CN102079519A - Preparation method and production equipment for controllably growing carbon nanotubes - Google Patents
Preparation method and production equipment for controllably growing carbon nanotubes Download PDFInfo
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- CN102079519A CN102079519A CN2009103098547A CN200910309854A CN102079519A CN 102079519 A CN102079519 A CN 102079519A CN 2009103098547 A CN2009103098547 A CN 2009103098547A CN 200910309854 A CN200910309854 A CN 200910309854A CN 102079519 A CN102079519 A CN 102079519A
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Abstract
The invention relates to a preparation method and production equipment for controllably growing carbon nanotubes. The technical scheme is that: a catalyst is made of bimetal, and magnesium oxide is taken as a catalyst carrier; a carbon-containing compound is introduced at a preparation temperature; chemical vapor deposition and cooling are performed successively; the bimetal is iron and molybdenum or nickel or the molybdenum in a ratio of 1:(0-3), and the iron or the nickel accounts for 1.8 to 9 mole percent; and the production equipment comprises a catalyst sample introduction device, and a reaction device and a sample collection device which are connected with the catalyst sample introduction device. Through the technical scheme of the preparation method and the production equipment, the diameter of the carbon nanotubes prepared by a chemical vapor deposition method can be controlled, high-quality carbon nanotubes are produced, a semi-continuous batch production device is designed, the preparation process is perfected, and the diameter-controllable carbon nanotubes are produced in batches.
Description
Technical field
The present invention relates to a kind of preparation method and production unit thereof of controllable growth carbon nanotube.
Background technology
Carbon nanotube is seamless, the hollow tube body that is curled into by the Graphene lamella that carbon atom forms.Carbon nanotube should have the excellent conducting performance of similar graphite in theory, but in fact it also will depend on the diameter and the helix angle of carbon nanotube.Its performance difference of the carbon nanotube of different structure is very big, electric property particularly, and carbon nanotube can be conductor and semiconductive with the structure difference.
Carbon atom in the carbon nanotube is with sp
2Hydridization is so but owing to exist certain curvature wherein to have sub-fraction carbon to belong to sp
3Hydridization.At the bending or the vary in diameter place of carbon nanotube, inside and outside carbon pentagon and the carbon heptagon introduced respectively just can make entire structure obtain continuity.The existence of defective has very big influence to the performance of carbon nanotube.
Transition-metal Fe, Co, Ni are the most frequently used catalyzer of preparation carbon nanotube.In recent years, the different types of new catalyst of a large amount of research and development is arranged, as Au, Ag, Cu, even semi-conductor and oxide nano particles.Discover that the bimetallic catalyst that metal catalyst forms after compound can significantly improve the output and the quality of carbon nanotube.Bimetallic catalyst [P.Coquay such as Fe-Co, Ti-Co, W-Co as report, A.Peigney, E.D.Grave, et al.J.Phys.Chem.B109 (2005) 17813, S.Sato, A.Kawabata, D.Kondo, et al.Chem.Phys.Lett.402 (2005) 149, P.Landois, A.Peigney, Ch.Laurent, et al.Carbon 47 (2009) 789.].。In transition-metal Fe, Co, Ni, add metal M o, can improve quality [B.K.Singh, the S.-W.Cho of carbon nanotube equally, K.S.Bartwal, et al.Solid State Commun.144 (2007) 498, L.-P.Zhou, K.Ohta, K.Kuroda, et al.J.Phys.Chem.B 109 (2005) 4439, H.Y.Miao, J.T.Lue, S.Y.Chen, et al.Thin Solid Films 484 (2005) 58.].With respect to single-metal reforming catalyst, the carbon nanotube defective of bimetallic catalyst preparation is few, the output height.
The preparation method of carbon nanotube mainly contains: graphite arc method, laser evaporation method and chemical Vapor deposition process.Graphite arc method and laser evaporation method are produced carbon nanotube all to be needed the graphite evaporation, consumes lot of energy, production process is wayward, facility investment is big, and output is little, therefore is difficult to amplify the technology as producing usefulness in enormous quantities.Chemical Vapor deposition process has that method is simple, the production process of carbon nanotube is controlled, facility investment is low and be easy to scale production, therefore is the main method of producing carbon nanotube in batches.The technology of serialization at present, mass preparation carbon nanotube is more, as fixed-bed catalytic cracking technology, ebullated bed Deep Catalytic Cracking process, continuous carbon nano-tube preparation by rotary moving-bed reactor.
The controlledly synthesis of high quality carbon nanotube is the basis of carbon nanotube performance study and application.As mentioned above, existing equipment and technology can realize the suitability for industrialized production of carbon nanotube.Yet there is the bigger and more defective of diameter Distribution in the carbon nanotube of existing prepared, has limited the research of carbon nanotube fundamental property, more is difficult to reach application requiring.
Summary of the invention
Deficiency at the prior art existence, the invention provides a kind of diameter that can control the carbon nanotube of chemical Vapor deposition process preparation, the carbon nanotube of growing high-quality, and designed a kind of semicontinuous batch process device, improve preparation technology, produce the preparation method and the production unit thereof of the carbon nanotube of controllable diameter in batches.
For achieving the above object, preparation method of the present invention is: the bimetal of employing adjustable proportion is logical makes catalyzer, and its carrier is a magnesium oxide; Add carbon compound then; Heating; Mix with reactant gases; Cooling; Described bimetal is an iron and the mixing of molybdenum or nickel and molybdenum, and the ratio of described iron and molybdenum or nickel and molybdenum is 1: 0-3, and the per-cent that iron or nickel account for total amount of substance is 1.8%-9%.
Wherein, carbon compound is a methane, and the volume percent that methane accounts for total gas is 25-56%, and Heating temperature is 800-1000 ℃, and the time is 15-45 minute, and reactant gases is made up of methane and diluent gas, and flow rate of reactive gas is 1800-3000sccm.Diluent gas is the mixed gas of hydrogen or hydrogen and nitrogen.
Catalyzer makes by combustion method.The Preparation of catalysts process: at first nitrate and the ammonium molybdate with iron or nickel is dissolved in the distilled water, evaporating solvent is to spumescence, stop heating, then it is carried out drying, drying temperature is 130 ℃, removes the intravital crystal water of crystallization, blast back collection powder heats up, it is carried out sintering, and sintering temperature is 450 ℃-550 ℃, and the time is 0.5-1.5 hour.
Above-mentioned preparation method can come the controlling carbon nanotube diameter by bimetallic ratio in the adjusting catalyzer, wherein, when adopting iron and molybdenum or nickel and molybdenum, along with the increase of molybdenum content as bimetallic catalyst, the diameter of carbon nanotubes grown can increase gradually, and the output of carbon nanotube also improves thereupon; This preparation method is simple, handled easily.Adopting magnesium oxide is because magnesium oxide is easily removed in product purification as carrier.
Production unit of the present invention is: the reaction unit and the sample collection device that include the catalyzer sampling device, are connected with the catalyzer sampling device.
Wherein, sample collection device, reaction unit and catalyzer sampling device are vertical arrangement.The catalyzer sampling device includes tank body and opening for feed, described collection device is an accumulator tanks, described reaction unit be located between tank body and the accumulator tanks, its two ends respectively with the conduit of tank body and accumulator tanks conducting, this conduit includes preheating reduction zone and heating zone, described preheating reduction zone is near the tank body setting, the heating zone is near the accumulator tanks setting, and place, preheating reduction zone is provided with air inlet/outlet.
Adopt this equipment, can implement the carbon nanotube of semicontinuous batch and batch process controllable diameter, make the high quality carbon nanotube realize suitability for industrialized production, improved the output of carbon nanotube.
Below in conjunction with accompanying drawing the present invention is further described:
Description of drawings
Fig. 1 is iron in the embodiment of the invention: the molybdenum mol ratio is the microscope figure of unpurified carbon nanotube of 1: 1 bimetallic catalyst preparation;
Fig. 2 is iron in the embodiment of the invention: the molybdenum mol ratio is the high power transmission electron microscope figure of unpurified carbon nanotube of 1: 1 bimetallic catalyst preparation;
Fig. 3 is iron in the embodiment of the invention: the molybdenum mol ratio is the Raman spectrogram of unpurified carbon nanotube of 1: 1 bimetallic catalyst preparation;
Fig. 4 is along with increase, the number of plies of carbon nanotube and the numerical tabular of vary in diameter of molybdenum content in the bimetallic catalyst in the embodiment of the invention.
Fig. 5 is the structural representation of production unit in the embodiment of the invention.
Embodiment
As Fig. 1, Fig. 2, Fig. 3, shown in Figure 4, preparation method of the present invention is: adopt the bimetal of adjustable proportion to make catalyzer, its carrier is a magnesium oxide; Under temperature of reaction, feed carbon compound; The chemical vapour deposition postcooling; Described bimetal is an iron and the mixing of molybdenum or nickel and molybdenum, and the ratio of described iron and molybdenum or nickel and molybdenum is 1: 0-3, and iron to account for total material per-cent that rubs be 1.8%-9%.Carbon compound is a methane, the volume percent that methane accounts for total gas is 25-56%, Heating temperature is 800-1000 ℃, time is 15-45 minute, reactant gases is made up of methane and diluent gas, diluent gas is hydrogen or hydrogen and the mixing of nitrogen, and flow rate of reactive gas is 1800-3000sccm.
Catalyzer makes by burning, its making processes is as follows: be dissolved in the nitrate and the ammonium molybdate of iron or nickel metal in the distilled water fully, evaporating solvent stops heating to spumescence, then it is carried out drying, drying temperature is 130 ℃, remove the intravital crystal water of crystallization, the intensification after-explosion is collected powder and then it is carried out sintering, sintering temperature is 450 ℃-550 ℃, and the time is 0.5-1.5 hour.
Production unit of the present invention includes catalyzer sampling device 1, the reaction unit 2 that is connected with catalyzer sampling device 1 and sample collection device 3.Described sample collection device 3, reaction unit 2 and catalyzer sampling device 1 are vertical arrangement; Catalyzer sampling device 1 includes tank body 11 and opening for feed 12, described collection device 3 is an accumulator tanks 31, described reaction unit 2 for be located between tank body 11 and the accumulator tanks 31, its two ends respectively with the conduit 21 of tank body 11 and accumulator tanks 31 conductings, this conduit 21 includes preheating reduction zone 22 and heating zone 23, described preheating reduction zone 22 is provided with near tank body 11, heating zone 23 is provided with near accumulator tanks 31, and 22 places, preheating reduction zone are provided with air inlet/outlet 221.
In the embodiment of the invention 1, prepare catalyzer with combustion method.According to mol ratio is Fe: Mo: MgO=1: 1: 10 preparation a certain amount of iron nitrate, magnesium nitrate and ammonium molybdate aqueous solution, and adding citric acid and glycine, the heating evaporation solvent put it in the air dry oven before solvent soon evaporates, 130 ℃ of dryings 12 hours are removed crystal water.Behind dry the end, be heated, make it to blast.Collect the dust that explosion time generates, put into 550 ℃ of sintering of retort furnace 1 hour, promptly get and test used catalyst fines.
Need to prove that above-mentioned prescription also can also can prepare by in the horizontal pipe furnace, and catalyst fines is tiled in the quartz boat, puts into the silica tube central authorities of horizontal pipe furnace, airtight whole system.1000 ℃ of design temperatures begin heating, feed nitrogen purge gas simultaneously, and the flow of nitrogen is 500sccm.When temperature rises to 500 ℃, feed hydrogen, flow is 250sccm.When equitemperature arrives design temperature, close nitrogen, the flow of hydrogen is increased to 1500sccm, feed methane simultaneously, flow is 1000sccm.React after 30 minutes, close methane, stop heating.After 5 minutes, close hydrogen, feed the nitrogen cooling.
After the cooling, reaction product is taken out.The scanning electron microscope diagram sheet of unpurified carbon nanotube as shown in Figure 1, the high power transmission electron micrograph as shown in Figure 2, Raman spectrogram is as shown in Figure 3.The structure of carbon nanotube and the characterization result of pattern are shown the defective of the carbon nanotube of the present invention's preparation is few, the carbon nanotube tube wall is smooth.
In the embodiment of the invention 2, prepare catalyzer with combustion method.According to mol ratio is Ni: Mo: MgO=1: 1: 10 preparation a certain amount of nickelous nitrate, magnesium nitrate and ammonium molybdate aqueous solution, and adding citric acid and glycine, the heating evaporation solvent put it in the air dry oven before solvent soon evaporates, 130 ℃ of dryings 12 hours are removed crystal water.Behind dry the end, be heated, make it to blast.Collect the dust that explosion time generates, put into 450 ℃ of sintering of retort furnace 1.5 hours, promptly get and test used catalyst fines.
The preparation of employing horizontal pipe furnace is tiled in catalyst fines in the quartz boat, puts into the silica tube central authorities of horizontal pipe furnace, airtight whole system.800 ℃ of design temperatures begin heating, feed nitrogen purge gas simultaneously, and the flow of nitrogen is 500sccm.When temperature rises to 500 ℃, feed hydrogen, flow is 250sccm.When equitemperature arrives design temperature, close nitrogen, the flow of hydrogen is increased to 2000sccm, feed methane simultaneously, flow is 1000sccm.React after 30 minutes, close methane, stop heating.After 5 minutes, close hydrogen, feed the nitrogen cooling.
In the embodiment of the invention 3, adopt the vertical tubular furnace preparation, catalyst fines is put into vertical continuous production equipment of the present invention, promptly shown in Figure 5.Airtight whole reaction system is with the air in the nitrogen heat-extraction system.Design temperature is 1000 ℃, and heating rate is less than 15 ℃/min.After arriving design temperature, open the hydrogen valve, catalyst fines is brought in the stove by hydrogen.Simultaneously, feed methane.The flow of methane is 800sccm, and the total flux of hydrogen is 1000sccm.
Reaction is closed methane and hydrogen after finishing.System is cooled off under nitrogen atmosphere.After the cooling, take out carbon nanotube.The tube wall of carbon nanotube and diameter are with the ratio of two kinds of metals in the catalyzer not
Change together.As shown in Figure 4, under the certain situation of Fe content, along with the increase of Mo content, the tube wall of carbon nanotube and diameter also increase thereupon.
Claims (8)
1. the preparation method of a controllable growth carbon nanotube is characterized in that: adopt bimetal to make catalyzer, its carrier is a magnesium oxide; Under preparation temperature, feed carbon compound; The chemical vapour deposition postcooling; Described bimetal is iron and molybdenum or nickel and molybdenum, and the ratio of described iron and molybdenum or nickel and molybdenum is 1: 0-3, and the per-cent that iron or nickel account for total amount of substance is 1.8%-9%.
2. the preparation method of controllable growth carbon nanotube according to claim 1, it is characterized in that: described carbon compound is a methane, the volume percent that methane accounts for reactant gases is 25-56%, preparation temperature is 800-1000 ℃, time is 15-45 minute, reactant gases is made up of methane and diluent gas, and the total flux of reactant gases is 1800-3000sccm.
3. the preparation method of controllable growth carbon nanotube according to claim 2 is characterized in that: described diluent gas is the mixed gas of hydrogen or hydrogen and nitrogen.
4. the preparation method of controllable growth carbon nanotube according to claim 1 is characterized in that: described catalyzer makes by combustion method.
5. the preparation method of controllable growth carbon nanotube according to claim 3, it is characterized in that: the nitrate and the ammonium molybdate of metallic iron or nickel are dissolved in the distilled water, evaporating solvent stops heating to spumescence, then it is carried out drying, drying temperature is 130 ℃, remove the intravital crystal water of crystallization, the blast that heats up is then collected powder it is carried out sintering, sintering temperature is 450 ℃-550 ℃, and the time is 0.5-1.5 hour.
6. the production unit of above-mentioned controllable growth carbon nanotube: the reaction unit and the sample collection device that include the catalyzer sampling device, are connected with the catalyzer sampling device.
7. the production unit of controllable growth carbon nanotube according to claim 6 is characterized in that: described sample collection device, reaction unit and catalyzer sampling device are vertical arrangement.
8. according to the production unit of claim 6 or 7 described controllable growth carbon nanotubes, it is characterized in that: described catalyzer sampling device includes tank body and opening for feed, described collection device is an accumulator tanks, described reaction unit be located between tank body and the accumulator tanks, its two ends respectively with the conduit of tank body and accumulator tanks conducting, this conduit includes preheating reduction zone and heating zone, described preheating reduction zone is near the tank body setting, the heating zone is near the accumulator tanks setting, and place, preheating reduction zone is provided with air inlet/outlet.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395774A (en) * | 2013-07-24 | 2013-11-20 | 中国石油大学(北京) | Reaction device and method for producing graphene or carbon nanotubes |
| CN109351359A (en) * | 2018-10-18 | 2019-02-19 | 吉林师范大学 | It is a kind of using carbon nanotube as the preparation method of the more metal carbides of Material synthesis |
| CN109678138A (en) * | 2019-01-09 | 2019-04-26 | 温州大学 | A kind of preparation method of unidextrality single-walled carbon nanotube |
| CN110028055A (en) * | 2019-04-11 | 2019-07-19 | 温州大学 | A method of semi-conductive single-walled carbon nanotubes are prepared based on methylation modification |
| CN110961115A (en) * | 2019-11-26 | 2020-04-07 | 厦门大学 | Catalyst for preparing multi-walled carbon nanotube and preparation method and application thereof |
| CN111799448A (en) * | 2019-04-08 | 2020-10-20 | 江苏天奈科技股份有限公司 | Method for growing carbon nano-tube in situ by silicon or oxide thereof |
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2009
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395774A (en) * | 2013-07-24 | 2013-11-20 | 中国石油大学(北京) | Reaction device and method for producing graphene or carbon nanotubes |
| CN103395774B (en) * | 2013-07-24 | 2015-05-27 | 中国石油大学(北京) | Reaction device and method for producing graphene or carbon nanotubes |
| CN109351359A (en) * | 2018-10-18 | 2019-02-19 | 吉林师范大学 | It is a kind of using carbon nanotube as the preparation method of the more metal carbides of Material synthesis |
| CN109678138A (en) * | 2019-01-09 | 2019-04-26 | 温州大学 | A kind of preparation method of unidextrality single-walled carbon nanotube |
| CN109678138B (en) * | 2019-01-09 | 2022-04-26 | 温州大学 | Preparation method of single-chiral single-walled carbon nanotube |
| CN111799448A (en) * | 2019-04-08 | 2020-10-20 | 江苏天奈科技股份有限公司 | Method for growing carbon nano-tube in situ by silicon or oxide thereof |
| CN110028055A (en) * | 2019-04-11 | 2019-07-19 | 温州大学 | A method of semi-conductive single-walled carbon nanotubes are prepared based on methylation modification |
| CN110961115A (en) * | 2019-11-26 | 2020-04-07 | 厦门大学 | Catalyst for preparing multi-walled carbon nanotube and preparation method and application thereof |
| CN110961115B (en) * | 2019-11-26 | 2022-03-29 | 厦门大学 | Catalyst for preparing multi-walled carbon nanotube and preparation method and application thereof |
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Application publication date: 20110601 |