CN102515140A - Method for large-scale preparation for nitrogen-doped carbon nanotube aligned array - Google Patents
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Abstract
A method for large-scale preparation for a nitrogen-doped carbon nanotube aligned array is disclosed, which comprises the following steps of: using high-density catalyst particles with a micro flat surface structure, for example, sheet-shaped particles, laminar particles, spherical particles and the like; and charging a carbon source and a nitrogen source at a high temperature to form a nitrogen-doped carbon nanotube aligned array with an aligned arrangement on the catalyst. Compared with traditional preparation technology, the method enhances the utilization of the specific surface area of growth matrix, and reactors suitable for batch preparation such as fluidized bed and moving bed can also be used for perform large-scale preparation; and the process operation of the method is relatively simple and easy to perform continuous operation, so that the problem of low efficiency brought by the utilization of large-area planar substrate during traditional preparation process for nitrogen-doped carbon nanotube aligned array is solved, and propulsion on batch preparation and large-scale application for nitrogen-doped carbon nanotube aligned array is contributed.
Description
Invention field
The present invention relates to a kind of extraordinary preparation method of carbon nano-tube, relate in particular to a kind of method of mass preparation nitrogen-doped carbon nanometer pipe directional array.
Background technology
Transmission electron microscope high resolution structure (Iijima S.Nature, 1991 of Iijima reported first carbon nanotube in 1991; 364:56), because it is at mechanics, optics, numerous areas such as electricity all have excellent properties, have caused many scientists and engineers' extensive concern.The preparation of carbon nano-tube oriented array and application are also shown great attention to, and can on particle, carry out batch preparations (Wei Fei etc., publication number: CN101073934 through reactor types such as fluidized-beds at present; Wei Fei etc., publication number: CN101348249).Nitrogen-doped carbon nanometer pipe is one type of extraordinary carbon nanotube, with nitrogen-atoms introduce in the carbon nanotube can the modulation carbon nanotube structure and surface property, thereby make inert carbon nanotube tube wall present certain chemically reactive.At present, the nitrogen doped carbon nanotubes is comprising electrochemical reaction, and numerous areas such as catalysis all have wide practical use.For instance, realizational portion fake capacitance performance when nitrogen-doped carbon nanometer pipe is used as electrode material for super capacitor, performance is much better than pure nano-carbon tube; It can directly be used for hydrogen reduction (Chen Z, et al.Carbon, 2010 as catalyzer; 48:3057), dehydration (Amadou A, et al.Catalysis Today, 2008; 138:62) wait in the reaction; It also can be used as the good metal support of the catalyst and is used for ammonia and decomposes that (Chen JL, et al.Chemical Engineering Journal 2010:156:404) wait in the reaction.Irregular alignment gathers a nitrogen-doped carbon nanometer pipe in many cases owing to reasons such as diffusion can't be given full play to performance then; In this case; The directional array of nitrogen-doped carbon nanometer pipe has combined characteristics such as performance and directional array length homogeneous, the pore distribution of nitrogen-doped carbon nanometer pipe be even, can bring into play better properties.As in feds (Ghosh K, et al.Carbon, 2010; 48:191), fuel cell (Gong KP, et al.Science, 2009; 323:760), the nitrogen-doped carbon nanometer pipe directional array all embodies excellent performance.But the most important prerequisite that realizes these concrete applicable industryization is exactly controlled low-cost batch preparation nitrogen-doped carbon nanometer pipe directional array.
Up to now, the main preparation means of nitrogen-doped carbon nanometer pipe is for gathering a nitrogen-doped carbon nanometer pipe (Shalagina AE, et al.Carbon, 2007 based on fine catalyst; 45:1808; A. Wolf etc., publication number: CN101903289A).The preparation of nitrogen-doped carbon nanometer pipe directional array utilizes fixed-bed reactor to realize (He MS, etal.The Journal of Physical Chemistry B, 2005 mainly on some planar substrates (like silicon chip, quartz plate etc.) surface; 109:9275).Because the output of nitrogen-doped carbon nanometer pipe directional array is directly proportional with the surface-area of growth substrate; And adopt the fixed-bed reactor space availability ratio of plate shape substrates lower; Nitrogen-doped carbon nanometer pipe directional array preparation efficiency is extremely low under the preparation condition at present, has limited its concrete application as the advanced function material.
This shows; If can overcome the low problem of present nitrogen-doped carbon nanometer pipe directional array preparation efficiency; Develop a kind of method of mass preparation nitrogen-doped carbon nanometer pipe directional array; And reduce the cost of preparation process through the engineering means, can effectively promote the supply of nitrogen-doped carbon nanometer pipe directional array and follow-up concrete application, thereby solution is provided for material based on the functionalized application of this kind material.
Summary of the invention
The objective of the invention is to overcome present nitrogen-doped carbon nanometer pipe directional array and prepare and utilize planar substrates in the process, the problem that preparation cost is high, production efficiency is low.Utilize particulate bigger serface characteristics, realize the efficient production and the extensive supply of nitrogen-doped carbon nanometer pipe directional array.
The present invention provides a kind of method of mass preparation nitrogen-doped carbon nanometer pipe directional array, and this method may further comprise the steps:
1) adopts and to contain particle that the surface curvature radius is not less than 500 nanometers, active constituent loading to the particulate surfaces externally and internally, is put into reactor drum with catalyzer then as support of the catalyst; Said active ingredient is molysite, nickel salt, cobalt salt or their mixture;
2) in the reactor drum of nitrogen-doped carbon nanometer pipe directional array growth; Feed the mixed gas of carbon source, nitrogenous source, hydrogen and carrier gas; Temperature of reaction is 500-1000 ℃; Gas speed is the 0.005-2 meter per second, and the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1 in the mixed gas: 0.01-100: 0-5: 0.1-30, and said carbon source is one or more the mixed gas in the following low-carbon (LC) hydro carbons of carbon monoxide and eight carbon; Said nitrogenous source is the mixed gas of ammonia and one or more in the nitrogenous hydro carbons below eight carbon; Obtain the nitrogen-doped carbon nanometer pipe directional array.
The exterior appearance of said support of the catalyst is: spherical particle, cylindrical particle or lamella stacked particle.
Said step 2) air speed of reaction process is 5-10000 hour in
-1, bed density remains on the 10-1500 kilograms per cubic meter in the reactor drum.
Said reactor drum adopts fixed bed, fluidized-bed, moving-bed, rotary drum reactor drum or their unitized construction.
Another technical scheme of the present invention may further comprise the steps:
1) adopts and to contain particle that the surface curvature radius is not less than 500 nanometers, catalyzer is put into reactor drum as support of the catalyst;
2) metallocene or carbonyl metallic compound are dissolved in the lower carbon number hydrocarbons kind solvent, make compound dissolution; This solution is heated to more than the boiling point of varsol and metallic compound, makes vaporizer; Varsol adopts the nonnitrogenous varsol of five carbon to two, ten carbon or is the nitrogenous varsols of two carbon to two, ten carbon, and this varsol partly or entirely serves as carbon source, or carbon source and nitrogenous source;
3) the metallic compound solvent after will gasifying feeds in the reactor drum, and catalyst precursor and part carbon source or nitrogenous source are provided, and temperature of reaction is 500-1000 ℃; Feed the mixed gas of hydrogen and carrier gas simultaneously, or feed the mixed gas of hydrogen, carrier gas, carbon-source gas and nitrogen source gas; The mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.01-100: 0-5: 0.1-30, carbon-source gas are one or more the mixed gas in the following low-carbon (LC) hydro carbons of carbon monoxide and eight carbon; Nitrogenous source is the mixed gas of ammonia and one or more in the nitrogenous hydro carbons below eight carbon; Obtain the nitrogen-doped carbon nanometer pipe directional array.
The exterior appearance of said support of the catalyst is: spherical particle, cylindrical particle or lamella stacked particle.
Said metallocene or carbonyl metallic compound comprise: the mixture of one or more in ferrocene, nickelocene, dicyclopentadienylcobalt, iron carbonyl, nickle carbonoxide and the cobalt-carbonyl.
The air speed of reaction process is 5-10000 hour in the said step 3)
-1, bed density remains on the 10-1500 kilograms per cubic meter in the reactor drum.
Said reactor drum adopts fixed bed, fluidized-bed, moving-bed, rotary drum reactor drum or their unitized construction.
The present invention compares prior art; Have following advantage and high-lighting effect: the present invention adopts the particle have greater than 500 nanometer radius-of-curvature surface as support of the catalyst; In growth atmosphere, introduce nitrogenous source simultaneously, successfully realized the preparation of particle surface nitrogen-doped carbon nanometer pipe directional array.Compare traditional technology of preparing; Promptly improved the use of growing substrate specific surface area; Simultaneously also can adopt fluidized-bed, the reactor drum of suitable batch preparations such as moving-bed carries out scale preparation, and this technological operation is simple relatively and be prone to carry out continuous operation; Solve traditional nitrogen-doped carbon nanometer pipe directional array and prepared the low efficiency problem of using the large-area planar substrate to bring in the process, helped to advance the batch preparations of nitrogen-doped carbon nanometer pipe directional array and mass-producing to use.
Description of drawings
Fig. 1 vermiculite particulate scan electron micrograph, this particle is made up of laminar structured, and the surface that is used for the growth of nitrogen-doped carbon nanometer pipe directional array in a large number can be provided.
The nitrogen-doped carbon nanometer pipe directional array electron scanning micrograph of growing on Fig. 2 vermiculite particle, this directional array is in the laminated structure growth inside, and length is about 20 microns.Expand the interlayer spacing of vermiculite granule in the process of growth, made full use of growth surface.
Transmission electron microscope photo after the typical nitrogen-doped carbon nanometer pipe directional array of Fig. 3 disperses, this nano tube structure embodies the constitutional features of typical ring shape nitrogen-doped carbon nanometer pipe.
The electron scanning micrograph of the irregular quartz particles of Fig. 4, this particle size have the microcosmic flat surface of a large amount of curvature more than 500 nanometers in the millimeter level.
The electron scanning micrograph of the epontic nitrogen-doped carbon nanometer pipe directional array of the irregular quartz particles of Fig. 5, this directional array length is about 100 microns.
The photo of the epontic nitrogen-doped carbon nanometer pipe directional array of Fig. 6 diameter 1 millimeter Ceramic Balls.
Embodiment:
Employing contains particle that the surface curvature radius is not less than 500 nanometers as support of the catalyst, and active constituent loading to the particulate surfaces externally and internally, is put into reactor drum with catalyzer then; In reactor drum; Feed the mixed gas of carbon source, nitrogenous source, hydrogen and carrier gas; Temperature of reaction is 500-1000 ℃, and gas speed is the 0.005-2 meter per second, and the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1 in the mixed gas: 0.01-100: 0-5: 0.1-30;
Said active ingredient is molysite, nickel salt, cobalt salt or their mixture; Said carbon source is one or more the mixed gas in the following low-carbon (LC) hydro carbons of carbon monoxide and eight carbon; Said nitrogenous source is the mixed gas of ammonia and one or more in the nitrogenous hydro carbons below eight carbon; The exterior appearance of said support of the catalyst is: spherical particle, cylindrical particle or lamella stacked particle; The air speed of reaction process is 5-10000 hour, and bed density remains on the 10-1500 kilograms per cubic meter in the reactor drum; Said reactor drum adopts fixed bed, fluidized-bed, moving-bed, rotary drum reactor drum or their unitized construction.
Another technical scheme of the present invention is following:
Employing contains particle that the surface curvature radius is not less than 500 nanometers as support of the catalyst, and catalyzer is put into reactor drum; Metallocene or carbonyl metallic compound are dissolved in the lower carbon number hydrocarbons kind solvent, make compound dissolution; This solution is heated to more than the boiling point of varsol and metallic compound, makes vaporizer; Metallic compound solvent after the gasification is fed in the reactor drum, catalyst precursor and part carbon source or nitrogenous source are provided, temperature of reaction is 500-1000 ℃; Feed the mixed gas of hydrogen and carrier gas simultaneously, or feed the mixed gas of hydrogen, carrier gas, carbon-source gas and nitrogen source gas; The mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.01-100: 0-5: 0.1-30;
Said varsol adopts the nonnitrogenous varsol of five carbon to two, ten carbon or is the nitrogenous varsols of two carbon to two, ten carbon, and this varsol partly or entirely serves as carbon source, or carbon source and nitrogenous source; Said carbon-source gas is one or more the mixed gas in the following low-carbon (LC) hydro carbons of carbon monoxide and eight carbon; Nitrogenous source is the mixed gas of ammonia and one or more in the nitrogenous hydro carbons below eight carbon; Obtain the nitrogen-doped carbon nanometer pipe directional array; The exterior appearance of said support of the catalyst is: spherical particle, cylindrical particle or lamella stacked particle; Said metallocene or carbonyl metallic compound comprise: the mixture of one or more in ferrocene, nickelocene, dicyclopentadienylcobalt, iron carbonyl, nickle carbonoxide and the cobalt-carbonyl; The air speed of said reaction process is 5-10000 hour
-1, bed density remains on the 10-1500 kilograms per cubic meter in the reactor drum; Said reactor drum adopts fixed bed, fluidized-bed, moving-bed, rotary drum reactor drum or their unitized construction.
Come the present invention is further described through several specific embodiments below:
Embodiment 1:
Adopt vermiculite as support of the catalyst, vermiculite is a kind of natural lamellar aluminosilicate compound, and range upon range of vermiculite in flake comprises tens thousand of planes lamella each other, shown in accompanying drawing 1.Adopt the Fe/Mo system as the activity of such catalysts component, adopt the solution impregnation vermiculite catalyst carrier of iron nitrate and ammonium molybdate, obtain nitrogen-doped carbon nanometer pipe directional array growth catalyst.Granules of catalyst is sent in the fluidized-bed reactor, under 700 ℃ of temperature of reaction, fed the mixed gas of ethene, ammonia, hydrogen, argon gas, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.5: 2: 5.The air speed of reaction process is 200 hours-1, and the void tower flow velocity of gas is 0.1 meter per second, and bed density is 200 kilograms per cubic meter.The nitrogen-doped carbon nanometer pipe directional array is grown in the sheet interlayer of vermiculite with the form of intercalation, shown in accompanying drawing 2.Accompanying drawing 3 is the transmission electron microscope photo of above-mentioned sample, from figure, can find out the typical bamboo knot shaped structure of nitrogen-doped carbon nanometer pipe.
Embodiment 2:
Employing has irregular quartz particles that radius-of-curvature is about 500 Nanosurfaces as support of the catalyst (shown in accompanying drawing 4), and the solution that utilizes nickelous nitrate obtains nitrogen-doped carbon nanometer pipe directional array growth catalyst as this support of the catalyst of activity component impregnation.Catalyzer is put into the vertical fixing bed bioreactor, under 500 ℃ temperature of reaction, feed the mixed gas of acetylene, quadrol, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, carrier gas molecules is 1: 0.01: 0.1.Air speed in the reaction process is 5 hours
-1, the void tower flow velocity of gas is 0.005 meter per second, bed density is 1500 kilograms per cubic meter.The nitrogen-doped carbon nanometer pipe directional array is grown on the outside surface of quartz particles (shown in accompanying drawing 5).
Embodiment 3:
Employing has wollastonite elongated piece that radius-of-curvature is about 10 microns surfaces as support of the catalyst, and the solution that utilizes NSC 51149 obtains nitrogen-doped carbon nanometer pipe directional array growth catalyst as this support of the catalyst of activity component impregnation.Catalyzer is put into moving-burden bed reactor, under 600 ℃ temperature of reaction, feed the mixed gas of propylene, diethylamine, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.1: 0.1: 5.Air speed in the reaction process is 20 hours
-1, the void tower flow velocity of gas is 0.01 meter per second, bed density is 1200 kilograms per cubic meter.Growth obtains the structure that the nitrogen-doped carbon nanometer pipe directional array is grown in wollastonite particle outside surface.
Embodiment 4:
The employing radius-of-curvature is about 0.5 millimeter ceramic spherical particle as support of the catalyst, utilizes NSC 51149 and iron nitrate mixing salt solution as this support of the catalyst of activity component impregnation, obtains nitrogen-doped carbon nanometer pipe directional array growth catalyst.Catalyzer is put into rotary drum, under 800 ℃ temperature of reaction, feed the mixed gas of hexanaphthene, pyridine and ammonia, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 1: 0.5: 1.Air speed in the reaction process is 100 hours
-1, the void tower flow velocity of gas is 0.01 meter per second, bed density is 1000 kilograms per cubic meter.Growth obtains the structure that the nitrogen-doped carbon nanometer pipe directional array is distributed in the particle outside surface, and length is about 100 microns (accompanying drawings 6).
Embodiment 5:
Adopt radius-of-curvature to be about 2 millimeters the directly substrate of conduct growth of hollow aluminium sesquioxide ball, particle is put into the horizontal fixed bed bioreactor.Ferrocene is dissolved in the solution that obtains in the YLENE as catalyst precursor; Under 850 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of pentamethylene, ammonia and quadrol mixed gas, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 100: 5: 30.Air speed in the reaction process is 500 hours
-1, the void tower flow velocity of gas is 0.05 meter per second, bed density is 800 kilograms per cubic meter.Growth obtains the nitrogen-doped carbon nanometer pipe directional array and is distributed in hollow ball particulate surfaces externally and internally.
Embodiment 6:
Adopt granularity to be about 60 microns, have the bigger vermiculite granule of laminate structure and lamella radius-of-curvature, particle is put into fluidized-bed reactor directly as the substrate of growth.Dicyclopentadienylcobalt is dissolved in 18 tertiary amines after the heating as catalyst precursor and carbon source, nitrogenous source; Under 850 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of ammonia and quadrol mixed gas, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 3: 1: 5.Air speed in the reaction process is 1000 hours
-1, the void tower flow velocity of gas is 0.05 meter per second, bed density is 300 kilograms per cubic meter.Growth obtains the nitrogen-doped carbon nanometer pipe directional array and is distributed in the structure of vermiculite in flake between layer by layer.
Embodiment 7:
Employing has radius-of-curvature and is about the surperficial preparing spherical SiO 2 particle of 10-50 micron as growth substrate, and particle is put into the vertical fixing bed bioreactor.Iron carbonyl is dissolved in the mixing solutions of toluene and pyridine as catalyst precursor and carbon source, nitrogenous source; Under 900 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 1: 2: 5.Air speed in the reaction process is 10000 hours
-1, the void tower flow velocity of gas is 2 meter per seconds, bed density is 500 kilograms per cubic meter.Growth obtains the nitrogen-doped carbon nanometer pipe directional array and is distributed in the spherical surface.
Embodiment 8:
The employing radius-of-curvature is about 0.5 millimeter ceramic spherical particle as growth substrate, and particle is put into vertical reactor.Ferrocene and nickle carbonoxide mixture are dissolved in the diethylamine as catalyst precursor and carbon source, nitrogenous source; Under 1000 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of octylame, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 1: 3: 10.Air speed in the reaction process is 5000 hours
-1, the void tower flow velocity of gas is 1 meter per second, bed density is double centner/cubic meter.Growth obtains the surface that the nitrogen-doped carbon nanometer pipe directional array is distributed in spherical ceramic particles.
Embodiment 9:
Adopt granularity to be about 60 microns, the directly substrate of conduct growth of vermiculite particle that the laminate structure radius-of-curvature is bigger is put into fluidized-bed with particle.Nickle carbonoxide is dissolved in the pentamethylene as catalyst precursor and carbon source; Under 950 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of diethylamine, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.3: 2: 5.Air speed in the reaction process is 2000 hours
-1, the void tower flow velocity of gas is 0.5 meter per second, bed density is 50 kilograms per cubic meter.The particle of one-step growth acquisition just is blown in the rotary drum reactor drum; Under 750 ℃ temperature of reaction, feed the mixed gas of ethylene butene mixed gas, diethylamine, hydrogen and argon gas; Carry out diauxic growth; The mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.1: 2: 5, and empty tower gas velocity is 1.5 meter per seconds, bed density is 10 kilograms per cubic meter.The nitrogen-doped carbon nanometer pipe directional array intercalation shape that growth obtains grows in the vermiculite granule interlayer.
Embodiment 10:
The employing radius-of-curvature is about 10 microns wollastonite elongated piece as growth substrate, and particle is put into fixed-bed reactor.Adopt cobalt-carbonyl to be dissolved in solution in the eicosane as catalyst precursor and carbon source; Under 950 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of ammonia, hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 50: 4: 20.Air speed in the reaction process is 50 hours
-1, the void tower flow velocity of gas is 0.3 meter per second, bed density is 700 kilograms per cubic meter.The nitrogen-doped carbon nanometer pipe directional array that obtains is grown in acicular wollastonite particle outside surface.
Embodiment 11:
Adopt about 500 microns of granularities, have irregular quartz particles that radius-of-curvature is about 500 Nanosurfaces, particle is put into moving-burden bed reactor as growth substrate.Adopt nickelocene to be dissolved in solution in the quadrol as catalyst precursor and carbon source, nitrogenous source; Under 750 ℃ temperature of reaction, feed catalyst precursor; And feeding the mixed gas of hydrogen, nitrogen, the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 1: 2: 5.Air speed in the reaction process is 500 hours
-1, the void tower flow velocity of gas is 0.8 meter per second, bed density is 80 kilograms per cubic meter.The nitrogen-doped carbon nanometer pipe directional array that obtains is grown in irregular quartz particles outside surface.
Claims (9)
1. the method for a mass preparation nitrogen-doped carbon nanometer pipe directional array is characterized in that this method comprises the following steps:
1) adopts and to contain particle that the surface curvature radius is not less than 500 nanometers, active constituent loading to the particulate surfaces externally and internally, is put into reactor drum with catalyzer then as support of the catalyst; Said active ingredient is molysite, nickel salt, cobalt salt or their mixture;
2) in the reactor drum of nitrogen-doped carbon nanometer pipe directional array growth; Feed the mixed gas of carbon source, nitrogenous source, hydrogen and carrier gas; Temperature of reaction is 500-1000 ℃; Gas speed is the 0.005-2 meter per second, and the mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1 in the mixed gas: 0.01-100: 0-5: 0.1-30, and said carbon source is one or more the mixed gas in the following low-carbon (LC) hydro carbons of carbon monoxide and eight carbon; Said nitrogenous source is the mixed gas of ammonia and one or more in the nitrogenous hydro carbons below eight carbon; Obtain the nitrogen-doped carbon nanometer pipe directional array.
2. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 1 directional array, it is characterized in that: the exterior appearance of said support of the catalyst is: spherical particle, cylindrical particle or lamella stacked particle.
3. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 1 directional array, it is characterized in that: step 2) in the air speed of reaction process be 5-10000 hour
-1, bed density remains on the 10-1500 kilograms per cubic meter in the reactor drum.
4. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 1 directional array, it is characterized in that: reactor drum adopts fixed bed, fluidized-bed, moving-bed, rotary drum reactor drum or their unitized construction.
5. the method for a mass preparation nitrogen-doped carbon nanometer pipe directional array is characterized in that this method comprises following each step:
1) adopts and to contain particle that the surface curvature radius is not less than 500 nanometers, catalyzer is put into reactor drum as support of the catalyst;
2) metallocene or carbonyl metallic compound are dissolved in the lower carbon number hydrocarbons kind solvent, make compound dissolution; This solution is heated to more than the boiling point of varsol and metallic compound, makes vaporizer; Varsol adopts the nonnitrogenous varsol of five carbon to two, ten carbon or is the nitrogenous varsols of two carbon to two, ten carbon, and this varsol partly or entirely serves as carbon source, or carbon source and nitrogenous source;
3) the metallic compound solvent after will gasifying feeds in the reactor drum, and catalyst precursor and part carbon source or nitrogenous source are provided, and temperature of reaction is 500-1000 ℃; Feed the mixed gas of hydrogen and carrier gas simultaneously, or feed the mixed gas of hydrogen, carrier gas, carbon-source gas and nitrogen source gas; The mol ratio of carbon atom, nitrogen-atoms, hydrogen molecule, carrier gas molecules is 1: 0.01-100: 0-5: 0.1-30, carbon-source gas are one or more the mixed gas in the following low-carbon (LC) hydro carbons of carbon monoxide and eight carbon; Nitrogenous source is the mixed gas of ammonia and one or more in the nitrogenous hydro carbons below eight carbon; Obtain the nitrogen-doped carbon nanometer pipe directional array.
6. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 5 directional array, it is characterized in that: the exterior appearance of said support of the catalyst is: spherical particle, cylindrical particle or lamella stacked particle.
7. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 5 directional array, it is characterized in that: described metallocene or carbonyl metallic compound comprise: the mixture of one or more in ferrocene, nickelocene, dicyclopentadienylcobalt, iron carbonyl, nickle carbonoxide and the cobalt-carbonyl.
8. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 5 directional array, it is characterized in that: the air speed of reaction process is 5-10000 hour in the step 3)
-1, bed density remains on the 10-1500 kilograms per cubic meter in the reactor drum.
9. according to the method for the described mass preparation nitrogen-doped carbon nanometer pipe of claim 5 directional array, it is characterized in that: reactor drum adopts fixed bed, fluidized-bed, moving-bed, rotary drum reactor drum or their unitized construction.
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| CN103407982A (en) * | 2013-07-16 | 2013-11-27 | 清华大学 | Nitrogen-doped carbon nano-tube array and graphene hybrid and preparation method thereof |
| CN104944410A (en) * | 2015-06-01 | 2015-09-30 | 北京理工大学 | Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material |
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| 《物理化学学报》 20041130 朱素冰等 "以吡啶为原料制备氮掺杂碳纳米管!" 第1320-1323页 1-9 第20卷, 第11期 * |
| 朱素冰等: ""以吡啶为原料制备氮掺杂碳纳米管!"", 《物理化学学报》, vol. 20, no. 11, 30 November 2004 (2004-11-30), pages 1320 - 1323 * |
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