CN117816058A - Single-double-wall carbon nano tube rapid discharging device and preparation method thereof - Google Patents
Single-double-wall carbon nano tube rapid discharging device and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
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- 239000012495 reaction gas Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
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- 238000005336 cracking Methods 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
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- 150000001875 compounds Chemical class 0.000 claims description 3
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
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Abstract
The invention discloses a single-wall and double-wall carbon nano tube rapid discharging device and a preparation method thereof. According to the preparation method, catalyst particles are uniformly sprayed into a plurality of positions at the upper part of a horizontal high-temperature synthesis unit, the catalyst particles enter a high-temperature reaction zone, raw gas is added to the bottom of the catalyst particles to grow carbon nanotubes, an array air inlet pipe is arranged at the end part of the reactor, and the generated carbon nanotubes can be quickly purged to the tail part by introducing atmospheric flow. Meanwhile, the rotary telescopic collecting device at the tail part can collect the generated carbon tube products. The device method can rapidly generate a large number of single-wall and double-wall carbon nanotubes, simultaneously, carbon tube products can be rapidly discharged, the condition that no products are accumulated in a hearth is ensured, and the method can be used for stably preparing high-yield single tubes for a long timeThe double-wall carbon nano tube has important commercial application value. The yield of the single-wall and double-wall carbon nanotube initial product prepared simultaneously reaches more than 500g/h, the purity is more than 70%, and the Raman characterization I G /I D The yield and the quality are high when the ratio is more than 40.
Description
Technical Field
The invention belongs to the technical field of nano material preparation devices, and relates to a single-double-wall carbon nano tube rapid discharging device and a preparation method thereof.
Background
Since Carbon Nanotubes (CNTs) were first discovered, more and more different methods for synthesizing different types of CNTs have been reported. Among them, multi-walled carbon nanotubes (MWCNTs) have been industrialized in the first place by means of industrial fluidized bed reactors and the like. Single-wall carbon nanotubes (SWCNTs) and double-wall carbon nanotubes (DWCNTs) are formed by crimping single-layer and double-layer concentric cylindrical graphene layers, and have more perfect physical structures, so that the single-wall carbon nanotubes (SWCNTs) and the double-wall carbon nanotubes (DWCNTs) have excellent performances in the aspects of mechanics, electrochemistry, electronic devices and the like. At present, a great deal of research and development is put into SWCNTs at home and abroad, and the Russian OCSIAl company is the only enterprise for realizing the mass production of SWCNTs. In our studies, SWCNTs often accompany the formation of certain amounts of DWCNTs during the formation process, which we have ascertained has a significant relationship with the type and amount of promoter in the catalyst and can achieve a controlled preparation. However, it is still challenging to realize mass production of single-wall and double-wall carbon nanotubes with high quality, purity and yield.
In the preparation of SWCNT, it is desirable to provide a more uniform temperature field and higher temperatures. In the floating method preparation process, a uniform thermal field can be provided, and the prepared SWCNT product has high quality. However, the yield of the floating method process product is difficult to be improved and large-scale preparation cannot be realized due to the limitation of the introduced amount of the catalyst and other factors. In another process for preparing SWCNTs by a plasma arc method, the arc core has an ultra-high temperature (5000-20000 ℃) which can enable a large amount of catalyst to be rapidly evaporated to form nano particles, and the method has the most potential for preparing SWCNTs on a large scale because the ultra-high temperature is radiated to the surrounding area of the arc and has a temperature field of about 2000 ℃. We have also previously made a great deal of research work on the plasma arc process for SWCNTs, but the problem of discharge has not been well solved. In the preparation process of the SWCNTs, the generated SWCNTs often form a filiform structure, and the filiform structure has strong adhesiveness and can remain in a hearth and be continuously enriched, so that the smooth discharging of a product is affected. The enriched area of SWCNTs remained in the hearth is gradually increased, so that the new growth process of the carbon tube is affected, the subsequent growth cannot be continued, the hearth is required to be cleaned by stopping the furnace, and the method is also a common problem in the process of researching SWCNTs. Numerous researches cannot solve the problem of quality and yield at present, and the design of a furnace body structure and discharge is very important.
Disclosure of Invention
The invention discloses a single-wall and double-wall carbon nano tube rapid discharging device and a preparation method thereof, which are used for solving any one of the above and other potential problems in the prior art.
In order to solve the problems, the technical scheme of the invention is as follows: a device for rapidly discharging single and double walled carbon nanotubes, the device comprising:
the horizontal high-temperature synthesis unit is used for forming a high-temperature reaction zone with uniform temperature at the central position, and can quickly crack and synthesize a carbon tube product by the raw material gas and a catalyst system entering the high-temperature reaction zone at the central position;
the end purging unit is used for intermittently providing high-pressure pulse purging gas and purging the generated carbon tube product out of the horizontal high-temperature synthesis unit;
the catalyst introducing unit is used for uniformly spraying the catalyst system into the high-temperature reaction zone under the drive of the pre-reaction air flow;
the raw material gas supplementing unit is used for supplementing carbon source gas during the cracking of the synthesized carbon tube, and forms a hedging gas flow with the mixed gas flow introduced by the catalyst introducing unit, and fully contacts with the evaporated underreacted catalyst nano particles in the gas flow;
the collecting unit is used for collecting the carbon tube products blown by the end blowing unit;
wherein the end blowing unit and the collecting unit are respectively arranged at two ends of the horizontal high-temperature synthesis unit, the catalyst introducing unit is positioned on the side wall of the right upper end of the horizontal high-temperature synthesis unit, the opening end is aligned with the central line of the horizontal high-temperature synthesis unit,
the feed gas supplementing unit is positioned on the side wall of the lowest end of the horizontal high-temperature synthesizing unit, and the opening end of the feed gas supplementing unit is aligned with the central line of the horizontal high-temperature synthesizing unit;
and the catalyst introducing unit and the raw material gas supplementing unit are symmetrically arranged.
Further, the apparatus further comprises: an end rotation auxiliary collection unit and a purge unit;
the tail end rotation auxiliary collecting unit is used for mechanically winding out a small amount of residual carbon tube products in the horizontal high-temperature synthesizing unit;
and the purging unit is used for cleaning carbon tube products wound on the auxiliary collecting unit.
Further, the horizontal high temperature synthesis unit includes: a hearth with an equal diameter cylinder structure and a plurality of heating components;
wherein, the hearth of the equal diameter cylinder structure is horizontally arranged, and both ends are open ends;
the inner lining is arranged in the hearth of the equal-diameter cylinder structure, and the heating assemblies are equidistantly arranged on the side wall of the inner lining.
Further, the diameter of the hearth of the equal-diameter cylinder structure is 300-1500 mm, and the lining is a graphite tube;
the heating component is an induction plasma heating component, a resistance wire heating component or a microwave heating component.
Further, the end purging component is an array-type arranged pulse air inlet;
the pulse air inlets arranged in an array mode are arranged at the end portion of one end of the hearth of the equal-diameter cylinder structure through flanges;
the catalyst introducing unit and the raw material gas supplementing unit are provided with a plurality of groups of nozzles; the multiple groups of nozzles are all arranged at equal intervals in a linear manner, the distance between the nozzles is 200-600 mm, and the center line of each nozzle is equal to the center point of the hearth of the equivalent diameter cylinder structure.
Further, the terminal rotation auxiliary collection unit includes: rotating the telescopic motor and the paddle;
the purging unit is an air gun;
the top of the collecting unit is provided with a tail gas filtering outlet, and the air gun is arranged on the inner side wall of the collecting unit below the tail gas filtering outlet;
one end of the collecting unit is connected with the other end of the hearth of the equal-diameter cylinder structure, and the rotary telescopic motor is arranged on the outer side wall of the other end of the collecting unit and is positioned at the same height with the opening of the hearth of the equal-diameter cylinder structure;
the blade is mounted at an end of an output shaft of the rotary telescopic motor inside the collecting unit.
Another object of the present invention is to provide a method for preparing single-wall and double-wall carbon nanotubes using the above device, which specifically includes the following steps:
s1) preparing a catalyst system according to a proportion, and adding the catalyst system into a storage chamber for standby;
s2) preheating the horizontal high-temperature synthesis unit to a reaction temperature, and spraying the catalyst system in the S1) into a high-temperature reaction area of the horizontal high-temperature synthesis unit through a catalyst introducing unit under the drive of a pre-reaction air flow at a certain flow rate to uniformly disperse;
s3) quickly evaporating the dispersed catalyst particles in a high-temperature reaction zone to form nano particles, cracking the nano particles with raw material gas in a pre-reaction gas flow to generate a carbon tube product, and fully contacting the nano particles of the catalyst which are not fully reacted with the carbon source gas introduced by a raw material gas supplementing unit in a central zone to form a hedging gas flow to further generate the carbon tube product;
s4) intermittently providing high-pressure pulse sweeping gas by the end sweeping unit in the middle of the synthesis process, and collecting carbon tube products into the collecting unit to obtain the single-wall and double-wall carbon nanotubes.
Further, the catalyst system in S1) includes a catalyst and a promoter, and the mass ratio of the catalyst to the promoter is 14-35: 0.1 to 7;
the catalyst is at least one of iron powder, nickel powder, cobalt powder, ferrocene, cobaltocene, nickel dichloride, ferric sulfate, carbon-based iron powder, ferric oxide powder and ferrous sulfate powder;
the promoter is a compound containing at least one of sulfur, selenium and tellurium;
the catalyst system is a particle system or a solution system, and the average particle size of the particle system is 10-150 mu m;
the solution system is to dissolve or disperse the catalyst and the accelerator into at least one solvent of water, ethanol, toluene, phenol, benzene and xylene.
Further, the reaction temperature in the S2) is 800-3000 ℃;
the flow rate of the pre-reaction gas flow is 20-500L/min; the pre-reaction gas stream comprises argon, hydrogen and a carbon source gas. And the flow ratio of the argon, the hydrogen and the carbon source gas is (1-50): (0.5-20): 1, a step of;
the particle size of the catalyst nano particles in the S3) is 0.5-15 nm;
the flow rate of the carbon source gas introduced by the raw material gas supplementing unit is 10-200L/min;
the number of pulse air inlets of the end part purging unit in the S4) is 5-30, the purging gas is argon, and the total flow is 100-1500L/min.
The single-wall and double-wall carbon nano tube is prepared by the method, the yield of the initial product of the single-wall and double-wall carbon nano tube reaches more than 500g/h, the purity is more than 70%, and the Raman characterization I G /I D Is 40 or more.
The beneficial effects of the invention are as follows: by adopting the technical scheme, the catalyst introducing unit of the device sprays catalyst particles with certain granularity or a prepared catalyst solution system into the hearth, so that the catalyst system can be dispersed for the first time, and the uniformly dispersed catalyst particles are quickly evaporated to form nano particles after being injected into a high-temperature area in the hearth, thereby ensuring the uniformity of the catalyst particles;
simultaneously, the catalyst introducing unit drives carbon source gas and catalyst into the hearth together, so that the sufficient contact of the carbon source gas and the catalyst is ensured, and simultaneously, a high-concentration carbon source core area can be formed in the reaction area by supplementing the carbon source at the position, which is right opposite to the upper feed inlet, of the bottom of the hearth, so that the sufficiency of the carbon source in the reaction process is ensured, the area of the reaction area can be increased, the catalytic efficiency is improved, and the yield is finally improved;
the carbon tube product generated in the hearth can be discharged quickly in time by adopting a mode of sweeping and/or a synergistic effect of cleaning and discharging by a rotary telescopic machine, so that the problem of coking caused by carbon tube stay in the hearth is avoided, and the difficult problem of discharging of the carbon tube preparation is successfully solved;
the horizontal high-temperature synthesis unit is of a large-scale expandable horizontal structure, and the horizontal structure has the advantages of smooth furnace body, easiness in heat preservation, contribution to quick discharging, large temperature area, high temperature uniformity and capability of providing a stable heat source, and can prolong the furnace body to increase the feed inlets according to production requirements to realize expansion;
by adopting the rapid discharging device, continuous preparation can be carried out, coking influence can not be generated in a hearth, and the single-wall and double-wall carbon nano tube with high yield and high crystallinity can be prepared.
Drawings
Fig. 1 is a schematic structural diagram of a single-double-wall carbon nanotube rapid discharging device according to the present invention.
Fig. 2 is a schematic structural view of an apparatus according to another embodiment of the present invention.
Fig. 3 is a schematic view of the structure of the end purge unit of the present invention.
Fig. 4 is a scanning electron micrograph of a single double walled carbon nanotube prepared in example 1 using the apparatus and method of the present invention.
Fig. 5 is a transmission electron micrograph of single and double walled carbon nanotubes prepared in example 1 of the present invention using the apparatus and method of the present invention.
Fig. 6 is a graph of raman spectra of single and double walled carbon nanotubes prepared in example 1 of the present invention using the apparatus and method of the present invention.
Fig. 7 is a thermal gravimetric test graph of single and double walled carbon nanotubes prepared in example 1 of the present invention using the apparatus and method of the present invention.
Fig. 8 is a scanning electron micrograph of single and double walled carbon nanotubes prepared in example 2 of the present invention using the apparatus and method of the present invention.
Fig. 9 is a scanning electron micrograph of single and double walled carbon nanotubes prepared in example 3 of the present invention using the apparatus and method of the present invention.
In the figure:
1. an end purge unit; 2. a catalyst introduction unit; 3. a horizontal high-temperature synthesis unit; 4. a raw material gas supplementing unit; 5. an end rotation auxiliary collection unit; 5-1, rotating a telescopic motor; 5-2, paddles; 6. a collection unit; 7. a tail gas filtering gas outlet; 8. and a purge unit.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific examples.
As shown in fig. 1, the device for rapidly discharging single-wall and double-wall carbon nanotubes according to the present invention comprises:
the horizontal high-temperature synthesis unit 3 is used for forming a high-temperature reaction zone with uniform temperature at the central position, and can quickly crack and synthesize a carbon tube product by the raw material gas and a catalyst system entering the high-temperature reaction zone at the central position;
the end purging unit 1 is used for intermittently providing high-pressure pulse purging gas and purging the generated carbon tube product out of the horizontal high-temperature synthesis unit 3;
the catalyst introducing unit 2 is used for uniformly spraying the catalyst system into the high-temperature reaction zone under the drive of the pre-reaction air flow;
a raw material gas supplementing unit 4, configured to supplement carbon source gas during the pyrolysis of the synthesized carbon tube, and form a hedging gas stream with the mixed gas stream introduced by the catalyst introducing unit 2, and fully contact with the insufficiently reacted catalyst nanoparticles evaporated in the gas stream;
a collecting unit 6 for collecting the carbon tube product blown out by the end blowing unit 1;
wherein the end blowing unit 1 and the collecting unit 6 are respectively arranged at two ends of the horizontal high-temperature synthesis unit 3 and communicated with the horizontal high-temperature synthesis unit 3, the catalyst introducing unit 2 is positioned on the side wall of the right upper end of the horizontal high-temperature synthesis unit 3, the opening end is aligned with the central line of the horizontal high-temperature synthesis unit 3,
the raw material gas supplementing unit 4 is positioned on the side wall of the lower end of the horizontal high-temperature synthesizing unit 3, and the opening end is aligned with the central line of the horizontal high-temperature synthesizing unit 3;
and the catalyst introducing unit 2 and the raw material gas supplementing unit are symmetrically arranged.
The horizontal high temperature synthesis unit 3 includes: a hearth with an equal diameter cylinder structure and a plurality of heating components;
wherein, the hearth of the equal diameter cylinder structure is horizontally arranged, and both ends are open ends;
the inner lining is arranged in the hearth of the equal-diameter cylinder structure, and the heating assemblies are equidistantly arranged on the side wall of the inner lining. The heating components are all of the same power, and the temperature difference is controlled between +5 ℃ and-5 ℃;
the diameter of the hearth of the equal-diameter cylinder structure is 300-1500 mm, and the lining is a graphite tube;
the heating component is an induction plasma heating component, a resistance wire heating component or a microwave heating component.
As shown in fig. 2, another embodiment of the device of the present invention: the apparatus further comprises: an end rotation auxiliary collection unit 5 and a purge unit 8;
the tail end rotation auxiliary collecting unit 5 is used for mechanically winding out a small amount of residual carbon tube products in the horizontal high-temperature synthesizing unit 3;
the purging unit 8 is used for cleaning carbon tube products wound on the auxiliary collecting unit 5;
wherein the tip rotation auxiliary collection unit 5 includes: a rotary telescopic motor 5-1 and a paddle 5-2;
the purging unit 8 is an air gun;
the top of the collecting unit 6 is provided with a tail gas filtering outlet 7, and the air gun is arranged on the inner side wall of the collecting unit 6 below the tail gas filtering outlet 7;
one end of the collecting unit 6 is connected with one end of the hearth of the equal-diameter cylinder structure, the rotary telescopic motor 5-1 is installed on the outer side wall of the other end of the collecting unit 6 and is located at the same height with the opening of the hearth of the equal-diameter cylinder structure, and the blade 5-2 is installed at the end part of the output shaft of the rotary telescopic motor inside the collecting unit 6 and can reciprocate in the hearth of the equal-diameter cylinder structure.
As shown in fig. 3, the end purging unit 1 is an array-type pulse air inlet;
the pulse air inlets arranged in an array mode are arranged at the end portion of one end of the hearth of the equal-diameter cylinder structure through flanges;
the catalyst introducing unit 2 and the raw material gas supplementing unit 4 are provided with a plurality of groups of nozzles; the multiple groups of nozzles are all arranged at equal intervals in a linear manner, the distance between the nozzles is 200-600 mm, and the center line of each nozzle is equal to the center point of the hearth of the equivalent diameter cylinder structure.
The method for preparing the single-wall and double-wall carbon nano tube by adopting the device comprises the following steps:
s1) preparing a catalyst system according to a proportion, and adding the catalyst system into a storage chamber for standby;
s2) preheating the horizontal high-temperature synthesis unit 3 to a reaction temperature, and spraying the catalyst system in the S1) into a high-temperature reaction area of the horizontal high-temperature synthesis unit 3 through a catalyst introducing unit 2 under the drive of a pre-reaction air flow at a certain flow rate and uniformly dispersing;
s3) quickly evaporating the dispersed catalyst particles in a high-temperature reaction zone to form nano particles, cracking the nano particles with raw material gas in a pre-reaction gas flow to generate a carbon tube product, and fully contacting the nano particles of the catalyst which are not fully reacted with the carbon source gas introduced by the raw material gas supplementing unit 4 in a central zone to form a hedging gas flow to further generate the carbon tube product;
s4) the end part purging unit 1 intermittently provides high-pressure pulse purging gas in the middle of the synthesis process, purging is performed once at intervals of 3-50S, and carbon tube products are collected and enter the collecting unit 6, so that the single-wall and double-wall carbon nanotubes are obtained.
The catalyst system in the S1) comprises a catalyst and a promoter, wherein the mass ratio of the catalyst to the promoter is 14-35: 0.1 to 7;
the catalyst is at least one of iron powder, nickel powder, cobalt powder, ferrocene, cobaltocene, nickel dichloride, ferric sulfate, carbon-based iron powder, ferric oxide powder and ferrous sulfate powder;
the promoter is a compound containing at least one of sulfur, selenium and tellurium;
the catalyst system is a particle system or a solution system, and the average particle size of the particle system is 10-150 mu m;
the solution system is to dissolve or disperse the catalyst and the accelerator into at least one solvent of water, ethanol, toluene, phenol, benzene and xylene.
The reaction temperature in the S2) is 800-3000 ℃;
the flow rate of the pre-reaction gas flow is 20-500L/min; the pre-reaction gas stream comprises argon, hydrogen and a carbon source gas. And the flow ratio of the argon, the hydrogen and the carbon source gas is (1-50): (0.5-20): 1, a step of;
the particle size of the catalyst nano particles in the S3) is 0.5-15 nm;
the flow rate of the carbon source gas introduced by the raw material gas supplementing unit is 10-200L/min;
the number of pulse air inlets of the end part purging unit in the S4) is 5-30, the purging gas is argon, and the total flow is 100-1500L/min;
the single-wall and double-wall carbon nano tube is prepared by the method, the yield of the initial product of the single-wall and double-wall carbon nano tube reaches more than 500g/h, the purity is more than 70%, and the Raman characterization I G /I D Is 40 or more.
Example 1
Iron powder and ferrous sulfide powder are respectively weighed according to the mass ratio of 4:1 and are uniformly mixed, the average particle size of the mixed particles is controlled to be 50 mu m, and the mixed particles are added into a storage chamber for standby. Preheating an induction plasma hearth to 2000 ℃ in advance, spraying the prepared catalyst system into a high-temperature furnace body through a catalyst guiding unit 2 under the drive of airflow, and controlling the gas flow to be 150L/min, 20L/min and 20L/min of methane at the momentL/min. The catalyst system enters the center of the furnace chamber for 0.1m 3 The catalyst particles dispersed in the area volume are rapidly evaporated to form 10nm nano particles under the action of high temperature in the hearth, and the raw material gas supplementing unit 4 is introduced into the methane with the flow rate of 40L/min to be combined with the formed catalyst nano particles for reaction, so that the single-wall and double-wall carbon nano tube is synthesized;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at the flow rate of 500L/min by adopting 10 groups of air inlet pipes at intervals of 10s for purging. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive to rotate through the rotary telescopic motor 5-1, the paddles 5-2 extend into the end part of the furnace body, the generated carbon tube products are wound on the paddles 5-2 by the rotary paddles 5-2 and slowly pulled out into the collecting unit 6, residual carbon tube products which are not blown out in the furnace chamber are cleaned for the second time, and the influence of the products in the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through the purging unit 8 of high-pressure inert gas, and the bottom of the collector can compress and then collect the purged fluffy carbon tube products, so that the continuous collection capability is ensured.
The reaction can be continuously carried out with a continuous supply of fresh catalyst, and the yield is calculated to be 550g/h by taking out the product from the collection unit and carrying out characterization. As shown in a scanning electron microscope photograph of the obtained product in FIG. 4, a large number of carbon tube products are stuck together in a bundle shape with different thicknesses to form a flat sheet layer, the length of the carbon tubes in the bundle shape can be clearly observed to be several micrometers, the appearance of the sample is very clean, and few large particle impurities appear; transmission electron micrographs are shown in fig. 5, where it can be seen that a plurality of carbon tubes are stuck together, and by careful identification, it can be seen that all of the carbon tubes are composed of single-walled and double-walled carbon nanotubes; the Raman spectrum is shown in FIG. 6, the laser wavelength is 532nm, 150cm -1 The characteristic peak of the single-wall carbon nano tube which is obvious nearby-RBM peak can be calculated to obtain I G /I D 46, has higher crystallinity; as shown in FIG. 7, the thermal gravimetric test curve of the product shows that the sample starts to decompose rapidly at 600 ℃ to 800 ℃ and then to decompose completely, and has high thermal stability and a residual amount of 9.3% or so, less residual impurities and higher sample purity.
Example 2
And (3) weighing ferrocene and ferrous sulfide powder according to the mass ratio of 5:1, uniformly mixing, controlling the average particle size of the mixed particles to be 40 mu m, and adding the mixed particles into a storage chamber for standby. The induction plasma hearth is preheated to 1800 ℃ in advance, the prepared catalyst system is sprayed into the high-temperature furnace body through the catalyst guiding unit 2 under the drive of air flow, and at the moment, the gas flow is controlled to be 100L/min for argon, 30L/min for hydrogen and 30L/min for methane. The catalyst system enters the center of the furnace chamber for 0.15m 3 The catalyst particles dispersed in the area volume are rapidly evaporated to form 10nm nano particles under the action of high temperature in the hearth, and the raw material gas supplementing unit 4 is introduced into the methane with the flow rate of 50L/min to be combined with the formed catalyst nano particles for reaction, so that the single-wall and double-wall carbon nano tube is synthesized;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at a flow rate of 400L/min by adopting 10 groups of air inlet pipes at intervals of 15s for purging. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive the rotary blade 5-2 through the rotary telescopic motor 5-1, the blade 5-2 stretches into the end part of the furnace body, the rotary blade 5-2 winds the generated carbon tube product onto the blade 5-2 and slowly pulls out the carbon tube product into the collecting unit 6, the residual carbon tube product which is not blown out in the furnace chamber is cleaned for the second time, and the influence of the internal product of the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through an air gun of high-pressure inert gas, and the bottom of the collector can compress and then collect the blown fluffy carbon tube products, so that the continuous collection capacity is ensured.
The reaction can be continuously carried out with a continuous supply of fresh catalyst, and the yield is 610g/h calculated by taking out the product from the collection unit and weighing the product, and then the product is characterized. The scanning electron micrograph of the resulting product is shown in FIG. 8, which is very close to the sample observed in example 1, and a large number of carbon tube products are bonded together in bundles of varying thickness and length of several microns to form a flat sheet, with small amounts of particulate impurities present on the sample surface.
Example 3
And (3) weighing ferrocene and thiophene according to the mass ratio of 7:1, mixing, adding the mixture into ethanol, preparing a solution system, and adding the solution system into a storage chamber for standby. The induction plasma hearth is preheated to 1500 ℃ in advance, the prepared catalyst solution system is sprayed into the high-temperature furnace body through the catalyst introducing unit 2 under the drive of heating airflow, and at the moment, the gas flow is controlled to be argon 250L/min, hydrogen 50L/min and methane 50L/min. The catalyst system enters the center of the furnace chamber for 0.15m 3 The catalyst particles dispersed in the area volume are rapidly evaporated to form 5nm nano particles under the action of high temperature in the hearth, and the raw material gas supplementing unit 4 is introduced into the methane with the flow rate of 100L/min to be combined with the formed catalyst nano particles for reaction, so that the single-wall and double-wall carbon nano tube is synthesized;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at a flow rate of 500L/min by adopting 15 groups of air inlet pipes every 10 s. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive the rotary blade 5-2 through the rotary telescopic motor 5-1, the blade 5-2 stretches into the end part of the furnace body, the rotary blade 5-2 winds the generated carbon tube product onto the blade 5-2 and slowly pulls out the carbon tube product into the collecting unit 6, the residual carbon tube product which is not blown out in the furnace chamber is cleaned for the second time, and the influence of the internal product of the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through an air gun of high-pressure inert gas, and the bottom of the collector can compress and then collect the blown fluffy carbon tube products, so that the continuous collection capacity is ensured.
The reaction can be continuously carried out with a continuous supply of fresh catalyst, with a yield of 650g/h calculated by taking out the product from the collection unit 6 and characterizing it. The scanning electron micrograph of the resulting product is shown in FIG. 9, which also shows that a large number of carbon tube products are bonded together in bundles of varying thickness and length of several microns to form a flat sheet, and that small amounts of particulate impurities are present on the sample surface.
Example 4
And respectively weighing nickel and selenium powder according to the mass ratio of 3:1, uniformly mixing, controlling the average particle size of the mixed particles to be 60 mu m, and adding the mixed particles into a storage chamber for standby. Lifting handleThe induction plasma furnace is preheated to 2500 ℃, the prepared catalyst system is sprayed into the high-temperature furnace body through the catalyst guiding unit 2 under the drive of air flow, and at the moment, the gas flow is controlled to be 350L/min for argon, 30L/min for hydrogen and 30L/min for methane. The catalyst system enters the center of the furnace chamber for 0.2m 3 The catalyst particles dispersed in the area volume are rapidly evaporated to form 5nm nano particles under the action of high temperature in the hearth, and the raw material gas supplementing unit 4 is introduced into the methane with the flow rate of 50L/min to be combined with the formed catalyst nano particles for reaction, so that the single-wall and double-wall carbon nano tube is synthesized;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at the flow rate of 800L/min by adopting 20 groups of air inlet pipes every 5 s. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive the rotary blade 5-2 through the rotary telescopic motor 5-1, the blade 5-2 stretches into the end part of the furnace body, the rotary blade 5-2 winds the generated carbon tube product onto the blade 5-2 and slowly pulls out the carbon tube product into the collecting unit 6, the residual carbon tube product which is not blown out in the furnace chamber is cleaned for the second time, and the influence of the internal product of the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through an air gun of high-pressure inert gas, and the bottom of the collector can compress and then collect the blown fluffy carbon tube products, so that the continuous collection capacity is ensured. While the reaction was continuously carried out with a continuous supply of fresh catalyst, the yield was calculated to be 550g/h by taking out the product from the collection unit 6 and weighing it.
Example 5
The ferrocene and selenium powder are respectively weighed according to the mass ratio of 8:1, mixed and added into dimethylbenzene to prepare suspension, and added into a storage chamber for standby. The induction plasma hearth is preheated to 2200 ℃ in advance, the prepared catalyst solution system is sprayed into the high-temperature furnace body through the catalyst introducing unit 2 under the drive of heating airflow, and at the moment, the gas flow is controlled to be argon 250L/min, hydrogen 50L/min and methane 50L/min. The catalyst system enters the center of the furnace chamber for 0.15m 3 The catalyst particles dispersed in the area are rapidly evaporated to form 8nm nano particles under the action of high temperature in the hearth, and the raw material gas is fed into the furnaceThe supplementing unit 4 is introduced with methane flow of 70L/min to combine with the formed catalyst nano particles for reaction, so as to synthesize the single-wall and double-wall carbon nano tube;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at a flow rate of 600L/min by adopting 15 groups of air inlet pipes every 5s for purging. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive the rotary blade 5-2 through the rotary telescopic motor 5-1, the blade 5-2 stretches into the end part of the furnace body, the rotary blade 5-2 winds the generated carbon tube product onto the blade 5-2 and slowly pulls out the carbon tube product into the collecting unit 6, the residual carbon tube product which is not blown out in the furnace chamber is cleaned for the second time, and the influence of the internal product of the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through an air gun of high-pressure inert gas, and the bottom of the collector can compress and then collect the blown fluffy carbon tube products, so that the continuous collection capacity is ensured. Meanwhile, the reaction can continuously supply fresh catalyst for continuous preparation, and the yield is 510g/h by taking out the product from the collecting unit and weighing the product.
Example 6
Weighing cobaltocene and tellurium powder according to the mass ratio of 9:1 respectively, mixing and adding into toluene to prepare suspension, and adding into a storage chamber for standby. The induction plasma hearth is preheated to 2500 ℃ in advance, the prepared catalyst solution system is sprayed into the high-temperature furnace body through the catalyst introducing unit 2 under the drive of heating airflow, and at the moment, the gas flow is controlled to be argon 250L/min, hydrogen 50L/min and methane 50L/min. The catalyst system enters the volume of a 0.15m < 3 > region in the center of the hearth and is rapidly dispersed, the dispersed catalyst particles are rapidly evaporated to form 8nm nano particles under the action of high temperature in the hearth, and the raw material gas supplementing unit 4 is introduced into methane with the flow rate of 70L/min to be combined with the formed catalyst nano particles for reaction, so that the single-wall and double-wall carbon nano tube is synthesized;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at a flow rate of 600L/min by adopting 15 groups of air inlet pipes every 5s for purging. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive the rotary blade 5-2 through the rotary telescopic motor 5-1, the blade 5-2 stretches into the end part of the furnace body, the rotary blade 5-2 winds the generated carbon tube product onto the blade 5-2 and slowly pulls out the carbon tube product into the collecting unit 6, the residual carbon tube product which is not blown out in the furnace chamber is cleaned for the second time, and the influence of the internal product of the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through an air gun of high-pressure inert gas, and the bottom of the collector can compress and then collect the blown fluffy carbon tube products, so that the continuous collection capacity is ensured. Meanwhile, the reaction can continuously supply fresh catalyst for continuous preparation, and the yield is 520g/h by taking out the product from the collecting unit and weighing the product.
Example 7
Cobalt powder and tellurium powder are respectively weighed according to the mass ratio of 4:1 and are uniformly mixed, the average particle size of the mixed particles is controlled to be 30 mu m, and the mixed particles are added into a storage chamber for standby. The induction plasma hearth is preheated to 2700 ℃ in advance, the prepared catalyst system is sprayed into the high-temperature furnace body through the catalyst guiding unit 2 under the drive of airflow, and at the moment, the gas flow is controlled to be 350L/min for argon, 30L/min for hydrogen and 30L/min for methane. The catalyst system enters the center of the furnace chamber for 0.1m 3 The catalyst particles dispersed in the area volume are rapidly evaporated to form 12nm nano particles under the action of high temperature in the hearth, and the raw material gas supplementing unit 4 is introduced into the methane with the flow rate of 50L/min to be combined with the formed catalyst nano particles for reaction, so that the single-wall and double-wall carbon nano tube is synthesized;
in the synthesis process, the end part purging unit 1 is started, and argon is introduced into the end part purging unit at the flow rate of 500L/min by adopting 10 groups of air inlet pipes every 5 s. Simultaneously, the tail end rotary auxiliary collecting unit 5 is started to drive the rotary blade 5-2 through the rotary telescopic motor 5-1, the blade 5-2 stretches into the end part of the furnace body, the rotary blade 5-2 winds the generated carbon tube product onto the blade 5-2 and slowly pulls out the carbon tube product into the collecting unit 6, the residual carbon tube product which is not blown out in the furnace chamber is cleaned for the second time, and the influence of the internal product of the furnace chamber in the growth process is ensured. Finally, the products on the blade 5-2 can be cleaned through an air gun of high-pressure inert gas, and the bottom of the collector can compress and then collect the blown fluffy carbon tube products, so that the continuous collection capacity is ensured. Meanwhile, the reaction can continuously supply fresh catalyst for continuous preparation, and the yield is 530g/h by taking out the product from the collecting unit and weighing the product.
The embodiment of the application provides a single-double-wall carbon nano tube rapid discharging device and a preparation method thereof, which are described in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product 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 product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (10)
1. A device for rapid discharge of single and double walled carbon nanotubes, the device comprising:
the horizontal high-temperature synthesis unit is used for forming a high-temperature reaction zone with uniform temperature at the central position, and can quickly crack and synthesize a carbon tube product by the raw material gas and a catalyst system entering the high-temperature reaction zone at the central position;
the end purging unit is used for intermittently providing high-pressure pulse purging gas and purging the generated carbon tube product out of the horizontal high-temperature synthesis unit;
the catalyst introducing unit is used for uniformly spraying the catalyst system into the high-temperature reaction zone under the drive of the pre-reaction air flow;
the raw material gas supplementing unit is used for supplementing carbon source gas during cracking of the synthetic carbon tubes, and forms a hedging gas flow with the mixed gas flow introduced by the catalyst introducing unit, and fully contacts with the evaporated underreacted catalyst nano particles in the gas flow;
the collecting unit is used for collecting the carbon tube products blown by the end blowing unit;
wherein the end blowing unit and the collecting unit are respectively arranged at two ends of the horizontal high-temperature synthesis unit, the catalyst introducing unit is positioned on the side wall of the right upper end of the horizontal high-temperature synthesis unit, the opening end is aligned with the central line of the horizontal high-temperature synthesis unit,
the feed gas supplementing unit is positioned on the side wall of the lowest end of the horizontal high-temperature synthesizing unit, and the opening end of the feed gas supplementing unit is aligned with the central line of the horizontal high-temperature synthesizing unit;
and the catalyst introducing unit and the raw material gas supplementing unit are symmetrically arranged.
2. The apparatus of claim 1, wherein the apparatus further comprises: an end rotation auxiliary collection unit and a purge unit;
the tail end rotation auxiliary collecting unit is used for mechanically winding out a small amount of residual carbon tube products in the horizontal high-temperature synthesizing unit;
and the purging unit is used for cleaning carbon tube products wound on the auxiliary collecting unit.
3. The apparatus of claim 2, wherein the horizontal high temperature synthesis unit comprises: a hearth with an equal diameter cylinder structure and a plurality of heating components;
wherein, the hearth of the equal diameter cylinder structure is horizontally arranged, and both ends are open ends;
the inner lining is arranged in the hearth of the equal-diameter cylinder structure, and the heating assemblies are equidistantly arranged on the side wall of the inner lining.
4. A device according to claim 3, wherein the diameter of the hearth of the constant diameter cylinder structure is 300-1500 mm, and the inner liner is a graphite tube;
the heating component is an induction plasma heating component, a resistance wire heating component or a microwave heating component.
5. A device according to claim 3, wherein the end purge means is an array of pulsed air inlets;
the pulse air inlets arranged in an array mode are arranged at the end portion of one end of the hearth of the equal-diameter cylinder structure through flanges;
the catalyst introducing unit and the raw material gas supplementing unit are provided with a plurality of groups of nozzles; the multiple groups of nozzles are linearly distributed at equal intervals, the distance is 200-600 mm, and the center line of each nozzle is opposite to the center point of the hearth of the equal-diameter cylinder structure.
6. A device according to claim 3, wherein the terminal rotation assist collection unit comprises: rotating the telescopic motor and the paddle;
the purging unit is an air gun;
the top of the collecting unit is provided with a tail gas filtering outlet, and the air gun is arranged on the inner side wall of the collecting unit below the tail gas filtering outlet;
one end of the collecting unit is connected with the other end of the hearth of the equal-diameter cylinder structure, and the rotary telescopic motor is arranged on the outer side wall of the other end of the collecting unit and is positioned at the same height with the opening of the hearth of the equal-diameter cylinder structure;
the blade is mounted at an end of an output shaft of the rotary telescopic motor inside the collecting unit.
7. A method for preparing single-double-walled carbon nanotubes using the apparatus of any of claims 1-6, comprising the steps of:
s1) preparing a catalyst system according to a proportion for standby;
s2) preheating the horizontal high-temperature synthesis unit to a reaction temperature, and spraying the catalyst system in the S1) into a high-temperature reaction area of the horizontal high-temperature synthesis unit through a catalyst introducing unit under the drive of a pre-reaction air flow at a certain flow rate to uniformly disperse;
s3) quickly evaporating the dispersed catalyst particles in a high-temperature reaction zone to form nano particles, cracking the nano particles with raw material gas in a pre-reaction gas flow to generate a carbon tube product, and fully contacting the nano particles of the catalyst which are not fully reacted with the carbon source gas introduced by a raw material gas supplementing unit in a central zone to form a hedging gas flow to further generate the carbon tube product;
s4) the end part purging unit intermittently provides high-pressure pulse purging gas in the middle of the synthesis process, and the carbon tube product is collected and enters the collecting unit to obtain the single-double-wall carbon nanotube.
8. The method according to claim 7, wherein the catalyst system in S1) comprises a catalyst and a promoter, and the mass ratio of the catalyst to the promoter is 14-35: 0.1 to 7;
the catalyst is at least one of iron powder, nickel powder, cobalt powder, ferrocene, cobaltocene, nickel dichloride, ferric sulfate, carbon-based iron powder, ferric oxide powder and ferrous sulfate powder;
the promoter is a compound containing at least one of sulfur, selenium and tellurium;
the catalyst system is a particle system or a solution system, and the average particle size of the particle system is 10-150 mu m;
the solution system is to dissolve or disperse the catalyst and the accelerator into at least one solvent of water, ethanol, toluene, phenol, benzene and xylene.
9. The method according to claim 7, wherein the reaction temperature in S2) is 800 to 3000 ℃;
the flow rate of the pre-reaction gas flow is 20-500L/min; the pre-reaction gas stream comprises argon, hydrogen and carbon source gas; and the flow ratio of the argon, the hydrogen and the carbon source gas is 1-50: 0.5 to 20:1, a step of;
the particle size of the catalyst nano particles in the S3) is 0.5-15 nm;
the flow rate of the carbon source gas introduced by the raw material gas supplementing unit is 10-200L/min;
the number of pulse air inlets of the end part purging unit in the S4) is 5-30, the purging gas is argon, and the total flow is 100-1500L/min.
10. A single-double-walled carbon nanotube, wherein the single-double-walled carbon nanotube is prepared by the method of any one of claims 7-9, the yield of the initial product of the single-double-walled carbon nanotube is more than 500g/h, the purity is more than 70%, and the raman characterization is I G /I D Is 40 or more.
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