CN109761220A - A kind of method of fluidized bed process continuous production helical form carbon material - Google Patents
A kind of method of fluidized bed process continuous production helical form carbon material Download PDFInfo
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- CN109761220A CN109761220A CN201910233917.9A CN201910233917A CN109761220A CN 109761220 A CN109761220 A CN 109761220A CN 201910233917 A CN201910233917 A CN 201910233917A CN 109761220 A CN109761220 A CN 109761220A
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Abstract
The present invention relates to a kind of methods of fluidized bed process continuous production helical form carbon material, belong to helical form carbon material preparation field.Method includes the following steps: that reaction zone is first heated to 600-1000 DEG C, reactant gas and non-interactive gas are passed through into reaction zone from the bottom of reaction zone again, then the particle for being supported with catalyst is added in reaction zone, is suspended in particle in reaction zone under the blowing of gas；In catalyst surface catalytic pyrolysis reaction occurs for the reactant gas being passed through, and helical form carbon material is gradually grown in the particle surface to swim；Growth spiral shape carbon material, which reaches, on particle blows out reaction zone by gas after the scheduled reaction time, then supplement is supported with the particle of catalyst into reaction zone；It repeats the above steps, forms continuous production.The present invention breaches the bottleneck for preparing helical form carbon material in the prior art, realizes helical form carbon material serialization and largely produces, and lays a solid foundation for helical form carbon material practical application.
Description
Technical field
The present invention relates to a kind of methods of fluidized bed process continuous production helical form carbon material, belong to the preparation of helical form carbon material
Field.
Background technique
Helical form carbon material includes spiral carbon nanotubes (also known as carbon nanocoil, nano-sized carbon spiral), spiral carbon Nanowire
Dimension, spiral carbon micrometer fibers (also known as carbon micron coil), in addition to outstanding electric conductivity and thermal conductivity possessed by carbon nanotube
In addition, also there is its Spiral morphology bring very good mechanical properties and mechanical property and electromagnetic performance.With spiral carbon nanotubes
For, with very high mechanical strength, it can be made into high-intensitive composite material full of elasticity；It is compared with other nano materials,
The dispersion performance of spiral carbon nanotubes is excellent, can be homogeneously dispersed among resin, to be effectively reduced additive amount and make
The high performance composite material of light weight, while its conductive network structure formed can make highly sensitive stretching and pressure sensing
Device.The unique Spiral morphology of spiral carbon nanotubes and screw diameter and screw pitch and length are adjustable, have excellent high-efficient wide-frequency
The performance of electromagnetic wave absorption has broad application prospects in terms of the production of invisible coating or film.Spiral carbon nanometer simultaneously
Pipe has great specific surface area and chemical modifiability, electric conductivity and physical and chemical stability, in adsorption, catalysis, electricity
Also there is huge application market in the fields such as pond electrode.
However compared with carbon nanotube, spiral carbon nanomaterial finds the producer for being actually suitable for largely preparing not yet
Method, this just hinders its application in practice.
The spiral carbon material synthetic method having disclosed at present mainly uses chemical vapor deposition method, and using laterally
It is prepared by horizontal reacting furnace.And generally use flat substrate as the carrying body of catalyst in this approach, one prepared
Journey needs to charge, heating, keeps the process of (in reaction temperature), cooling and feeding, and is not easy continuous production, therefore cannot
For industrial mass production spiral carbon material.
Summary of the invention
The present invention by a kind of low cost, serialization, can mass production helical form carbon material method, solve above-mentioned
Problem.
The present invention provides a kind of methods of fluidized bed process continuous production helical form carbon material, and the method includes walking as follows
It is rapid: by can with the catalyst loading of growth spiral shape carbon material on particle, catalyst be the chemical combination containing ferro element and tin element
Object, the compound containing ferro element and phosphide element, the compound containing ferro element, tin element and phosphide element, iron content element compound and
The mixture of stanniferous element compound, the mixture of iron content element compound and the compound containing phosphide element, iron content element compound,
Stanniferous element compound and the mixture of the compound containing phosphide element, the mixture of iron powder and glass putty, iron powder and indium powder mixture,
The mixture of iron powder, glass putty and indium powder；Reaction zone is first heated to 600-1000 DEG C, then from the bottom of reaction zone into reaction zone
It is passed through reactant gas and non-interactive gas, then the particle for being supported with catalyst is added in reaction zone, in reactivity
It is suspended in particle in reaction zone under the blowing of gas and non-interactive gas, reactant gas is the gas containing carbon and hydrogen；
In catalyst surface catalytic pyrolysis reaction occurs for the gas containing carbon and hydrogen being passed through, and helical form carbon material is in the particle table to swim
Face is gradually grown, reaction time > 5min；Growth spiral shape carbon material reaches non-live after the scheduled reaction time on particle
The mixed gas for sprinkling property gas or reactant gas and non-interactive gas blows out reaction zone, then supplements and support into reaction zone
There is the particle of catalyst；It repeats the above steps, forms continuous production.
The present invention is preferably that the shape for being supported with catalyst granules is spherical or Polyhedral.
The present invention is preferably that the size for being supported with catalyst granules is 10nm-10mm.
The present invention is preferably that the material of the particle is aluminium oxide, silica, silicon carbide, silicon nitride, polystyrene, gathers
Ethylene or polyvinyl chloride.
The present invention is preferably that the reactant gas is acetylene, ethylene, methane or alcohol vapor.
The present invention is preferably that the non-interactive gas is nitrogen, argon gas or helium.
The present invention is preferably that the flow-rate ratio of the reactant gas and non-interactive gas is 1:4-100.
The present invention is preferably that the helical form carbon material is spiral carbon nanotubes, spiral carbon nano-fiber and spiral carbon micron
Fiber.
The invention has the following beneficial effects:
The present invention breaches the bottleneck for preparing helical form carbon material in the prior art, realizes helical form carbon material serialization
A large amount of production, lays a solid foundation for helical form carbon material practical application.
Detailed description of the invention
7 width of attached drawing of the present invention,
Fig. 1 is the flow chart of the method for the invention；
Fig. 2 is electron micrograph of the spiral carbon nanotubes of the preparation of embodiment 1 in the case where amplifying 30 times of states；
Fig. 3 is electron micrograph of the spiral carbon nanotubes of the preparation of embodiment 1 in the case where amplifying 2400 times of states；
Fig. 4 is electron micrograph of the spiral carbon nanotubes of the preparation of embodiment 2 in the case where amplifying 34 times of states；
Fig. 5 is electron micrograph of the spiral carbon nanotubes of the preparation of embodiment 2 in the case where amplifying 2200 times of states；
Fig. 6 is electron micrograph of the spiral carbon nanotubes of the preparation of embodiment 3 in the case where amplifying 34 times of states；
Fig. 7 is electron micrograph of the spiral carbon nanotubes of the preparation of embodiment 3 in the case where amplifying 1700 times of states.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Following method for preparing catalyst containing ferro element and tin element be (referring to Chinese Patent Application No.:
201811189147.4): by Fe (NO3)3·9H2O and SnCl4·5H2O (molar ratio of Fe atom and Sn atom is 10:1) dissolution
In n,N-Dimethylformamide, it is sufficiently stirred and moves back into pyroreaction kettle, 180 DEG C of reaction 30h, cooled to room temperature,
Red precipitate is catalyst in product, is respectively adopted after acetone, alcohol, deionized water cleaning for use.
Embodiment 1
A kind of method of fluidized bed process continuous production spiral carbon nanotubes, described method includes following steps:
By can with the catalyst loading of growth spiral shape carbon material on particle, catalyst be it is above-mentioned containing ferro element and tin member
The compound of element, the material of particle are aluminium oxide, and the particle for being supported with catalyst is diameter 1mm spherical；
Reaction zone is first heated to 710 DEG C, then is passed through acetylene and argon gas into reaction zone from the bottom of reaction zone, acetylene and
The flow-rate ratio of argon gas is 1:9, then the particle for being supported with catalyst is added in reaction zone, under the blowing of acetylene and argon gas
It is suspended in particle in reaction zone；
The acetylene being passed through catalyst surface occur catalytic pyrolysis reaction, spiral carbon nanotubes the particle surface to swim by
One-step growth, reaction time 30min；
Growth spiral carbon nanotube, which reaches, on particle blows out reaction zone, then Xiang Fanying by acetylene and argon gas after the reaction time
Supplement is supported with the particle of catalyst in area；
It repeats the above steps, forms continuous production.
Embodiment 2
A kind of method of fluidized bed process continuous production spiral carbon nanotubes, it is characterised in that: the method includes walking as follows
It is rapid:
By can with the catalyst loading of growth spiral shape carbon material on particle, catalyst be it is above-mentioned containing ferro element and tin member
The compound of element, the material of particle are aluminium oxide, and being supported with catalyst granules is size 0.5mm Polyhedral；
Reaction zone is first heated to 710 DEG C, then is passed through acetylene and argon gas into reaction zone from the bottom of reaction zone, acetylene and
The flow-rate ratio of argon gas is 1:9, and then the particle for being supported with catalyst is added in reaction zone, makes particle under the blowing of argon gas
It is suspended in reaction zone；
The acetylene being passed through catalyst surface occur catalytic pyrolysis reaction, spiral carbon nanotubes the particle surface to swim by
One-step growth, reaction time 30min；
Growth spiral carbon nanotube, which reaches, on particle blows out reaction zone, then Xiang Fanying by acetylene and argon gas after the reaction time
Supplement is supported with the particle of catalyst in area；
It repeats the above steps, forms continuous production.
Embodiment 3
A kind of method of fluidized bed process continuous production spiral carbon nanotubes, described method includes following steps:
By can with the catalyst loading of growth spiral shape carbon material on particle, catalyst be it is above-mentioned containing ferro element and tin member
The compound of element, the material of particle are aluminium oxide, and being supported with catalyst granules is 20 μm of spherical shapes of diameter；
Reaction zone is first heated to 710 DEG C, then is passed through acetylene and argon gas from the bottom of reaction zone to reaction zone, it then will load
The particle for being loaded with catalyst is added in reaction zone, is suspended in particle in reaction zone under the blowing of acetylene and argon gas, acetylene
Flow-rate ratio with argon gas is 1:9；
The acetylene being passed through catalyst surface occur catalytic pyrolysis reaction, spiral carbon nanotubes the particle surface to swim by
One-step growth, reaction time 30min；
Growth spiral carbon nanotube, which reaches, on particle blows out reaction zone, then Xiang Fanying by acetylene and argon gas after the reaction time
Supplement is supported with the particle of catalyst in area；
It repeats the above steps, forms continuous production.
Claims (8)
1. a kind of method of fluidized bed process continuous production helical form carbon material, it is characterised in that: described method includes following steps:
By can with the catalyst loading of growth spiral shape carbon material on particle, catalyst be the chemical combination containing ferro element and tin element
Object, the compound containing ferro element and phosphide element, the compound containing ferro element, tin element and phosphide element, iron content element compound and
The mixture of stanniferous element compound, the mixture of iron content element compound and the compound containing phosphide element, iron content element compound,
Stanniferous element compound and the mixture of the compound containing phosphide element, the mixture of iron powder and glass putty, iron powder and indium powder mixture,
The mixture of iron powder, glass putty and indium powder；
Reaction zone is first heated to 600-1000 DEG C, then is passed through reactant gas and non-live into reaction zone from the bottom of reaction zone
Property gas is sprinkled, then the particle for being supported with catalyst is added in reaction zone, in reactant gas and non-interactive gas
Blowing down is suspended in particle in reaction zone, and reactant gas is the gas containing carbon and hydrogen；
In catalyst surface catalytic pyrolysis reaction occurs for the gas containing carbon and hydrogen being passed through, and helical form carbon material is in swim
Grain surface is gradually grown, reaction time > 5min；
On particle growth spiral shape carbon material reach after the scheduled reaction time by non-interactive gas or reactant gas and
The mixed gas of non-interactive gas blows out reaction zone, then supplement is supported with the particle of catalyst into reaction zone；
It repeats the above steps, forms continuous production.
2. the method for fluidized bed process continuous production helical form carbon material according to claim 1, it is characterised in that: described to support
There is the shape of catalyst granules for spherical or Polyhedral.
3. the method for fluidized bed process continuous production helical form carbon material according to claim 2, it is characterised in that: described to support
The size for having catalyst granules is 10nm-10mm.
4. the method for fluidized bed process continuous production helical form carbon material according to claim 3, it is characterised in that: the particle
Material be aluminium oxide, silica, silicon carbide, silicon nitride, polystyrene, polyethylene or polyvinyl chloride.
5. the method for fluidized bed process continuous production helical form carbon material according to claim 4, it is characterised in that: the reaction
Property gas be acetylene, ethylene, methane or alcohol vapor.
6. the method for fluidized bed process continuous production helical form carbon material according to claim 5, it is characterised in that: described non-live
Sprinkling property gas is nitrogen, argon gas or helium.
7. the method for fluidized bed process continuous production helical form carbon material according to claim 6, it is characterised in that: the reaction
Property gas and non-interactive gas flow-rate ratio be 1:4-100.
8. the method for fluidized bed process continuous production helical form carbon material according to claim 7, it is characterised in that: the spiral
Shape carbon material is spiral carbon nanotubes, spiral carbon nano-fiber and spiral carbon micrometer fibers.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| CN106395795A (en) * | 2016-08-31 | 2017-02-15 | 潍坊昊晟碳材料有限公司 | Continuous carbon nanotube fluidized bed preparation method |
| CN107311150A (en) * | 2017-08-25 | 2017-11-03 | 安徽智博新材料科技有限公司 | A kind of method that high efficiency continuously fluid bed prepares CNT |
| CN109201068A (en) * | 2018-10-12 | 2019-01-15 | 大连理工大学 | A kind of preparation method and applications for the carbon nanocoil catalyst for synthesizing reducing by-product carbon-coating |
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- 2019-03-26 CN CN201910233917.9A patent/CN109761220A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348249A (en) * | 2008-09-05 | 2009-01-21 | 清华大学 | Method for preparing carbon nano-tube array on particle interior surface |
| CN106395795A (en) * | 2016-08-31 | 2017-02-15 | 潍坊昊晟碳材料有限公司 | Continuous carbon nanotube fluidized bed preparation method |
| CN107311150A (en) * | 2017-08-25 | 2017-11-03 | 安徽智博新材料科技有限公司 | A kind of method that high efficiency continuously fluid bed prepares CNT |
| CN109201068A (en) * | 2018-10-12 | 2019-01-15 | 大连理工大学 | A kind of preparation method and applications for the carbon nanocoil catalyst for synthesizing reducing by-product carbon-coating |
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