CN106430150B - A kind of carbon nanotube fluidized bed preparation method of continuous high-efficient - Google Patents
A kind of carbon nanotube fluidized bed preparation method of continuous high-efficient Download PDFInfo
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Abstract
The present invention provides a kind of carbon nanotube fluidized bed preparation methods of continuous high-efficient, the carbon nanotube fluidized bed preparation method of the continuous high-efficient is made of catalyst reduction activation and carburizing reagent two parts, wherein carbon nano tube growth reactor is divided into the fluidized-bed reactor of two sections, carbon nano tube growth reaction process carries out in the biggish upper section fluidized bed with circulation of internal diameter, operating linear velocity control is being higher than catalyst and the short grained minimum fluidization velocity of carbon nanotube, and it is lower than the minimum fluidization velocity of carbon nanotube agglomerate bulky grain, come to make this part carbon nanotube agglomerate bulky grain screen out from the multiple dimensioned particle stream of carbon nanotube reactor, continuously into lower section fluidized bed, collector as carbon nanotube agglomerate bulky grain, use inert gas for fluidizing agent, it is at loosening state, convenient for from anti- It answers device to remove, really realizes serialization preparation.
Description
Technical field
The invention belongs to carbon material preparation technical fields, are related to a kind of continuous carbon nanotube fluidized bed preparation method.
Background technique
Carbon nanotube is considered as a kind of new function material and structural material haveing excellent performance, and becomes and grinds in the latest 20 years
The hot spot studied carefully.Up to the present, preparation carbon nanotube is there are many method, but most important method only there are three types of, i.e., arc process,
Laser ablation method and catalystic pyrolysis.Catalystic pyrolysis is with nano-level iron, brill or silver for catalyst, and low-carbon is short, oxidation of coal closes
Object or carbon monoxide are unstripped gas, and the method for catalytic cracking reaction growth carbon nanotube occurs at high temperature.This method is produced
Carbon nano pipe purity is high, specification is controllable, and is easy to industrial amplification, it is considered to be most has the preparation carbon nanotube of development prospect
Method.
In the catalystic pyrolysis mostly used in terms of the carbon nanotube production at present, prior art is using fluidized-bed reaction
Device, but before carbon nanotube preparation, it needs to carry out reduction activation to its catalyst, because the control of every batch of carbon is catalyzed for required for
Dosage is few, and reduction activation condition is special, needs to carry out in another individual reactor, and connect with carbonation reaction
It carries out, process is cumbersome, complicated, can not achieve serialization preparation truly.Meanwhile fluidized-bed reactor is because of temperature point
The endothermic character of cloth characteristic and the reaction of hydrocarbon gas Pintsch process, is unable to the production carbon nanotube of high yield.
Therefore, it is necessary to a kind of new high efficiency continuously preparation method be provided, to overcome drawbacks described above.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of carbon nanotube fluidized bed systems of continuous high-efficient
Preparation Method, the reduction activation and carburizing reagent of catalyst carry out in same reactor in this method, and process is simple, realizes carbon
It is prepared by the high efficiency continuously of nanotube.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of carbon nanotube fluidized bed preparation method of continuous high-efficient, comprising the following steps:
(1) it is activated by catalyst reduction；
(2) catalyst for completing reduction activation carburizing reagent: is transmitted to the fluidisation with circulation using screw conveyer mode
In bed carbonization reactor, maintaining temperature is 550~750 DEG C, respectively in the inner cylinder distributor of circulation fluidized bed and annular space distributor
It is passed through the mixed gas of carbon-source gas and inert gas, gas mixing ratio is carbon-source gas: inert gas=0.5~2.0:1, mixing
The linear speed control of gas is higher than catalyst and the short grained minimum fluidization velocity of carbon nanotube in 0.5~1.5m/s, and is lower than carbon
The minimum fluidization velocity of Nanotube Aggregates bulky grain, circular fluidized-bed reactor inner cylinder or annular space air speed control 0.6~
1.5hr-1, carbon nano tube growth reaction process carries out in the biggish upper section fluidized bed with circulation of internal diameter；
(3) carbon nanotube midwifery is long and collects: carbon nano tube growth reaction is carried out in the biggish upper section fluidized bed of internal diameter,
With the progress of carburizing reagent, carbon nanotube agglomerate bulky grain is constantly from the multiple dimensioned particle stream of carbon nanotube reactor
It screens out and, be collection carbon nanotube agglomerate bulky grain by lower section fluidized bed continuously into lower section fluidized bed, and continuous
Equably removed from reactor.
Preferably, the catalyst reduction activating process are as follows: by way of screw conveyer continuously and uniformly by catalyst
It send into reduction activation fluidized-bed reactor, temperature control is 350~650 DEG C, is passed through the gaseous mixture of hydrogen and nitrogen or argon gas
In body to reactor, gas mixing ratio is hydrogen: nitrogen or argon gas=0.5~2.0, the air speed of reduction activation process is 100~
5000 hours -1, linear gas velocity control is 0.05~2.0m/s.
Preferably, the collection process of the carbon nanotube are as follows: use inert gas for fluidizing agent, control linear speed is 0.1
~0.5m/s makes collector be in loosening state, is removed by screw conveyer mode or air pulse injection from reactor.
Preferably, the inner/outer tube radius ratio of the circulation fluidized bed of carbonization reactor controls r/R=0.3~0.8；Inner cylinder Gao Jing
Than controlling l/r=4~9；Inner/outer tube gas line Transmission Ratio Control 2~4；
Preferably, the carbon source is the following hydrocarbon of five carbon, methanol, ethyl alcohol or propyl alcohol；
6, a kind of carbon nanotube fluidized bed preparation method of continuous high-efficient according to claim 1, feature exist
In the catalyst is single-phase transition metal or its alloy, or the organic compound containing above-mentioned metal or alloy.
Beneficial effects of the present invention: the present invention provides a kind of continuous carbon nanotube fluidized bed preparation method, in this method
The reduction activation and carburizing reagent of catalyst carry out in same reactor, and process is simple, realize efficiently connecting for carbon nanotube
Continuousization preparation.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the schematic diagram of the embodiment of the present invention 1.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
Embodiment 1:
Present embodiments provide a kind of continuous carbon nanotube fluidized bed preparation method, comprising the following steps: process is as schemed
1:
(1) it is activated by catalyst reduction: catalyst 1 is continuously and uniformly sent by way of screw conveyer to reduction activation
In fluidized-bed reactor 101, temperature control is 350~650 DEG C, is passed through hydrogen and the mixed gas 2 of nitrogen or argon gas to reacting
In device, gas mixing ratio is hydrogen: nitrogen or argon gas=0.5~2.0, and the air speed of reduction activation process is 100~5000 hours -1,
Linear gas velocity control is 0.05~2.0m/s.
(2) carburizing reagent: by same mass flowrate will complete the catalyst 3 of reduction activation using screw conveyer in a manner of
102 are transmitted in fluidized bed carbonization reactor 103.
The temperature for maintaining circulation fluidized bed 103 is 550~750 DEG C.Then, respectively in the inner cylinder distributor of circulation fluidized bed
1031, annular space distributor 1032 is passed through the mixed gas 4 of the following lower carbon number hydrocarbons of five carbon and nitrogen or argon gas, and gas mixing ratio is carbon source gas
Body: nitrogen or argon gas=0.5~2.0 exist in the linear speed control of circular fluidized-bed reactor inner cylinder or annular space, mixed gas 4
0.5~1.5m/s is higher than catalyst and the short grained minimum fluidization velocity of carbon nanotube, and is lower than carbon nanotube agglomerate big
The minimum fluidization velocity of grain, circular fluidized-bed reactor inner cylinder or annular space air speed control 0.6~1.5hr-1.
The inner/outer tube radius ratio of circular fluidized-bed reactor 103 controls r/R=0.3~0.8；Inner cylinder ratio of height to diameter controls l/r
=4~9；Inner/outer tube gas line Transmission Ratio Control 2~4.
(3) carbon nanotube midwifery is long and collects: with the progress of carburizing reagent, carbon nanotube agglomerate bulky grain is constantly
It screens out and from the multiple dimensioned particle stream of carbon nanotube reactor 103, continuously into lower section fluidized bed 104, received as carbon
The collector of mitron aggregation bulky grain uses such as nitrogen or the argon gas of inert gas 5 for fluidizing agent, by distributor 1041 into
Enter 104 bottoms, control linear speed is 0.1~0.5m/s, is at loosening state, is sprayed by screw conveyer mode or air pulse
It penetrates mode and removes product 6 from lower section fluidized bed collector 104, really realize serialization preparation.
Carburizing reagent cracking gas 7 is discharged at the top of carbonization reactor 103.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in process, method, article or equipment including the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (3)
1. a kind of carbon nanotube fluidized bed preparation method of continuous high-efficient, which comprises the following steps:
(1) it is activated by catalyst reduction；
(2) catalyst for completing reduction activation carburizing reagent: is transmitted to the fluidized bed carbon with circulation using screw conveyer mode
Change in reactor, maintaining temperature is 550~750 DEG C, is passed through respectively in the inner cylinder distributor of circulation fluidized bed and annular space distributor
The mixed gas of carbon-source gas and inert gas, gas mixing ratio are carbon-source gas: inert gas=0.5~2.0:1, mixed gas
Linear speed control in 0.5~1.5m/s, be higher than catalyst and the short grained minimum fluidization velocity of carbon nanotube, and be lower than carbon nanometer
The minimum fluidization velocity of pipe aggregation bulky grain, circular fluidized-bed reactor inner cylinder or annular space air speed control 0.6~1.5hr-1,
Carbon nano tube growth reaction process carries out in the biggish upper section fluidized bed with circulation of internal diameter；
(3) carbon nano tube growth and collection: carbon nano tube growth reaction is carried out in the biggish upper section fluidized bed of internal diameter, with carbon
Change the progress of reaction, carbon nanotube agglomerate bulky grain is constantly screened out from the multiple dimensioned particle stream of carbon nanotube reactor
Come, is collection carbon nanotube agglomerate bulky grain by lower section fluidized bed continuously into lower section fluidized bed, and continuously and uniformly
It is removed from reactor；
The catalyst reduction activating process are as follows: continuously and uniformly send catalyst to reduction activation by way of screw conveyer
In fluidized-bed reactor, temperature control is 350~650 DEG C, is passed through in the mixed gas to reactor of hydrogen and nitrogen or argon gas,
Gas mixing ratio is hydrogen: nitrogen or argon gas=0.5~2.0, and the air speed of reduction activation process is 100~5000 hours-1, gas line
Speed control is 0.05~2.0m/s；
The collection process of the carbon nanotube are as follows: use inert gas for fluidizing agent, control linear speed is 0.1~0.5m/s, is made
Collector is in loosening state, is removed by screw conveyer mode or air pulse injection from reactor；The ring of carbonization reactor
The inner/outer tube radius ratio for flowing fluidized bed controls r/R=0.3~0.8；Inner cylinder ratio of height to diameter controls l/r=4~9；Inner/outer tube gas line
Transmission Ratio Control 2~4.
2. a kind of carbon nanotube fluidized bed preparation method of continuous high-efficient according to claim 1, which is characterized in that described
Carbon source be the following hydrocarbon of five carbon, methanol, ethyl alcohol or propyl alcohol.
3. a kind of carbon nanotube fluidized bed preparation method of continuous high-efficient according to claim 1, which is characterized in that described
Catalyst be single-phase transition metal or its alloy, or the organic compound containing above-mentioned metal or alloy.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327943A (en) * | 2001-05-25 | 2001-12-26 | 清华大学 | Process and reactor for continuously preparing nm carbon tubes with fluidized bed |
| CN101049927A (en) * | 2007-04-18 | 2007-10-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
| CN102120570A (en) * | 2011-01-22 | 2011-07-13 | 广州市白云化工实业有限公司 | Device and process method for continuously producing carbon nanotubes |
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| US6413487B1 (en) * | 2000-06-02 | 2002-07-02 | The Board Of Regents Of The University Of Oklahoma | Method and apparatus for producing carbon nanotubes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1327943A (en) * | 2001-05-25 | 2001-12-26 | 清华大学 | Process and reactor for continuously preparing nm carbon tubes with fluidized bed |
| CN101049927A (en) * | 2007-04-18 | 2007-10-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
| CN102120570A (en) * | 2011-01-22 | 2011-07-13 | 广州市白云化工实业有限公司 | Device and process method for continuously producing carbon nanotubes |
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