CN1994562A - Catalyst for producing carbon nanotube - Google Patents
Catalyst for producing carbon nanotube Download PDFInfo
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- CN1994562A CN1994562A CN 200610172183 CN200610172183A CN1994562A CN 1994562 A CN1994562 A CN 1994562A CN 200610172183 CN200610172183 CN 200610172183 CN 200610172183 A CN200610172183 A CN 200610172183A CN 1994562 A CN1994562 A CN 1994562A
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Abstract
The invention relates to a catalyst which can prepare carbon nanometer tube, wherein said catalyst comprises at least one VB metal element as V, Nb or Ta, and at least one VIII metal element as Fe, Co, Ni, Pd or Pt; the metal element is deposited on the carrier to form catalyst or via gel burning composing method to prepare the composite oxide catalyst with metal element and carrier element. The inventive catalyst via catalysis chemical gas deposit method can prepare single-wall carbon nanometer tube with high purity, dual-wall carbon nanometer tube or multi-wall carbon nanometer tube with better linearity.
Description
Technical field
The invention belongs to field of nano material preparation, particularly adopt catalytic chemical vapor deposition technique to prepare CNT.
Background technology
CNT was clearly set forth [Nature, 354 (1991), 56] first by Japanese Electronic Speculum expert Ijima in 1991.It has unique mechanical, electricity and chemical property and unique accurate one dimension tracheary element structure, in numerous areas such as microelectronics, the energy, national defence and space flight and aviation, demonstrate many potential using values, become the research focus in fields such as chemistry, physics and material science.
At present, the preparation method of CNT mainly contains: arc discharge method, catalytic chemical vapor deposition technique, laser ablation method.Wherein catalytic chemical vapor deposition technique enjoys researcher's attention, because that this method has equipment is simple, easy and simple to handle, can high efficiency preparation CNT, and be a kind of method of optimal large-scale production CNT.The key that catalytic chemical vapor deposition technique is produced CNT is a catalyst, and the catalyst that bibliographical information adopts this legal system to be equipped with CNT is generally metal Co, Ni or the Fe that is selected from VIII family.For preparing high-quality CNT, generally adopt bimetallic catalyst under suitable temperature, to contact with carbon-source gas.Chinese invention patent CN 1495127 discloses a kind of Co and Mo and has been supported on bimetallic catalyst on the MgO, under suitable temperature, contact with methane, can highly-selective preparation SWCN or multi-walled carbon nano-tubes, but the prepared CNT productive rate of this catalyst is low, and remainder catalyst is difficult to remove.The catalyst system of seeking the efficient production CNT is the challenge that this area faces always.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that can high efficiency prepares CNT.This catalyst also contains at least a metallic element that is selected from periodic table of elements VB family when containing at least a metallic element that is selected from period of element Table VIII family.Described metallic element can be supported on the carrier or form composite oxides with material as carrier material.Under appropriate condition, adopt this catalyst can prepare high-purity SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
Catalyst particle of the present invention can contain (1) more than one the metallic element of VB family and the metallic element of a kind of VIII of being selected from family; (2) metallic element of a kind of VB family and more than one the metallic element that is selected from VIII family; (3) more than one metallic elements that are selected from VB family are selected from the metallic element of VIII family with more than one.
Catalyst provided by the invention is bimetal element at least.At least the metallic element that contains a kind of VB of being selected from family in the bimetal element catalyst, for example V, Nb or Ta and contain the metallic element of a kind of VIII of being selected from family, for example Fe, Co, Ni, Pd or Pt.There is cooperative effect between two kinds of metallic element components in the bimetal element catalyst.Compare with the catalyst that only contains VB family metallic element or with the catalyst that only contains VIII family metallic element, bimetal element catalyst of the present invention can more effective acquisition high-purity SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
The instantiation that can be used for bimetallic catalyst of the present invention comprises Fe-V, Fe-Nb, Fe-Ta, Co-V, Co-Nb, Co-Ta, Ni-V, Ni-Nb, Ni-Ta, Ru-V, Ru-Nb, Ru-Ta, Rh-V, Rh-Nb, Rh-Ta, Pd-V, Pd-Nb, Pd-Ta, Os-V, Os-Nb, Os-Ta, Ir-V, Ir-Nb, Ir-Ta, Pt-V, Pt-Nb and Pt-Ta.The particularly preferred catalyst of the present invention comprises Co-V, Fe-V, Ni-V.
Catalyst of the present invention can have carrier, and carrier is SiO
2, Si, MCM-41, Al
2O
3, MgO, CaO, La
2O
3, Mg (Al) Ox, SiO
2-Al
2O
3, Mg (Si) Ox, ZrO
2, quartz or molecular sieve zeolites or two kinds in these carriers and two or more mixtures.
Catalyst of the present invention can be by simply making two kinds of metallic element compound, be mixed together with carrier in case of necessity and make, also can form, be about to precursor compound and be dissolved in water or the organic solvent, mix the back pyrolytic and make by decomposing precursor compound.Precursor compound can be slaines such as cobalt nitrate, ferric nitrate, cobalt acetate, nickel nitrate and vanadic sulfate etc.Catalyst of the present invention can also by persons skilled in the art known method such as dipping, coating, evaporated metal mixture planar substrate as surfaces such as quartzy, silicon and aluminium oxide on or make on the conventional carrier.
Catalyst of the present invention can also be by the synthetic method preparation of gel combustion, being about to cobalt nitrate, vanadic sulfate, aluminum nitrate or magnesium nitrate and citric acid etc. is dissolved in the aqueous solution, evaporate the formation gel down at 80～150 ℃, burning obtains catalyst of the present invention in 500～700 ℃ of following air atmosphere again.
The preferred group of catalyst of the present invention becomes V
xCo
yMg
1-x-yO
z, x=0.01～0.5 wherein, y=0.01～0.5, z＞1.0.
Adopt the suitable carbon-source gas of Preparation of Catalyst CNT of the present invention to comprise: saturated and undersaturated aliphatic hydrocarbon, for example methane, ethane, propane, ethene, third rare etc.; Carbon monoxide; The hydrocarbon of oxidation, for example acetone, acetylene, methyl alcohol, ethanol etc.; Aromatic hydrocarbon, for example toluene, benzene and naphthalene; And the mixture of above material.Carbon-source gas can randomly mix with diluent gas, for example helium, argon gas, nitrogen and hydrogen.
Adopt Preparation of Catalyst CNT of the present invention can adopt fixed bed reactors, fluidized-bed reactor, moving-burden bed reactor or motion column plate reactor etc.
Catalyst of the present invention is particularly suitable for preparing high-purity SWCN or high-purity double-walled carbon nano-tube, also is fit to the good tubule footpath multi-walled carbon nano-tubes of preparation linearity.
Description of drawings
Fig. 1 is the TEM photo of the SWCN of Preparation of Catalyst of the present invention.
Fig. 2 is the TEM photo of the double-walled carbon nano-tube of Preparation of Catalyst of the present invention.
The specific embodiment
The present invention will be described in more detail catalyst by following examples and form, prepares and use.But embodiment only is used to thinking of the present invention is described, limits the scope of the invention and be not used in.
Embodiment 1:
Ferric nitrate, vanadic sulfate are dissolved in (mol ratio Fe: V: Al in an amount of methyl alcohol
2O
3=1: 0.2: 16), again with Al
2O
3(specific surface is 178m
2/ g) be dispersed in this solution ultrasonic dispersion 30min.Solution is in 90～100 ℃ of evaporations, dry 24h hour.After milling, at 400～500 ℃ of roasting 5h, milling obtains ferrovanadium aluminium composite oxide catalyst again.
The preparation of CNT is carried out in the quartz tube type reacting furnace.200mg ferrovanadium aluminium composite oxide catalyst is warming up to 900 ℃ under nitrogen atmosphere, the feeding flow is that hydrogen and the flow of 200ml/min is the methane of 50ml/min, and reaction 60min stops, and nitrogen protection is cooling down, collects product.Product is purified, washing, drying, obtains pure SWCN 56mg.
Embodiment 2
Take by weighing a certain amount of cobalt nitrate, vanadic sulfate, magnesium nitrate (mol ratio Co: V: Mg=1: 0.2: 19) and be dissolved in the distilled water, add excessive citric acid solution again.Solution is evaporated to solution gradually 80 ℃ of stirrings becomes thick, move in the baking oven and decompose, the back of milling is at 650 ℃ of roasting 10h of Muffle furnace, and cooling obtains cobalt vanadium Magnesium coumpoud oxide catalyst naturally.
The preparation of CNT is carried out in the quartz tube type reacting furnace.200mg cobalt vanadium Mg-Al composite oxide catalyst is warming up to 600 ℃ under nitrogen atmosphere, the feeding flow is that hydrogen and the flow of 200ml/min is the methane of 50ml/min, stops at 600～850 ℃ of reaction 60min, and nitrogen protection is cooling down, collects product.Product is purified, washing, drying, obtains pure SWCN 135mg, and product TEM photo is seen Fig. 1.
Embodiment 3
Take by weighing a certain amount of cobalt nitrate, vanadic sulfate, magnesium nitrate (mol ratio Co: V: Mg=1: 0.5: 18) and be dissolved in the distilled water, add excessive citric acid solution again.Solution is evaporated to solution gradually 80 ℃ of stirrings becomes thick, move in the baking oven and decompose, the back of milling is at 650 ℃ of roasting 10h of Muffle furnace, and cooling promptly obtains cobalt vanadium Magnesium coumpoud oxide catalyst naturally.
CNT must prepare in tubular react furnace and prepare; to be warming up to 600 ℃ under the 200mg cobalt vanadium Magnesium coumpoud oxide catalyst nitrogen atmosphere, the feeding flow is that methane and the flow of 50ml/min is the hydrogen of 200ml/min, stops at 900 ℃ of reaction 60min; nitrogen protection is cooling down, collects product.Product is purified, washing, drying, obtains linearity pure nano-carbon tube 435mg, and caliber is 2～4nm, and product TEM photo is seen Fig. 2.
Embodiment 4
Take by weighing a certain amount of nickel nitrate, NbOF
32KFH
2O, magnesium nitrate (mol ratio Ni: Nb: Mg=1: 0.4: 9) are dissolved in the distilled water, add excessive citric acid solution again.Solution is evaporated to solution gradually 80 ℃ of stirrings becomes thick, move in the baking oven and decompose, the back of milling is at 650 ℃ of roasting 10h of Muffle furnace, and cooling promptly obtains cobalt vanadium Magnesium coumpoud oxide catalyst naturally.
CNT must prepare in tubular react furnace and prepare; 200mg nickel niobium Magnesium coumpoud oxide catalyst is warming up to 600 ℃ under nitrogen atmosphere; the feeding flow is that methane and the flow of 50ml/min is the hydrogen of 200ml/min; stop at 700～1000 ℃ of reaction 60min; nitrogen protection is cooling down, collects product.Product is purified, washing, drying, obtains pure nano-carbon tube 508mg, and caliber is about 10nm, linearly property.
Claims (8)
1. catalyst for preparing CNT is characterized in that described catalyst contains a kind of metallic element that is selected from the metallic element of VB family in the periodic table of elements and contains a kind of VIII of being selected from family at least at least.
2. according to the catalyst of claim 1, it is characterized in that described metallic element and carrier form composite oxides or be deposited on the carrier by infusion process.
3. according to the catalyst of claim 1, the metallic element that it is characterized in that being selected from VB family in the periodic table of elements is V.
4. according to the catalyst of claim 1, the metallic element that it is characterized in that VIII family is Co, Fe, Ni or its mixture.
5. according to the catalyst of claim 2, it is characterized in that catalyst carrier is SiO
2, Si, MCM-41, Al
2O
3, MgO, CaO, La
2O
3, Mg (Al) Ox, SiO
2-Al
2O
3, Mg (Si) Ox, ZrO
2, quartz or molecular sieve zeolites.
6. according to the catalyst of claim 2, it is characterized in that the V that consists of of catalyst
xCo
yMg
1-x-yO
z, x=0.01～0.5, y=0.01～0.5, z＞1.0.
7. according to the catalyst of claim 1, it is characterized in that the mol ratio of the metallic element of the metallic element of VB family and VIII family is 1: 15 to 15: 1.
8. according to the catalyst of claim 1, it is characterized in that the weight percentage 1～30% of described metallic element in catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610172183 CN1994562A (en) | 2006-12-31 | 2006-12-31 | Catalyst for producing carbon nanotube |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610172183 CN1994562A (en) | 2006-12-31 | 2006-12-31 | Catalyst for producing carbon nanotube |
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|---|---|
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Family
ID=38249813
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905881A (en) * | 2010-08-02 | 2010-12-08 | 无锡诚信碳材料科技有限公司 | Preparation method of nano-carbon material with high graphitization degree |
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN103803522A (en) * | 2012-11-08 | 2014-05-21 | 北京大学 | Preparation method of semiconductor single-walled carbon nanotubes |
| CN104211044A (en) * | 2014-09-01 | 2014-12-17 | 中国科学院金属研究所 | Macro-controllable growth method of narrow chiral and semiconducting single-walled carbon nanotubes |
| CN105000543A (en) * | 2014-04-18 | 2015-10-28 | 中国科学院成都有机化学有限公司 | Method for preparing aligned carbon nanotubes |
| CN105056990A (en) * | 2015-09-11 | 2015-11-18 | 宁波海越新材料有限公司 | Propane dehydrogenation produced propylene catalyst and preparation method thereof |
| CN107626334A (en) * | 2017-10-19 | 2018-01-26 | 焦作集越纳米材料技术有限公司 | A kind of preparation method of carbon nano-tube catalyst |
| CN109433208A (en) * | 2018-09-30 | 2019-03-08 | 青岛科技大学 | It is used to prepare the Co catalysts and its preparation method and application of single-walled carbon nanotube |
| CN110339842A (en) * | 2019-06-26 | 2019-10-18 | 江西铜业技术研究院有限公司 | A kind of composite catalyst and preparation method thereof growing carbon nanotube |
| CN113148982A (en) * | 2021-03-11 | 2021-07-23 | 江西铜业技术研究院有限公司 | Preparation method of high-purity double-wall carbon nano tube |
| CN113663690A (en) * | 2021-08-30 | 2021-11-19 | 福建海梵领航科技有限公司 | Catalyst for preparing small-caliber single-walled carbon nanotube and preparation method and application thereof |
-
2006
- 2006-12-31 CN CN 200610172183 patent/CN1994562A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905881A (en) * | 2010-08-02 | 2010-12-08 | 无锡诚信碳材料科技有限公司 | Preparation method of nano-carbon material with high graphitization degree |
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN103803522A (en) * | 2012-11-08 | 2014-05-21 | 北京大学 | Preparation method of semiconductor single-walled carbon nanotubes |
| CN105000543A (en) * | 2014-04-18 | 2015-10-28 | 中国科学院成都有机化学有限公司 | Method for preparing aligned carbon nanotubes |
| CN104211044A (en) * | 2014-09-01 | 2014-12-17 | 中国科学院金属研究所 | Macro-controllable growth method of narrow chiral and semiconducting single-walled carbon nanotubes |
| CN105056990A (en) * | 2015-09-11 | 2015-11-18 | 宁波海越新材料有限公司 | Propane dehydrogenation produced propylene catalyst and preparation method thereof |
| CN107626334A (en) * | 2017-10-19 | 2018-01-26 | 焦作集越纳米材料技术有限公司 | A kind of preparation method of carbon nano-tube catalyst |
| CN109433208A (en) * | 2018-09-30 | 2019-03-08 | 青岛科技大学 | It is used to prepare the Co catalysts and its preparation method and application of single-walled carbon nanotube |
| CN109433208B (en) * | 2018-09-30 | 2021-08-06 | 青岛科技大学 | Cobalt catalyst for preparing single-walled carbon nanotube and preparation method and application thereof |
| CN110339842A (en) * | 2019-06-26 | 2019-10-18 | 江西铜业技术研究院有限公司 | A kind of composite catalyst and preparation method thereof growing carbon nanotube |
| CN113148982A (en) * | 2021-03-11 | 2021-07-23 | 江西铜业技术研究院有限公司 | Preparation method of high-purity double-wall carbon nano tube |
| CN113663690A (en) * | 2021-08-30 | 2021-11-19 | 福建海梵领航科技有限公司 | Catalyst for preparing small-caliber single-walled carbon nanotube and preparation method and application thereof |
| CN113663690B (en) * | 2021-08-30 | 2023-08-15 | 福建海梵领航科技有限公司 | Catalyst for preparing small-diameter single-wall carbon nano tube, preparation method and application |
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