CN1344674A - Prepn of nano-carbon tube - Google Patents
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- CN1344674A CN1344674A CN 00124600 CN00124600A CN1344674A CN 1344674 A CN1344674 A CN 1344674A CN 00124600 CN00124600 CN 00124600 CN 00124600 A CN00124600 A CN 00124600A CN 1344674 A CN1344674 A CN 1344674A
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Abstract
By using the hydrogen reducing product of oxide of alloy storing hydrogen as catalyst, the present invention prepares nanometer carbon tube through catalytic cracking hydrocarbon, natural gas, coal gas, liquefied gas, CO or CO2. Alloy storing hydrogen is oxided in air or oxygen at 373-1073 K, the oxide product is hydrogen reduced at 573-1073 K for 10-60 min, then the reactant gas mixture of hydrocarbon methanol, acetylene, ethylene or benzene vapor and carrier gas hydrogen, argon or nitrogen is led in for reaction of 10-180 min at gas flow rate of 5-500 ml/hr. The present invention has simple operation, low cost and stable performance.
Description
The present invention relates to the preparation of carbon nanotube, particularly utilize the hydrogen reduction product of hydrogen storage alloy oxide compound to be catalyzer, hydrocarbon polymer or Sweet natural gas or and CO or CO
2Catalytic pyrolysis prepares carbon nanotube.
Carbon nanotube has caused the extensive concern of scientific circles owing to have unique physical and chemical performance, is expected to play a significant role in fields such as gas storage, nanoelectronics, strongthener science, chemistry.On the preparation method, mainly contain arc discharge method, chemical Vapor deposition process and laser evaporation method at present.Chemical Vapor deposition process prepares carbon nanotube, and technology is simple, low cost and other advantages is widely adopted owing to having, and wherein the Preparation of Catalyst of high dispersing is extremely important.In the patent that discloses or authorize, the catalyzer of preparation carbon nanotube mainly adopts chemical method with transition metal oxide such as NiO, and CoO, CuO etc. are dispersed in alkaline earth metal oxide such as MgO, CaO etc. or rare-earth oxide such as La
2O
3, CeO
2Deng (CN 1170631A); Also have and adopt sol-gel method nano grade transition metal to be distributed to the catalyzer (ZL 96120461.3) that has in the nanometer level microporous silica template as growing nano-tube; In the continuous growth carbon nanotube, also can adopt Fe, the organic compound of Ni or Co is as catalyst for reaction (CN1221048A); In adopting the alloy as catalyst agent method, granularity the Ni-Cu alloy (S.Motojima etc. about 10nm of employing through special processing are also arranged, Applied Physics Letters, 27 (1989) 315) or Ni-Fe alloy firm (X.H.Chen etc., ThinSolid Film 339 (1999) are 6.).There is the problem of cost, dispersiveness and productive rate invention in various degree in above-mentioned preparation method.
Purpose of the present invention aims to provide a kind of preparation method of new carbon nanotube, can overcome the deficiency of existing technology of preparing.The present invention utilizes the hydrogen storage alloy oxide compound to prepare carbon nanotube as the precursor of catalyzer, low cost, good dispersity, productive rate height.This carbon nanotube can be applicable to hydrogen source, nickel metal hydride battery, the purification of hydrogen, organic hydrogenation catalyst, strongthener, field emmision material, nano-probe of mass-producing accumulating, the fuel cell of hydrogen etc.
The present invention utilizes the hydrogen reduction product of hydrogen storage alloy oxide compound to be catalyzer.It is in conjunction with the iron in the hydrogen storage material or/and cobalt or and nickel or/and molybdenums etc. have high dispersing, form evenly in alloy, the preparation and the advantage of control easily easily, with after the hydrogen storing alloy powder oxidation as the preparation carbon nanotube the complex catalyst precursor thing, this forerunner's oxide compound the required nano level iron of carbon nano tube growth can be provided behind hydrogen reducing or/and cobalt or/and nickel or/and the catalytic site of molybdenum, metal catalyst be dispersed in simultaneously in the hydrogen storage alloy component rare earth metal or/and zirconium or/and titanium or/and on the oxide carrier of magnesium.The alloy material storing hydrogen preparation method can be by Metal Melting method, powder metallurgic method, mechanize alloyage, chemical reduction diffusion process and codeposition chemical reduction diffusion process etc.Hydrogen storage alloy can be the hydrogen storage alloy that reclaims.
Key step of the present invention is as follows: the preparation of carbon nanotube is carried out on fixed bed gas continuous flow reaction formula device.With granularity is 0.01-200 μ m hydrogen storing alloy powder in air or oxygen under 373-1073K oxidation 2-100 minute, the hydrogen storage alloy oxidation products (accounting for the 1-30% of carbon nanotube output) of metering is placed on the fixed bed gas continuous flow reaction formula device (tube type resistance furnace), under 573-1073K hydrogen reducing 5-120 minute, nickel in the alloyed oxide or/and cobalt or/and iron or/and molybdenum etc. be reduced into metallic state and be dispersed in the hydrogen storage alloy component rare earth metal or/and zirconium or/and titanium or/and in the oxide compound of magnesium, become the catalyzer of carbon nano tube growth.Under 573-1373K, feed reactant gases or with the mixed gas of carrier gas, reactant gases is hydrocarbon polymer, Sweet natural gas, gas maked coal, liquefied gas, CO or CO
2, carrier gas is hydrogen, argon gas, helium or nitrogen.Gas flow rate be the 5-500 milliliter/hour, the ratio of reactant gases and carrier gas is 1/0.1-1/20 in the mixed gas, the reaction times is 10-180 minute.
Hydrogen storage alloy of the present invention is that rare earth nickel system, zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually
2Type, nickel titante series or ferrotianium are AB type, Magnuminium A
2Any one or two kinds of above binary or the polynary hydrogen storage alloys of Type B or non-crystaline amorphous metal; Hydrogen storage alloy middle-weight rare earths nickel system alloy consists of LNi
N-x-y-zCo
xN
yM
z, L is norium, La, Ce, Nd, Pr, Y, N and M are respectively Mn, V, Cr, Al, Fe, Cu, Zn, Sn, Mo or Si, 3≤n≤6,0≤x≤2,0≤y≤2,0≤z≤2; Zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually
2The type alloy composition is KNi
A-b-c-dV
bG
cJ
d, K is Zr, Ti, Hf, norium, La, Ce, Nd, Pr or Y, G and J are respectively Co, Mn, Cr, Al, Fe, Cu, Zn, Sn, Mo or Si, 1.2≤a≤3.0,0≤b≤2,0≤c≤2,0≤d≤2; Nickel titante series or ferrotianium are that AB type alloy composition is HNi
M-k-jFe
kP
j, H is Zr, Hf, P is Co, Mn, V, Cr, Al, Cu, Zn, Sn, Mo or Si, 0.6≤m≤1.5,0≤k≤1.5,0≤j≤1; Magnuminium A
2The Type B alloy composition is Mg
G-fE
fNi
L-p-qCo
pT
q, E is Ca, Zr, Ti, Hf, norium, La, Ce, Nd, Pr or Y, T is Mn, V, Cr, Al, Fe, Cu, Zn, Sn, Mo or Si, 1.0≤g≤3.0,0≤f≤1.5,0≤p≤1.0,0≤q≤1.0.
The present invention combine have in the hydrogen storage material composition evenly, in the reduzate of the advantage of preparation and easily control easily and alloyed oxide iron or/and the advantage of metal catalyst high dispersing such as cobalt or/and nickel or/and molybdenum; The technology of preparing of a kind of novel carbon nanotube of fourth is provided, and its stable performance is widely used.
The invention will be further described below by example:
Embodiment 1
LaNi with electric arc furnace smelting
5Be crushed to 20 μ m-50 μ m, heat treated was handled after 20 minutes under the 773K in air, promptly got prepared alloyed oxide catalyst samples.Made of carbon nanotubes is to carry out on fixed bed gas continuous flow reaction formula device.150mg alloyed oxide catalyzer is warming up to the 873K reductase 12 after 0 minute under the hydrogen atmosphere, is feeding flow velocity 15ml/cm
2The methane of min and the mixed gas of argon gas react and stop after 30 minutes, are cooled to room temperature under nitrogen atmosphere, collect product, and carbon nanotube output is 2.5g.Fig. 1 is the TEM photo of the carbon nanotube of preparation.
Embodiment 2
LaNi with electric arc furnace smelting
4.5Fe
0.5Be crushed to 20 μ m-40 μ m, heat treated was handled after 30 minutes under the 723K in air, promptly got prepared alloyed oxide catalyst samples.Made of carbon nanotubes is to carry out on fixed bed gas continuous flow reaction formula device.200mg alloyed oxide catalyzer is warming up to the 873K reductase 12 after 0 minute under the hydrogen atmosphere, is feeding flow velocity 10ml/cm
2The methane of min and the mixed gas of argon gas, methane is 1 to 10 with the argon gas ratio, reacts to stop after 60 minutes, is cooled to room temperature under argon gas atmosphere, collects product, carbon nanotube output is 2.1g.
Embodiment 3
ZrV with electric arc furnace smelting
0.2Mn
0.4Co
0.3Ni
1.2Alloy powder is broken to 10 μ m-30 μ m, and 873K degree oxide treatment 50 minutes under oxygen atmosphere promptly gets prepared alloyed oxide catalyst samples then.Made of carbon nanotubes is carried out on fixed bed gas continuous flow reaction formula device.The 150mg catalyzer is warming up to 873K under hydrogen atmosphere, stablize 30 minutes after, feed flow velocity 15ml/cm again
2The acetylene of min, acetylene is 1 to 5 with nitrogen ratios, reacts to stop after 120 minutes, is cooled to room temperature under nitrogen atmosphere, collects product, carbon nanotube output is 1.0g.
Embodiment 4
LFe with electric arc furnace smelting
0.5Ni
1.5(L is a norium) alloy powder is broken to 20 μ m-40 μ m, and 773K degree oxide treatment 20 minutes under oxygen atmosphere promptly gets prepared alloyed oxide catalyst samples then.Made of carbon nanotubes is carried out on fixed bed gas continuous flow reaction formula device.The 120mg catalyzer is warming up to 893K under hydrogen atmosphere, stablize 20 minutes after, feed flow velocity 15ml/cm again
2The liquefied gas of min, liquefied gas is 1 to 15 with the argon gas ratio, reacts to stop after 110 minutes, is cooled to room temperature under argon gas atmosphere, collects product, carbon nanotube output is 1.0g.
Real in example 5
TiFe with the electric arc furnace smelting preparation
0.7Ni
0.3Alloy powder is broken to 40 μ m-60 μ m, and heat treated was handled after 40 minutes under the 823K in air, promptly got prepared alloyed oxide catalyst samples.The preparation of carbon nanotube is carried out on fixed bed gas continuous flow reaction motion device.150mg alloyed oxide catalyzer is warming up to 973K under hydrogen atmosphere, reduces after 30 minutes, feed flow velocity 25ml/cm
2The ethene of min reacts and stops after 90 minutes, at H
2Be cooled to room temperature under the atmosphere, collect product, carbon nanotube output is 0.8g.
Embodiment 6
By 2 to 1 mixed in molar ratio, ball milling promptly got prepared Mg in 70 hours under the argon gas atmosphere condition then with Mg and Ni powder
2Ni amorphous alloy catalyst sample, non-crystaline amorphous metal crystal grain are the 100-200 nanometer.Made of carbon nanotubes is carried out on fixed bed gas continuous flow reaction formula device.The 150mg catalyzer is warming up to 873K under hydrogen atmosphere, stablize 30 minutes after, temperature is elevated to 1023K, feeds flow velocity 15ml/cm again
2The benzene vapor of min, benzene vapor is 1 to 5 with nitrogen ratios, reacts to stop after 120 minutes, at H
2Be cooled to room temperature under the atmosphere, collect product, carbon nanotube output is 1.3g.
Embodiment 7
LNi with induction melting
3.6Co
0.4Fe
0.4(L is a norium) alloy powder is broken to 30 μ m-60 μ m, and alloy powder oxide treatment 15 minutes in air promptly gets prepared alloyed oxide catalyst samples.Made of carbon nanotubes is carried out on fixed bed gas continuous flow reaction formula device.The 120mg catalyzer is warming up to 823K under hydrogen atmosphere, stablize 20 minutes after, turn off hydrogen, feed flow velocity 30ml/cm again
2The gas maked coal of min and the gas mixture of nitrogen, gas maked coal is 1 to 20 with nitrogen ratios, reacts to stop after 100 minutes, is cooled to room temperature under nitrogen atmosphere, collects product, carbon nanotube output is 1.9g.
Embodiment 8
LNi with induction melting
3.6Co
0.7Al
0.3Mn
0.4(L is a norium) alloy powder is broken to 60 μ m-80 μ m, ball milling promptly got prepared non-crystaline amorphous metal sample in 80 hours then, non-crystaline amorphous metal crystal grain is the 50-200 nanometer, and alloy sample oxide treatment 40 minutes in air promptly gets prepared alloyed oxide catalyst samples.Made of carbon nanotubes is carried out on fixed bed gas continuous flow reaction formula device.The 100mg catalyzer is warming up to 823K under hydrogen atmosphere, stablize 20 minutes after, turn off hydrogen, feed flow velocity 30ml/cm again
2The Sweet natural gas of min and the gas mixture of nitrogen, Sweet natural gas is 1 to 8 with nitrogen ratios, reacts to stop after 30 minutes, is cooled to room temperature under nitrogen atmosphere, collects product, carbon nanotube output is 1.7g.
Claims (6)
1, a kind of preparation method of carbon nanotube is characterized in that it comprises the steps:
(1) is 0.01-200 μ m hydrogen storing alloy powder in air or oxygen under 373-1073K oxidation 2-100 minute with granularity, obtains the hydrogen storage alloy oxidation products;
(2) the hydrogen storage alloy oxidation products with metering places fixed bed gas continuous flow reaction formula device, under 573-1073K hydrogen reducing 5-120 minute;
(3) mixed gas of carbonaceous reactant gases of feeding and carrier gas under 573-1373K; Gas flow rate be the 5-500 milliliter/hour, the ratio of reactant gases and carrier gas is 1/0.1-1/30 in the mixed gas, the reaction times is to get final product in 10-180 minute.The hydrogen reduction product that utilizes is catalyzer, and catalytic pyrolysis prepares carbon nanotube and carbon nano fiber.Carrier gas is hydrogen or argon gas or helium or nitrogen.Under 573-1373K, feed reactant gases or with the mixed gas of carrier gas, gas flow rate be the 5-500 milliliter/hour, the ratio of reactant gases and carrier gas is 1/0.1-1/20 in the mixed gas, the reaction times is 10-180 minute.
2, by the preparation method of the described carbon nanotube of claim 1, it is characterized in that described hydrogen storage alloy can be following composition:
LNi
N-x-y-zCo
xN
yM
z, L is norium, La, Ce, Nd, Pr, Y, N and M are respectively Mn, V, Cr, Al, Fe, Cu, Zn, Sn, Mo, Si, 3≤n≤6,0≤x≤2,0≤y≤2,0≤z≤2;
KNi
A-b-c-dV
bG
cJ
d, K is Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, G and J are respectively Co, Mn, Cr, Al, Fe, Cu, Zn, Sn, Mo, Si, 1.2≤a≤3.0,0≤b≤2,0≤c≤2,0≤d≤2;
HN
M-k-jFe
kP
j, H is Zr, Hf, P is Co, Mn, V, Cr, Al, Cu, Zn, Sn, Mo, Si, 0.6≤m≤1.5,0≤k≤1.5,0≤j≤1;
Mg
G-fE
fNi
1-p-qCo
pT
q, E is Ca, Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, T is Mn, V, Cr, Al, Fe, Cu, Zn, Sn, Mo, Si, 1.0≤g≤3.0,0≤f≤1.5,0≤p≤1.0,0≤q≤1.0;
Any one or two kinds of above binary or the polynary non-crystaline amorphous metals of perhaps above-mentioned hydrogen storage alloy.
3, by the preparation method of the described carbon nanotube of claim 1, it is characterized in that described hydrogen storage alloy oxidation products is the 1-30% that accounts for carbon nanotube output.
4, by the preparation method of the described carbon nanotube of claim 1, it is characterized in that described carbonaceous reactant gases is hydrocarbon polymer, Sweet natural gas, gas maked coal, liquefied gas, CO or CO
2
5, by the preparation method of the described carbon nanotube of claim 4, it is characterized in that described hydrocarbon polymer is methane, acetylene, ethene or benzene vapor.
6, by the preparation method of the described carbon nanotube of claim 1, it is characterized in that described carrier gas is hydrogen, argon gas, helium or nitrogen.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7147533B2 (en) * | 2002-09-26 | 2006-12-12 | Canon Kabushiki Kaisha | Method of producing electron emitting device using carbon fiber, electron source and image forming apparatus, and ink for producing carbon fiber |
| CN1301353C (en) * | 2002-05-22 | 2007-02-21 | 昭和电工株式会社 | Process for producing vapor-grown carbon fibers |
| CN1312033C (en) * | 2005-07-01 | 2007-04-25 | 清华大学 | Method for large-batch preparing overlength carbon nano pipe array and its apparatus |
| CN100411866C (en) * | 2005-04-30 | 2008-08-20 | 北京大学 | Carbon fiber composite single carbon nano tube and its preparing method |
| CN101906666A (en) * | 2010-03-17 | 2010-12-08 | 中南大学 | Method for preparing micron/nano tungsten crystal whisker/wire/bar |
| CN103153849A (en) * | 2010-10-26 | 2013-06-12 | 日立化成株式会社 | Process for production of carbon nanotubes |
| CN103180497A (en) * | 2010-10-20 | 2013-06-26 | 电气化学工业株式会社 | Method for producing carbon nanofibers, carbon composite and method for producing same |
| CN104619414A (en) * | 2012-09-25 | 2015-05-13 | 锦湖石油化学株式会社 | Catalyst composition for the synthesis of multi-walled carbon nanotube |
| CN111530462A (en) * | 2020-04-20 | 2020-08-14 | 无锡东恒新能源科技有限公司 | Synthetic array type carbon nanotube catalyst and preparation method and application thereof |
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2000
- 2000-09-26 CN CN 00124600 patent/CN1207185C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301353C (en) * | 2002-05-22 | 2007-02-21 | 昭和电工株式会社 | Process for producing vapor-grown carbon fibers |
| US7147533B2 (en) * | 2002-09-26 | 2006-12-12 | Canon Kabushiki Kaisha | Method of producing electron emitting device using carbon fiber, electron source and image forming apparatus, and ink for producing carbon fiber |
| CN100411866C (en) * | 2005-04-30 | 2008-08-20 | 北京大学 | Carbon fiber composite single carbon nano tube and its preparing method |
| CN1312033C (en) * | 2005-07-01 | 2007-04-25 | 清华大学 | Method for large-batch preparing overlength carbon nano pipe array and its apparatus |
| CN101906666A (en) * | 2010-03-17 | 2010-12-08 | 中南大学 | Method for preparing micron/nano tungsten crystal whisker/wire/bar |
| CN103180497A (en) * | 2010-10-20 | 2013-06-26 | 电气化学工业株式会社 | Method for producing carbon nanofibers, carbon composite and method for producing same |
| CN103180497B (en) * | 2010-10-20 | 2015-08-26 | 电气化学工业株式会社 | The manufacture method of carbon nano-fiber, carbon complex and manufacture method thereof |
| CN103153849A (en) * | 2010-10-26 | 2013-06-12 | 日立化成株式会社 | Process for production of carbon nanotubes |
| US9096435B2 (en) | 2010-10-26 | 2015-08-04 | Hitachi Chemical Company, Ltd. | Process for production of carbon nanotube |
| CN104619414A (en) * | 2012-09-25 | 2015-05-13 | 锦湖石油化学株式会社 | Catalyst composition for the synthesis of multi-walled carbon nanotube |
| CN111530462A (en) * | 2020-04-20 | 2020-08-14 | 无锡东恒新能源科技有限公司 | Synthetic array type carbon nanotube catalyst and preparation method and application thereof |
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