CN106517146A - Method for preparing composite nanocarbon material - Google Patents
Method for preparing composite nanocarbon material Download PDFInfo
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- CN106517146A CN106517146A CN201610993288.6A CN201610993288A CN106517146A CN 106517146 A CN106517146 A CN 106517146A CN 201610993288 A CN201610993288 A CN 201610993288A CN 106517146 A CN106517146 A CN 106517146A
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- catalyst
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- mixed liquor
- reaction tower
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention relates to the field of material synthesis and discloses a method for preparing a composite nanocarbon material. The method comprises introducing a single-walled carbon nanotube precursor and a multi-walled carbon nanotube precursor into a reaction tower through different paths, and carrying out high temperature cracking and catalytic growth to obtain uniformly dispersed single-walled and multi-walled composite carbon nanotubes. The method solves the problem that the single-walled carbon nanotube products are wound to form a bundle and are extremely difficult to disperse and use, improves the electrical conductivity, thermal conductivity and mechanical properties of the multi-walled carbon nanotube and has the advantages of simpleness, continuity and stability.
Description
Technical field
The present invention relates to material with carbon element synthesis field, more particularly, to a kind of preparation method of composite Nano material with carbon element.
Background technology
SWCN is the tubular structure curled into by the Graphene of monolayer, compares multi-walled carbon nano-tubes, is had
More excellent physical property.But due to there is stronger Van der Waals force between SWCN, there is mutually absorption, winding
Bunchy, extremely difficult dispersion, the shortcoming for using difficulty, this virtually limits the industrialized application of SWCN.
In order to solve the above problems, the present invention comes therefrom.
The content of the invention
The purpose of the present invention be overcome existing SWCN mutually to adsorb, wind bunchy, extremely difficult dispersion, using difficult
Shortcoming, there is provided a kind of magnanimity prepares the new method of single wall-many wall composite carbon nanometer tubes, can be with effectively solving SWCN
The difficult problem that product winding bunchy, extremely difficult dispersion are used, improves the conduction of multi-walled carbon nano-tubes, heat conduction, mechanical property again.We
Method has the advantages that process is simple, continuous, stable.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of composite Nano material with carbon element, which comprises the following steps：
(1) catalyst A presomas are added in organic carbon source and is configured to mixed liquor I, catalyst precursor B is added another
Mixed liquor I I is made in organic carbon source；
(2) aforesaid mixed liquor I, II are imported into reaction tower by different paths；Catalyst precursor through high temperature pyrolysis,
Vapour phase reduction, forms catalyst A and B；Alloys of the wherein catalyst A for particle diameter≤5nm, lists of the catalyst B for particle diameter≤20nm
Matter metal or alloy；Organic carbon source forms carbon atom and reducing atmosphere through high temperature pyrolysis；
(3) carbon atom generated in step (2) in catalyst A superficial growths into SWCN, in catalyst B surface
Grow into multi-walled carbon nano-tubes；The two floats in reaction tower atmosphere and mutually disperses, is interweaved, and naturally form mutually uniform
Scattered single wall-many wall composite carbon nanometer tubes.
Preferably, by regulation mixed liquor I and the inlet amount speed of mixed liquor I I, the list of different proportion content can be formed
Wall-many wall composite carbon nanometer tubes.
Preferably, in step (1) organic carbon source be CxHyOz compounds in one or more, wherein 1≤x≤
16,2≤y≤34,0≤z≤16；Preferably alkane, alkene, alkynes, aromatic hydrocarbon or alcohols；Be more preferably selected from benzene, toluene, two
Toluene, ethanol.
Preferably, in step (1), the presoma of catalyst A is selected from metal alkoxide, metallocene salt, metal-carbonyl chemical combination
Two or more in thing, acetyl acetone salt, the presoma of catalyst B are selected from metal alkoxide, metallocene salt, metal-carbonyl
One or more in compound, acetyl acetone salt.
Preferably, in step (2), catalyst A is selected from Fe, Co, Ni, Cu, Zn, V, Ti, Zr, Cr, Mn, W, Mo
Two or more.Preferably, in step (2), catalyst B is selected from one or more in Fe, Co, Ni.Before catalyst A
Driving body includes but is not limited to：Two or more in carbonyl cobalt, tungsten carbonyl, ferrocene；The presoma of catalyst B includes but does not limit
For one or more in ferrocene, dicyclopentadienyl nickel, cobaltocene.
Preferably, in step (1) in mixed liquor I catalyst A presoma content be 0.01～3wt%, mixed liquor
In II, the presoma content of catalyst B is 0.5～10wt%.
Preferably, the feed rate of the mixed liquor I and mixed liquor I I is 0.21L/h～1L/h.
Preferably, in step (4), in composite carbon nanometer tube, SWCN content is 1wt%-90wt%.
Mixed liquor I, II in the present invention imports reaction tower by " different paths ", and " different paths " here refer to mixed
Close liquid I, II and reaction tower can be imported from the top of reaction tower respectively, or can lead from the top of reaction tower or sidepiece respectively
Enter reaction tower.
For solving the above problems, the present invention proposes a kind of preparation method of single wall-many wall composite carbon nanometer tubes.By single wall
Carbon nanotube precursor, multi-walled carbon nano-tubes presoma import reaction tower by different paths, through Pintsch process, atmosphere also
Original, forms the catalyst of two kinds of different-grain diameters.Carbon atom is grown and to form SWCN in particle diameter≤5nm catalyst surfaces,
Grow and to form multi-walled carbon nano-tubes in particle diameter≤20nm catalyst surfaces.Single wall and multi-walled carbon nano-tubes are floated, are handed in synthesis zone
Converge, be interweaved, form homodisperse single wall-many wall composite carbon nanometer tubes.Speed is put into by regulating and controlling presoma, can be obtained
The single wall of different content ratio-many wall composite carbon nanometer tubes.The SWCN of gained is three-dimensional with multi-walled carbon nano-tubes to interweave
Growth, had both solved the difficult problem that SWCN product winds bunchy, extremely difficult dispersion is used, had improve multi-walled carbon nano-tubes again
Conduction, heat conduction, mechanical property.This method has the advantages that process is simple, continuous, stable.
It is an advantage of the current invention that：Compared with prior art, using different type catalyst, it is possible to achieve single wall-many walls
The three-dimensional growth that interweaves of composite carbon nanometer tube, had both solved the difficult problem that SWCN product winds bunchy, extremely difficult dispersion is used,
The conduction of multi-walled carbon nano-tubes, heat conduction, mechanical property is improve again.This method has the advantages that process is simple, continuous, stable.
Based on above advantage, the present invention is applied to large-scale production high-quality single wall-many wall composite carbon nanometer tubes.
Description of the drawings
The reaction tower that Fig. 1 is protected with air curtain, wherein：1 is tower body；11 is first material import；12 is material outlet；13 are
Air vent；14 is top tower wall；15 is middle part tower wall；16 is bottom tower wall；
2 is ring wall protective gas spraying system；21 is top pipe network；22 is middle part pipe network；23 is bottom pipe network；24 is gas
Pipe；25 is nozzle.
SEM photographs of the Fig. 2 for one preparation-obtained single wall of the embodiment of the present invention-many wall composite carbon nanometer tubes.
Specific embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the present invention.The implementation condition adopted in embodiment can be done according to the condition of concrete producer
Further adjust, not marked implementation condition is usually the condition in normal experiment.
Embodiment 1
The present embodiment is in a kind of reaction tower with air curtain protection (reaction tower with air curtain protection and its air inlet method, public affairs
The number of opening：CN103278008B carry out in), as shown in Figure 1.The reaction tower with air curtain protection, including tower body 1, pacifies in tower body 1
Equipped with the ring wall protective gas spraying system 2 that pipe network is constituted is connected into by trachea 24, a plurality of nozzles are dispersed with trachea 24
25；The ring wall protective gas spraying system 2 includes top pipe network 21, middle part pipe network 22 and the bottom pipe network connected by trachea 24
23 compositions；Top pipe network 21 be located at tower body 1 in epimere, the trachea 24 of top pipe network 21 centered on first material import 11,
And with 14 parallel radiation shape equidistantly distributed of top tower wall；Bottom pipe network 23 is located at the hypomere in tower body 1, with material outlet 12 is
Center, in the conical surface, radial equidistantly distributed is parallel with bottom tower wall 16；Middle part pipe network 22 is located at stage casing in tower body 1, and with
Portion's tower wall 15 is parallel, and cross section arrangement of the middle part pipe network 22 in tower body 1 is shaped as regular polygon, and trachea and middle part tower wall
Vertical interval is equal, and its 24 upper and lower ends of trachea connects top pipe network 21 and bottom pipe network 23 respectively.
Be passed through nitrogen protection atmosphere in the reaction tower protected with air curtain, three sections of temperature control areas (refer to the epimere of reaction tower, stage casing,
Hypomere) 1200 DEG C, 1400 DEG C, 1400 DEG C are warmed up to respectively, heating rate is 10 DEG C/min.By peristaltic pump by ethanol, ethanol
Ferrum, ethanol tungsten mixed liquor I from one material inlet of top import reaction tower in, wherein ethanol iron content be 0.34wt%, ethanol
W content is 0.66wt%, and feed rate is 0.5L/h；At the same time, by another peristaltic pump by the mixing of benzene and ferrocene
Liquid II is imported in reaction tower from another material inlet in top, and in mixed liquor, ferrocene content is 5.8wt%, and feed rate is 1L/
H, obtains single wall-many wall composite carbon nanometer tubes, and wherein SWCN content is 20wt%.To the single wall after synthesis-many walls
Composite carbon nanometer tube carries out SEM detections (such as Fig. 2), and SWCN not mutually absorption winding with multi-walled carbon nano-tubes is in
Reveal the structure that three-dimensional is interweaved.With respect to multi-walled carbon nano-tubes, the body electricity of single wall-many wall composite carbon nanometer tubes of the present embodiment
Resistance reduces by 80%, and heat conductivity increases by 30%.
Embodiment 2
The present embodiment is carried out in a kind of reaction tower with air curtain protection, is passed through nitrogen protection atmosphere, three sections of temperature control areas
(referring to the epimere of reaction tower, stage casing, hypomere) is warmed up to 1100 DEG C, 1300 DEG C, 1300 DEG C respectively, and heating rate is 10 DEG C/min.
The mixed liquor I of ethanol, carbonyl cobalt, tungsten carbonyl is imported in reaction tower from one material inlet of top by peristaltic pump, wherein carbonyl
Cobalt content is 0.25wt%, and carbonyl W content is 0.66wt%, and feed rate is 0.5L/h；At the same time, it is compacted by another
Mixed liquor I I of benzene and ferrocene is imported in reaction tower by dynamic pump from another material inlet in top, and in mixed liquor, ferrocene content is
5.8wt%, feed rate are 1L/h, obtain single wall-many wall composite carbon nanometer tubes, and wherein SWCN content is 5wt%.
With respect to multi-walled carbon nano-tubes, the bulk resistor of single wall-many wall composite carbon nanometer tubes of the present embodiment reduces by 30%, and heat conductivity increases
10%.
Embodiment 3
The present embodiment is carried out in a kind of reaction tower with air curtain protection, is passed through nitrogen protection atmosphere, three sections of temperature control areas
(referring to the epimere of reaction tower, stage casing, hypomere) is warmed up to 1100 DEG C, 1300 DEG C, 1300 DEG C respectively, and heating rate is 10 DEG C/min.
The mixed liquor I of ethanol, ethanol cobalt, molybdenum carbonyl is imported in reaction tower from one material inlet of top by peristaltic pump, wherein ethanol
Cobalt content is 0.34wt%, and carbonyl molybdenum content is 0.48wt%, and feed rate is 0.5L/h；Simultaneously, it is compacted by another
Mixed liquor I I of benzene and ferrocene is imported in reaction tower by dynamic pump from another material inlet in top, and in mixed liquor, ferrocene content is
5.8wt%, feed rate are 1L/h, obtain single wall-many wall composite carbon nanometer tubes, and wherein SWCN content is
10wt%.With respect to multi-walled carbon nano-tubes, the bulk resistor of single wall-many wall composite carbon nanometer tubes of the present embodiment reduces by 40%, heat conduction
Coefficient increases by 20%.
Examples detailed above technology design only to illustrate the invention and feature, its object is to allow the person skilled in the art be
Will appreciate that present disclosure and implement according to this, can not be limited the scope of the invention with this.It is all smart according to the present invention
Equivalent transformation or modification that refreshing essence is done, should all be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of composite Nano material with carbon element, which comprises the following steps：
(1) catalyst A presomas are added in organic carbon source and is configured to mixed liquor I, catalyst precursor B is added another organic
Mixed liquor I I is made in carbon source；
(2) aforesaid mixed liquor I, II are imported into reaction tower by different paths；Catalyst precursor is through high temperature pyrolysis, gas phase
Reduction, forms catalyst A and B respectively；Alloys of the wherein catalyst A for particle diameter≤5nm, lists of the catalyst B for particle diameter≤20nm
Matter metal or alloy；Organic carbon source forms carbon atom and reducing atmosphere through high temperature pyrolysis；
(3) carbon atom generated in step (2) is grown in catalyst B surface in catalyst A superficial growths into SWCN
Into multi-walled carbon nano-tubes；The two floats in reaction tower atmosphere, mutually disperses, is interweaved, and naturally form mutually uniform point
Scattered single wall-many wall composite carbon nanometer tubes.
2. preparation method according to claim 1, it is characterised in that organic carbon source is CxHyOzization in step (1)
One or more in compound, wherein 1≤x≤16,2≤y≤34,0≤z≤16.
3. preparation method according to claim 1 and 2, it is characterised in that organic carbon source is selected from alkane in step (1)
Hydrocarbon, alkene, alkynes, aromatic hydrocarbon or alcohols.
4. preparation method according to claim 1, it is characterised in that the presoma of catalyst A is selected from step (1)
Two or more in metal alkoxide, metallocene salt, metal carbonyl, acetyl acetone salt, the presoma of catalyst B
One or more in metal alkoxide, metallocene salt, metal carbonyl, acetyl acetone salt.
5. preparation method according to claim 1, it is characterised in that in step (2) catalyst A selected from Fe, Co,
Two or more in Ni, Cu, Zn, V, Ti, Zr, Cr, Mn, W, Mo.
6. preparation method according to claim 1, it is characterised in that catalyst B is selected from Fe, Co, Ni in step (2)
In one or more.
7. preparation method according to claim 1, it is characterised in that catalyst A in mixed liquor I in step (1)
Presoma content is 0.01～3wt%, and in mixed liquor I I, the presoma content of catalyst B is 0.5～10wt%.
8. preparation method according to claim 1, it is characterised in that reaction tower is that band air curtain is protected in step (2)
Reaction tower.
9. preparation method according to claim 1, it is characterised in that single wall in composite carbon nanometer tube in step (4)
Content of carbon nanotubes is 1wt%-90wt%.
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| CN201610993288.6A CN106517146A (en) | 2016-11-11 | 2016-11-11 | Method for preparing composite nanocarbon material |
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| CN201610993288.6A CN106517146A (en) | 2016-11-11 | 2016-11-11 | Method for preparing composite nanocarbon material |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696052A (en) * | 2004-05-10 | 2005-11-16 | 华东理工大学 | Method for preparing Nano carbon tubes |
| CN101665248A (en) * | 2009-09-11 | 2010-03-10 | 清华大学 | Method for preparing single-walled and double-walled carbon nanotubes based on layered dihydroxy metal hydroxide |
| CN101830455A (en) * | 2010-04-30 | 2010-09-15 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN102502589A (en) * | 2011-11-09 | 2012-06-20 | 清华大学 | Device and method for continuously preparing high-purity single/double-wall carbon nano tubes |
| CN102730673A (en) * | 2012-07-04 | 2012-10-17 | 清华大学 | Apparatus and method for continuously preparing thin-layer grapheme or hybrid combining thin-layer grapheme with thin-walled carbon nanotube |
| CN103278008A (en) * | 2013-05-17 | 2013-09-04 | 恒正科技（苏州）有限公司 | Reaction tower with air curtain protection and air intake method thereof |
-
2016
- 2016-11-11 CN CN201610993288.6A patent/CN106517146A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696052A (en) * | 2004-05-10 | 2005-11-16 | 华东理工大学 | Method for preparing Nano carbon tubes |
| CN101665248A (en) * | 2009-09-11 | 2010-03-10 | 清华大学 | Method for preparing single-walled and double-walled carbon nanotubes based on layered dihydroxy metal hydroxide |
| CN101830455A (en) * | 2010-04-30 | 2010-09-15 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN102502589A (en) * | 2011-11-09 | 2012-06-20 | 清华大学 | Device and method for continuously preparing high-purity single/double-wall carbon nano tubes |
| CN102730673A (en) * | 2012-07-04 | 2012-10-17 | 清华大学 | Apparatus and method for continuously preparing thin-layer grapheme or hybrid combining thin-layer grapheme with thin-walled carbon nanotube |
| CN103278008A (en) * | 2013-05-17 | 2013-09-04 | 恒正科技（苏州）有限公司 | Reaction tower with air curtain protection and air intake method thereof |
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Application publication date: 20170322 |
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