KR102017279B1 - Method for purifying CNT using a fluidized bed reactor - Google Patents
Method for purifying CNT using a fluidized bed reactor Download PDFInfo
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- KR102017279B1 KR102017279B1 KR1020150147657A KR20150147657A KR102017279B1 KR 102017279 B1 KR102017279 B1 KR 102017279B1 KR 1020150147657 A KR1020150147657 A KR 1020150147657A KR 20150147657 A KR20150147657 A KR 20150147657A KR 102017279 B1 KR102017279 B1 KR 102017279B1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- 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
Abstract
The present invention relates to a CNT purification method, characterized in that, in a fluidized bed reactor, carbon nanotubes containing impurities including residual metals are reacted and removed with a halogen-containing gas under an inert gas atmosphere. The method according to the present invention can be operated in a higher density than the conventional CNT refining method using a heating furnace by using a mixture of flow conditions and closed conditions, while reducing the time taken for the CNT refining process, Impurities such as metal catalysts can be effectively purified.
Description
The present invention relates to a carbon nanotube (CNT) purification method using a fluidized bed reactor.
CNTs are also widely used as conductive additives in electronic products such as batteries, conductive inks and conductive polymers. In the case of fine chemicals, when impurities other than CNTs are added together, the quality of the products may be degraded and unexpected defects may be generated. Therefore, in the CNT synthesis, it is important to remove impurities such as residual metal catalyst or amorphous carbon which may occur during the CNT synthesis process. In particular, it is necessary to remove the metal catalyst to prevent problems related to quality and defects.
The metal removal process in the conventional CNT refining process adopts a method using a wet fixed bed using liquid acid and a dry fixed bed injecting chlorine gas into a box-type furnace at high temperature.
Specifically, the metal removal method using the liquid acid may generate waste acid as a by-product, and may cause problems such as environmental pollution and waste acid treatment. In addition, the metal removal method using the heating furnace has the disadvantage that the output of the product may be reduced due to the consumption of raw materials such as cooling gas and time to control the heating and cooling of the heating furnace.
Therefore, there is a need for a technology development for a CNT purification method that can shorten the time required for the process while minimizing the production of by-products.
It is an object of the present invention to provide a method for purifying CNTs using a fluidized bed reactor.
It is another object of the present invention to provide a CNT treated by the above method.
In order to solve the above problems, the present invention is a fluidized bed reactor having a gas inlet and outlet, and a carbon nanotube (CNT) inlet and outlet, the carbon nanotubes containing impurities containing residual metal under an inert gas atmosphere Provided is a carbon nanotube (CNT) purification method that reacts with a halogen-containing gas to remove it.
The purification method includes a first step of heating a carbon nanotube containing impurities including a residual metal to a first temperature (T1) under an inert gas atmosphere and reacting with a halogen-containing gas to halogenate the impurities; And a second step of heating to a second temperature (T2) higher than the first temperature to evaporate the halogenated impurity to remove through a gas outlet, and to obtain purified carbon nanotubes through a CNT outlet. .
According to one embodiment, the first temperature (T1) may be 600 ℃ to 1000 ℃.
In addition, the second temperature T2 may be greater than or equal to T1 + 100 ° C.
According to one embodiment, the purification method may be carried out in a continuous process using one fluidized bed reactor.
In addition, the purification method may be performed in a continuous process using two fluidized bed reactors, the first step process may be carried out in the first fluidized bed reactor, the second step process may be carried out in the second fluidized bed reactor.
According to one embodiment, the method may further include cooling the purified CNT discharged through the CNT outlet.
According to one embodiment, the halogen-containing gas may be a gas containing fluorine, chlorine, bromine, iodine or a mixture thereof.
In addition, the halogen-containing gas may be a gas containing chlorine gas or trichloromethane gas or a mixed component thereof.
According to one embodiment, the inert gas may be a gas containing nitrogen, helium, neon, argon, krypton, xenon, radon or mixed components thereof.
According to one embodiment, the gas injection method may be a purge method, a pulse method, a continuous injection method or a combination of these injection methods.
According to one embodiment, the pressure of the inert gas may be 500torr to 800torr.
According to one embodiment, the pressure of the halogen-containing gas may be 500torr to 900torr.
According to one embodiment, the method may further include neutralizing the halogenated impurity recovered from the gas outlet.
In addition, the neutralization treatment includes silver nitrate (AgNO 3 ), sodium thiosulfate (Na 2 S 2 O 3 ), sodium chloride (NaCl), potassium thiocyanate (KSCN), ammonium thiocyanate (NH 4 SCN), aluminum salt compounds , Sodium hydroxide (NAOH), calcium hydroxide (Ca (OH) 2 ) or a combination thereof.
According to one embodiment, it is possible to provide purified CNTs by the above method.
Other specific details of embodiments of the present invention are included in the following detailed description.
According to the CNT purification method using the fluidized bed reactor according to the present invention, by performing the CNT purification reaction using the fluidized bed, the reactor is operated at a higher density than the CNT purification method using a heating furnace such as a conventional box furnace. Since the contact between the powder and the gas can be made effectively, the time taken for the CNT purification process can be shortened, and impurities such as a metal catalyst in the CNT can be effectively purified.
Figure 1 schematically shows a carbon nanotube purification system according to the present invention.
2 is an SEM image of CNTs according to Preparation Example 1 and Example 1. FIG.
As the present invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.
As used herein, the term "injection" may be used interchangeably with "injection, infusion" within this specification and may be understood to mean flowing or injecting liquid, gas, or heat to where necessary. have.
Hereinafter, a carbon nanotube (CNT) purification method according to an embodiment of the present invention will be described in more detail.
In order to obtain high purity CNTs, impurities may be removed through a purification step, which is a post-treatment of CNT synthesis. Impurities that may be included in the synthesized CNTs may include amorphous carbon materials, fullerenes, graphite, metal catalysts, and the like, and generally, CNTs are purified by removing such impurities by chemical and physical methods.
CNT purification method using a fluidized bed reactor according to the present invention, in a fluidized bed reactor having a gas inlet and outlet, and a carbon nanotube (CNT) inlet and outlet, inert carbon nanotubes containing impurities containing residual metal It is characterized by removing by reacting with a halogen-containing gas under a gas atmosphere.
1 schematically shows a carbon nanotube purification system as an embodiment of the present invention.
According to one embodiment, the purification method according to the present invention is a chemical agent for raising the carbon nanotubes containing impurities including residual metal to a first temperature (T1) under an inert gas atmosphere, reacting with a halogen-containing gas to halogenate the impurities Stage 1; And a second step of heating to a second temperature (T2) higher than the first temperature to evaporate the halogenated impurities to remove through a gas outlet, and to obtain purified carbon nanotubes through a CNT outlet.
The first step may include the step of purging the amount of halogen-containing gas and inert gas in a fluidized bed reactor at a constant concentration according to the flow conditions, then raising the temperature to the first temperature (T1), reacting for a predetermined time and purging Can be.
In addition, in the first step, after the inside of the fluidized bed reactor is generated in an inert gas atmosphere, the addition of the inert gas is stopped, the halogen-containing gas is added, and the temperature is raised to the first temperature T1 to form a fluidized bed or the fluidized bed. It may include the step of purging after the reaction for a certain time in a closed state of the reactor.
The closed state may mean a state in which all the valves of the fluidized bed reactor are closed or no gas is introduced or discharged in the reactor, and may include a vacuum atmosphere, and the vacuum atmosphere may mean a pressure of 1 torr or less. Can be.
The transferring may be purging with one or more gases selected from a halogen containing gas or an inert gas, for example, purging with an inert gas after reacting under the flow conditions, and reacting in the closed condition. After the step of purging may be purged with an inert gas, but is not limited thereto.
Among the steps included in the first step, the step of adding a halogen-containing gas, adding an inert gas, and raising the temperature to the first temperature T1 may be performed in any order within the first step. In addition, the first step may appropriately include the order and number of times of the reaction under the flow conditions and the reaction under a closed condition.
According to an embodiment, the first temperature T1 may be 600 ° C to 1000 ° C. When the first temperature T1 is less than the above temperature range, the chlorination reaction with respect to the metal impurities including the catalyst metal in the carbon material may not be smooth.
The second step may include removing a halogenated impurity containing a halogenated metal or the like from the first step, and may include raising the temperature to a second temperature T2. The second step may include adding a halogen-containing gas under an inert gas atmosphere or a vacuum atmosphere to react and remove impurities. The order and number of the inert gas atmosphere formation or the vacuum atmosphere formation and the halogen-containing gas addition are not particularly limited, and may be alternately or repeated as appropriate.
According to one embodiment, the second temperature (T2) may be higher than the first temperature, specifically, T2 may be a temperature of T1 + 100 ℃ or more. The second temperature T2 may be, for example, a temperature range of 700 ° C. to 1500 ° C., and more specifically, may be 900 ° C. to 1400 ° C. When the second temperature T2 is lower than the substrate range or lower than the first temperature, the removal reaction of impurities including halogenated metals is not smooth, and residual metals and halogenated metals remain in the carbon nanotubes and become impurities. It can act, which may be a factor to lower the physical properties of the carbon nanotubes. In addition, the graphitization of the catalyst by the residual metal occurs at a temperature above the substrate range, it may not be easy to remove impurities such as metal.
In the CNT purification method according to the present invention, the first step and the second step are not particularly limited in the order and number of times, and according to the crystallinity of the CNT to be purified and the type, purification rate, and the like of the catalytic metal used for CNT synthesis. Can be appropriately selected.
The catalyst metal is not particularly limited as long as it is a material that promotes the growth of carbon nanotubes. Examples of the catalyst metal include at least one metal selected from the group consisting of Groups 3 to 12 of the Group 18 periodic table. For example, it may be at least one metal selected from the group consisting of
According to one embodiment, carbon nanotube purification according to the present invention may be carried out in a continuous process through one fluidized bed reactor.
The process including the first step and the second step may be carried out in one fluidized bed reactor, and the fluidized bed reactor may specifically include a
In addition, according to one embodiment, the carbon nanotube purification of the present invention may be performed in a continuous process using two fluidized bed reactors. Specifically, the first step process may be performed in a first fluidized bed reactor, and the second step process may be performed in a second fluidized bed reactor.
According to one embodiment, the reaction time of the first step may be maintained, for example, for 10 minutes to 1 hour, the halogenation process of the residual metal within the above range can be made more completely, the reaction time is It can be adjusted according to the size of the carbon nanotubes and the reactor.
In addition, the reaction time of the second step may be maintained for 30 minutes to 300 minutes, and may be appropriately adjusted within a range capable of removing only impurities including residual metal and the like without affecting carbon nanotubes.
The treatment time and temperature may be appropriately adjusted by those skilled in the art according to the crystallinity of CNTs to be purified and the type of catalyst metal used for CNT synthesis.
Each of the above processes may be carried out in any combination, it is also possible to repeat the specific process.
According to one embodiment, the method may further include cooling the purified carbon nanotubes through a purification method including the first and second steps.
In addition, according to one embodiment, as shown in Figure 1 may further include the step of recovering the gas discharged from the
As the neutralizing solution, for example, a solution containing nitric acid or sulfuric acid may be used. Specifically, silver nitrate (AgNO 3 ), sodium thiosulfate (Na 2 S 2 O 3 ), sodium chloride (NaCl), thiocyanic acid Halides are removed using an aqueous solution of a material selected from potassium (KSCN), ammonium thiocyanate (NH 4 SCN), aluminum salt compounds, sodium hydroxide (NAOH), calcium hydroxide (Ca (OH) 2 ), or a combination thereof It is possible, but is not limited to the above examples.
According to one embodiment, the pressure of the halogen-containing gas may be supplied to 500torr to 900torr, for example, 600torr to 800torr, more specifically may be to supply at a pressure of 600torr to 700torr.
In addition, the pressure of the inert gas may be supplied to 500torr to 800torr, for example, 600torr to 800torr, more specifically may be to supply at a pressure of 600torr to 700torr.
The flow rates of the halogen-containing gas and the inert gas as described above can be shortened at high concentrations of halogen gas and can be long at low conditions, and can be appropriately adjusted by the user. In addition, since the reactivity of the halogen gas may also be affected by the environmental conditions such as the reactor material, it may be appropriately adjusted according to the environmental conditions such as the material, catalyst, reaction temperature of the reactor.
According to one embodiment, the halogen-containing gas may be a gas containing fluorine, chlorine, bromine, yorod or a mixture thereof, for example, chlorine-containing gas may be used, and more specifically, chlorine gas Or a gas containing trichloromethane gas or a mixed component thereof. By using such a halogen-containing gas, halogen ions having a high electron affinity can be used to remove impurities, particularly metal-containing impurities. For example, halogen ions have high reactivity with iron-containing impurities, and thus, these characteristics can be used to After reacting these, impurities covalently bonded with halogen ions and metal ions can be selectively removed as reaction products.
In addition, the inert gas may include, for example, a gas containing nitrogen, helium, neon, argon, krypton, xenon, radon, or a mixed component thereof, and specifically, nitrogen gas may be used. Since the inert gas is chemically very stable and does not want to exchange or share electrons, the inert gas may serve to flow and move the CNTs due to the inflow of the gas without reacting with the CNTs.
The gases may be introduced into the
In addition, halogen gas, inert gas, etc. used in the CNT purification method using a fluidized bed reactor can also be recycled and used.
The injection method of the gas is not particularly limited, and may include a purge method, a pulse method, a continuous input method or an injection method in combination thereof. For example, the purge method may include a method of intermittently and continuously injecting a gas, and the pulse method may include a method of injecting a predetermined amount of gas at a predetermined period. In addition, the continuous injection method may include a method of injecting a gas at a specific speed, the gas injection method as described above may be used in combination.
The CNT purification method according to the present invention has the advantage that the purification process and the cooling process may be separated and processed, that is, the step in which the purification process is performed and the step in which the cooling process is performed may be processed in separate spaces. Here, the purification process may mean a step of reacting the halogen-containing gas and impurities, and the cooling process may mean a step of lowering the temperature of the CNT after the purification process. For example, the cooling process, the carbon nanotubes from which impurities are removed according to the present invention may be processed after moving to the cooling and
In the conventional general cooling process, the method of treating the cooling due to natural convection by cutting off the heat supply to the heating furnace may take a long time to decrease the temperature, and thus the cooling water or the cooling gas consumed may increase. In contrast, according to the method according to the present invention, the CNTs recovered after the purification process are moved to separate the cooling process, so that the energy heated for the purification process can be used as it is in the next batch, while the next purification process is in progress. Since the recovered CNTs can be cooled, sufficient cooling time can be ensured. Accordingly, when the purification process and the cooling process are separately processed according to the present invention, it is possible to save the time taken for the recovery through the purification of CNTs and raw materials such as cooling water and cooling gas.
The
As described above, the purification process according to the present invention can be operated under flow conditions and closed conditions, the amount of gas consumed by performing the CNT purification process under flow conditions or closed conditions using an inert gas and a halogen-containing gas. Can be reduced, so that the process can be carried out efficiently.
According to the present invention, it is possible to provide CNTs purified with high purity by the method as described above, and such CNTs may exhibit the best performance in various fields. For example, CNTs have many application fields such as medical or engineering micro components, electronic devices, batteries, etc., in particular, electronic materials, etc., may cause disadvantages that may cause defects and deterioration in performance when impurities are contained. Therefore, when using the CNT purification method according to the present invention and the CNT purified by this method, this problem can be minimized.
The carbon nanotubes according to the present invention may be prepared by growing carbon nanotubes by chemical vapor deposition (CVD) through decomposition of a carbon source using a supported catalyst, and the catalyst metal supported on the supported catalyst is carbon nanotubes. It will not be restrict | limited in particular, if it is a substance which accelerates growth of.
Examples of such a catalytic metal include at least one metal selected from the group consisting of Groups 3 to 12 of the Group 18 periodic table recommended by IUPAC in 1990. Among them, at least one metal selected from the group consisting of
It is well known to control reaction activity by using 2 or more types of these catalyst metals and catalyst metal precursor compounds. For example, at least one element selected from iron (Fe), cobalt (Co) and nickel (Ni), and an element selected from titanium (Ti), vanadium (V) and chromium (Cr) and molybdenum (Mo) and tungsten What combined the element chosen from (W) can be illustrated. Preferably, it may be a metal catalyst containing cobalt (Co) as a main component and further including at least one metal selected from iron (Fe), molybdenum (Mo), chromium (Cr), and vanadium (V).
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
Preparation Example 1 Preparation of Carbon Nanotubes (CNT)
Carbon nanotube synthesis was tested in a laboratory scale fluidized bed reactor using a Co / Fe / Mo / V / Al-containing metal catalyst for CNT synthesis. Specifically, the CNT synthesis catalyst prepared in the above process and CNT were mixed and mounted in the middle of a quartz tube having an inner diameter of 55 mm, and then heated to 700 ° C. in a nitrogen atmosphere, and then maintained. The gas was synthesized for 2 hours while flowing at a flow rate of 900 sccm to synthesize an entangled carbon nanotube aggregate. A photograph of the prepared CNTs is shown in Preparation Example 1 of FIG. 2.
Examples 1-2 and Comparative Example 1: Purification of Carbon Nanotubes
Example 1
20 g of carbon nanotubes prepared in Preparation Example 1 were placed in a fluidized bed reactor. The reactor internal temperature was raised to 900 ° C while injecting N 2 at a flow rate of 1000 sccm. Next, halogen-containing gases Cl 2 and N 2 were supplied at a flow rate of 1000 sccm at a ratio of 1: 1 for 30 minutes.
After injecting only N 2 , the sample was transferred to a second high temperature reactor at 1200 ° C., and then cooled for 30 minutes under N 2 gas atmosphere. Photographs of CNTs subjected to this process are shown in the photographs of Example 1 of FIG.
Example 2
20 g of carbon nanotubes prepared in Preparation Example 1 were disposed in a fluidized bed reactor.
The reactor internal temperature was raised to 900 ° C while injecting N 2 at a flow rate of 1000 sccm. Next, the halogen-containing gases Cl 2 and N 2 are injected at a flow rate of 1000 sccm at a 1: 1 ratio for 5 minutes, and then only N 2 gas is supplied at 1000 sccm for 10 minutes. After again injecting Cl 2 gas and N 2 mixed gas, the process of supplying N 2 gas is repeated three times. After injecting only N 2 , the sample was transferred to a second high temperature reactor at 1200 ° C., and maintained for 30 minutes under a flow condition of an N 2 gas atmosphere, followed by cooling.
Comparative Example 1
20 g of carbon nanotubes prepared in Preparation Example 1 were disposed in a fluidized bed reactor.
After purging the inside of the reactor with an inert gas N 2 atmosphere, the temperature was raised to 1500 ° C. After 1 hour, the mixture was naturally cooled in a fixed bed condition of an N 2 atmosphere, and a metal foreign material removing process using only heat treatment was performed.
The carbon nanotubes of the examples and the comparative examples were analyzed by inductively coupled plasma spectrometry (ICP), and the contents of Fe, Co, Mo, V, and Cr in the carbon nanotubes were measured and shown in Table 1 below.
Continuous injection
Pulse injection
As can be seen above, according to the CNT purification method according to the present invention, it can be confirmed that the gas raw material and time consumed in the process can be saved, and the efficient process can be performed.
As described above in detail specific parts of the present invention, it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (16)
Reacting carbon nanotubes containing impurities including residual metals with a halogen-containing gas under an inert gas atmosphere to obtain purified carbon nanotubes; And
And transporting the purified carbon nanotubes to the recovery tank through the carbon nanotube outlet from the fluidized bed reactor to perform a cooling process.
Obtaining the purified carbon nanotubes is
A first step of heating a carbon nanotube containing an impurity including residual metal to a first temperature (T1) under an inert gas atmosphere and reacting with a halogen-containing gas to halogenate the impurity; And
A second step of heating to a second temperature (T2) higher than the first temperature to evaporate the halogenated impurities to remove them through a gas outlet, and to obtain purified carbon nanotubes through a CNT outlet;
Carbon nanotubes (CNT) purification method comprising a.
CNT purification method of the first temperature (T1) is 600 ℃ to 1000 ℃.
CNT purification method of the second temperature (T2) is T1 + 100 ℃ or more.
Obtaining the purified carbon nanotubes is a CNT purification method that is carried out in a continuous process using one fluidized bed reactor.
Obtaining the purified carbon nanotubes is carried out in a continuous process using two fluidized bed reactors, the first step is carried out in the first fluidized bed reactor, the second step is carried out in the second fluidized bed reactor Phosphorus CNT Purification Method.
And said halogen-containing gas is a gas containing fluorine, chlorine, bromine, iodine or a mixture thereof.
The halogen-containing gas is a gas containing chlorine gas or trichloromethane gas or a mixed component thereof.
Wherein said inert gas is a gas containing nitrogen, helium, neon, argon, krypton, xenon, radon, or a mixture thereof.
CNT purification method that the injection method of the gas comprises a purge method, a pulse method, a continuous injection method or a combination of these injection methods.
CNT purification method of 500 tortor to 800torr pressure of the inert gas.
CNT purification method of the halogen-containing gas is 500torr to 900torr.
CNT purification method further comprising the step of neutralizing the halogenated impurities recovered from the gas outlet.
The neutralization treatment includes silver nitrate (AgNO 3 ), sodium thiosulfate (Na 2 S 2 O 3 ), sodium chloride (NaCl), potassium thiocyanate (KSCN), ammonium thiocyanate (NH 4 SCN), aluminum salt compound, hydroxide CNT purification method carried out using a compound selected from sodium (NAOH), calcium hydroxide (Ca (OH) 2 ) or a combination thereof.
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| KR1020150147657A KR102017279B1 (en) | 2015-10-23 | 2015-10-23 | Method for purifying CNT using a fluidized bed reactor |
| CN201680004658.7A CN107108222A (en) | 2015-10-23 | 2016-08-29 | Utilize the CNT purification process of fluidized-bed reactor |
| PCT/KR2016/009568 WO2017069393A1 (en) | 2015-10-23 | 2016-08-29 | Cnt purification method using fluidized bed reactor |
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| CN108946704B (en) * | 2018-08-20 | 2020-03-31 | 山东晶石大展纳米科技有限公司 | Method and device for continuously preparing high-purity carbon nano tube |
| CN110655063A (en) * | 2019-11-07 | 2020-01-07 | 赛福纳米科技(徐州)有限公司 | Carbon nanotube purification device and purification method |
| CN111362255B (en) * | 2020-03-10 | 2021-10-22 | 内蒙古骏成新能源科技有限公司 | Carbon nano tube fluidization purification process method and fluidized bed reaction device |
| CN111498835A (en) * | 2020-04-27 | 2020-08-07 | 内蒙古骏成新能源科技有限公司 | Horizontal fluidizing device for gas-phase purification of carbon nano tube and fluidizing purification method |
| CN115215327B (en) * | 2022-02-23 | 2023-10-03 | 无锡东恒新能源科技有限公司 | Device and method for purifying carbon nano tube |
| CN116281964B (en) * | 2023-05-22 | 2023-08-11 | 湖南科晶新能源科技有限公司 | Efficient carbon nano tube purification method and purification equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020159944A1 (en) * | 2001-02-12 | 2002-10-31 | William Marsh Rice University | Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof |
| CN1475438A (en) * | 2003-07-18 | 2004-02-18 | 清华大学 | Purification method of carbon nano pipe and its device |
| US20080219913A1 (en) | 2004-06-21 | 2008-09-11 | Drexel University | Methods for Bulk Synthesis of Carbon Nanotubes |
| US20100119436A1 (en) | 2007-03-13 | 2010-05-13 | Toyo Tanso Co., Ltd. | Purification method for carbon material containing carbon nanotubes, carbon material produced by the same method, and resin molding, fiber, heat sink, slider, material for field electron emission source, conduction aid for electrode, catalyst support...... |
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| CN101631744A (en) * | 2007-03-13 | 2010-01-20 | 东洋炭素株式会社 | Method for purifying carbon material containing carbon nanotube, carbon material obtained by the purification method, and resin molded body, fiber, heat sink, sliding member, field emission source mat |
| CN103930603A (en) * | 2011-09-06 | 2014-07-16 | 西南纳米技术公司 | Single wall carbon nanotube purification process and improved single wall carbon nanotubes |
| CN103407984A (en) * | 2013-07-16 | 2013-11-27 | 清华大学 | Carbon nano-tube purification method based on weak oxidizing atmosphere oxidation assisted acid treatment |
| CN104401963A (en) * | 2014-10-27 | 2015-03-11 | 山东诚合新材料有限公司 | Carbon nanotube purification method capable of removing residual metals |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020159944A1 (en) * | 2001-02-12 | 2002-10-31 | William Marsh Rice University | Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof |
| CN1475438A (en) * | 2003-07-18 | 2004-02-18 | 清华大学 | Purification method of carbon nano pipe and its device |
| US20080219913A1 (en) | 2004-06-21 | 2008-09-11 | Drexel University | Methods for Bulk Synthesis of Carbon Nanotubes |
| US20100119436A1 (en) | 2007-03-13 | 2010-05-13 | Toyo Tanso Co., Ltd. | Purification method for carbon material containing carbon nanotubes, carbon material produced by the same method, and resin molding, fiber, heat sink, slider, material for field electron emission source, conduction aid for electrode, catalyst support...... |
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