atomizing head through an injection pump 224 at a speed of 36ml/h, and driving the atomizing head 226 to atomize the carbon nanotube precursor solution through a driver 222 to generate single-walled carbon nanotube aerogel in the reaction chamber;
the carbon nanotube gas collector 240 is driven by nitrogen gas at 25L/min under a pressure of 1.2MPa as a driving gas to collect the generated single-walled carbon nanotube aerogel and transport it into the collection chamber 250.
The carbon nano tube precursor solution is prepared according to the following scheme:
adding 2.2% of ferrocene into liquid carbon source acetone, heating to 35 ℃, stirring for 15min, then adding 0.6% of cyclopentadienyl tungsten tricarbonyl dimer, stirring for 30min under the condition of keeping the temperature at 35 ℃, finally cooling to 25 ℃, adding 0.1% of thiophene and 0.25% of carbon disulfide solution, and stirring for 30min to obtain the carbon nanotube precursor solution.
Example 5
Introducing helium gas of 6L/min, heating the reaction furnace to 1500 ℃, then introducing hydrogen gas of 14L/min, carbon dioxide of 0.3L/min and 0.3L/min, injecting the carbon nanotube precursor solution into the atomizing head 226 through the injection pump 224 at a speed of 36ml/h, and driving the atomizing head to atomize the carbon nanotube precursor solution through the driver to generate single-walled carbon nanotube aerogel in the reaction cavity;
the carbon nanotube gas collector 240 is driven by nitrogen gas at a pressure of 50L/min under 1.2MPa as a driving gas to collect the generated single-walled carbon nanotube aerogel and transport it into the collection chamber 250.
The carbon nano tube precursor solution is prepared according to the following scheme:
adding 1.8% of ferrocene into liquid carbon source acetone, heating to 35 ℃, stirring for 15min, then adding 0.2% of 1,1' -bis (diphenylphosphino) ferrocene, stirring for 30min under the condition of keeping the temperature at 35 ℃, finally cooling to 25 ℃, adding 0.15% of thiophene and 0.1% of sulfur, and stirring for 30min to obtain the carbon nano tube precursor solution.
Example 6:
introducing 2L/min argon gas, heating the reaction furnace to 1300 ℃, then introducing 5L/min hydrogen gas, 0.1L carbon dioxide and 0.2L/min carbon monoxide, injecting the carbon nanotube precursor solution into the atomizing head 226 through an injection pump at a speed of 36ml/h, driving the atomizing head to atomize the carbon nanotube precursor solution through a driver 222, and generating single-walled carbon nanotube aerogel in the reaction cavity;
the carbon nanotube gas collector 240 is driven by argon gas at a pressure of 20L/min under 1.5MPa as a driving gas to collect the generated single-walled carbon nanotube aerogel and transport it into a collection chamber.
The carbon nano tube precursor solution is prepared according to the following scheme:
adding 1.6% of ferrocene into liquid carbon source acetone, heating to 35 ℃, stirring for 15min, then adding 0.1% of 1,1' -bis (diphenylphosphino) ferrocene and 0.1% of tricresyl neodymium, stirring for 45min under the condition of keeping the temperature at 35 ℃, finally cooling to 25 ℃, adding 0.15% of thiophene and 0.1% of sulfur, and stirring for 30min to obtain the carbon nanotube precursor solution.
Comparative example 1 was prepared according to the same formulation and method as in example 1, except that the pressure and gas circuit of the nitrogen gas driver were adjusted to 10L/min at a pressure of 0.8 MPa.
Comparative example 2
The same formulation as in example 2 was used and the preparation was the same as in example 2 except that no carbon dioxide gas was added.
Comparative example 3
The same procedure was followed as in example 3, except that no praseodymium triscene was added to the formulation.
The G/D ratio of the obtained sample is shown in Table 1 to be 78, and the specific surface area is as high as 678m2(ii)/g; FIG. 6 shows that the residual mass of the thermogravimetric characterization product of the obtained sample is 15.6% higher than that of the sample of example 3, the scanning electron micrograph of the sample is shown in FIG. 4, and the comparison of FIG. 3 and FIG. 4 shows that the surface impurities of the sample obtained in example 3 are obviously lower than those of comparative example 3, and the purity of the sample is lower than that of the sample obtained in example 3. Namely, the addition of the praseodymium tribenoxide is beneficial to improving the utilization efficiency of the catalyst, reducing the residual quality and improving the purity of the carbon tube.
Comparative example 4
The same formulation and preparation method as in example 4 was used, except that the injection rate was reduced to 18 ml/h.
Comparative example 5
The same preparation as in example 5 was carried out, except that the thiophene content in the formulation was reduced to 0.1%.
Comparative example 6
The same procedure was followed as in example 6, except that 1,1' -bis (diphenylphosphino) ferrocene and 0.1% neodymium tricresyl were not added to the formulation.
TABLE 1 comparison of material Properties of an apparatus and method for continuous preparation of single-walled carbon nanotubes obtained under different formulations and process conditions
The apparatus and method for continuously preparing single-walled carbon nanotubes provided in the embodiments of the present application are described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in this specification and the appended claims, certain terms are used to refer to particular components, and various names may be used by a manufacturer of hardware to refer to a same component. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (10)
1. An apparatus for continuously preparing single-walled carbon nanotubes, the apparatus comprising:
the carbon nano tube precursor solution injector is used for inputting the carbon nano tube precursor solution into the reaction chamber and uniformly spraying the carbon nano tube precursor solution in an atomization mode;
a reaction cavity for forming a constant temperature area and cracking a carbon source to grow the single-walled carbon nanotube;
the carbon nano tube gas collector is used for forming a negative pressure space at the upper end in the reaction cavity by utilizing gas flow and collecting the single-wall carbon nano tubes, and simultaneously forming positive pressure blowing force at the lower end in the reaction cavity to blow the collected single-wall carbon nano tubes to the collecting chamber;
a collection chamber for storing single-walled carbon nanotubes.
2. The apparatus of claim 1, wherein the carbon nanotube precursor solution injector comprises: a carbon nano tube precursor solution delivery pipe, a carbon nano tube precursor solution injection pump, a driver and an atomizing head;
wherein, the carbon nano tube precursor solution delivery pipe is connected with an injection pump and an atomizing head; the atomizing head extends into the reaction cavity from the top of the reaction cavity, and a carrier gas injection port is also arranged between the carbon nano tube precursor solution injector and the reaction cavity;
the collecting chamber is arranged at the bottom of the reaction cavity and connected with the reaction cavity, and the carbon nano tube gas collector is arranged at the joint.
3. The apparatus of claim 2, the carbon nanotube gas collector is a gas amplifier; one end of the gas amplifier is connected with the bottom of the reaction cavity, the other end of the gas amplifier is connected with the top of the collection chamber, and a gas inlet is formed in the side wall of one side of the gas amplifier.
4. A method for preparing single-walled carbon nanotubes using the apparatus for continuously preparing single-walled carbon nanotubes of any one of claims 1 to 3, comprising the steps of:
s1) injecting inert gas into the reaction cavity through the carrier gas injection port, raising the temperature of the reaction cavity to 1100-1600 ℃, and keeping the temperature constant;
s2) injecting the reducing gas into the reaction cavity through the carrier gas;
s3) injecting the carbon nanotube precursor solution uniformly into the atomizing head through a carbon source injection pump, driving the atomizing head to atomize the carbon nanotube precursor solution through a driver, and generating single-walled carbon nanotube aerogel in the reaction cavity;
s4) introducing inert gas with set pressure and flow through the carbon nanotube gas collector, connecting the carbon nanotube gas collector with the reaction cavity, forming negative pressure suction at the upper end, and forming positive pressure blowing at the lower end to transport the single-wall carbon nanotube aerogel into the collection chamber.
5. The method according to claim 4, wherein the injection speed of the carbon nanotube precursor solution in S3) into the reaction chamber is 3-120 ml/h;
the carbon nano tube precursor solution comprises a composite catalyst, a liquid carbon source and a catalytic assistant;
the mass percent of the liquid carbon source is 96-99%, the mass percent of the composite catalyst is 0.5-4%, and the mass percent of the catalytic assistant is 0.05-0.5%.
6. The method according to claim 5, wherein the composite catalyst comprises a catalyst A and a catalyst B, the catalyst A accounts for 0.6-2.5% of the total mass of the composite catalyst, and the catalyst B accounts for 0.1-1.5% of the total mass of the composite catalyst.
7. The method of claim 5, wherein the promoter is one or a mixture of thiophene, carbon disulfide and sulfur powder.
8. The process according to claim 6, characterized in that the catalyst A is ferrocene;
the catalyst B is one or more of rare metal organic compounds of lanthanum cyclopentadienyl, cerium cyclopentadienyl, praseodymium cyclopentadienyl, neodymium cyclopentadienyl, samarium cyclopentadienyl or metallocene complex cyclopentadienyl tungsten tricarbonyl dimer, cyclopentadienyl molybdenum tricarbonyl dimer, cyclopentadienyl chromium tricarbonyl dimer, zirconocene dichloride or metallocene derivative ferrocene formaldehyde and 1,1' -bis (diphenylphosphine) ferrocene.
9. The method according to claim 4, wherein the total flow rate of the carrier gas in S2) is 2-20L/min;
the volume of the reducing gas accounts for 40-90%, and the volume of the inert gas accounts for 10-60%;
the inert gas is argon, nitrogen or helium;
the reducing gas is a mixed gas of hydrogen and carbon dioxide, wherein the hydrogen accounts for 98.5-99.9% of the volume of the carbon dioxide accounts for 0.02-1.5%.
10. The method as claimed in claim 4, wherein the pressure in S4) is 0.6-1.5 MPa, and the inert gas flow rate is 3-50L/min.
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