CN106395793B - A kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one - Google Patents
A kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one Download PDFInfo
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- CN106395793B CN106395793B CN201610782461.8A CN201610782461A CN106395793B CN 106395793 B CN106395793 B CN 106395793B CN 201610782461 A CN201610782461 A CN 201610782461A CN 106395793 B CN106395793 B CN 106395793B
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Abstract
This patent provides a kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one,Catalyst reduction activation and carburizing reagent are coupled in one by the present invention,By means of the waste heat of the cracked gas of carbon nano tube growth reaction process,The reduction activation of catalyst is completed in carbonisation,Save the operating time,Effectively improve the efficiency of entire reaction unit,Effectively avoid catalyst catalyst granules as caused by the charging of air pulse spray regime broken,Simultaneously,Carbon nano tube growth reactor is made of two sections with the fluidized bed of circulation,Effectively improve inside reactor heat and mass efficiency,Reinforce gas-solid contacting efficiency,Avoid the problem that conversion zone Temperature Distribution caused by carbon pipe fast-growth and reactant concentration are unevenly distributed,The problem of can also preventing the fluidized status as caused by the formation of carbon nanotube or graphene macroaggregate from deteriorating.
Description
Technical field
The invention belongs to carbon material preparation technical fields, and it is efficient to be related to reduction activation-reaction coupling one carbon nanotube
Preparation method.
Background technique
Carbon nanotube has extremely broad application prospect with its unique structure and excellent performance.Because it has good
Electric conductivity, physical and chemical stability and higher mechanical strength, they are in conductive additive, catalysis and composite strengthening toughening material
Material etc. has a good application prospect.
The premise that carbon nanomaterial is used widely is the development and maturation of inexpensive batch techniques, at present in carbon nanometer
Pipe production aspect mostly uses chemical vapor deposition method.Specific chemical vapor deposition method 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.In addition, easily being made during the good catalyst of reduction activation is conveyed and shifted toward carbonization reactor
At the broken of catalyst granules, the growth morphology and speed of carbon pipe are changed.The operating time of every batch of is long, entire reaction unit
It is inefficient.
Meanwhile the fluidized bed production reactor that existing technology proposes is because of temperature distributing characteristic and hydrocarbon gas Pintsch process
The endothermic character of reaction is unable to the production carbon nanotube of high yield.Therefore, it is necessary to a kind of new high efficiency preparation method is provided,
To overcome drawbacks described above.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of reduction activation-reaction coupling one carbon nanotube is high
Preparation method is imitated, it saves the operating time, effectively improves the efficiency of entire reaction unit, avoids catalyst due to air pulse
Catalyst granules caused by spray regime is fed is broken, improves carbon pipe growth morphology and speed.
Above-mentioned purpose of the invention is achieved through the following technical solutions, and is included the following steps：
A kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one, includes the following steps：
A kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one, includes the following steps：
(1) it is catalyzed reduction activation：The catalyst reduction activated reactor that will be made of a metallic material is placed on carbon nanotube
In reactor, by means of the cracked gas waste heat on the carbonization reactor top of carbon nano tube growth reaction process, catalyst is completed
Reduction activation process, the carbon nanotube carbonization growth reactor is by one section of circulation fluidized bed, two sections of circulation fluidized beds and sinks
Section composition drops；
(2) carburizing reagent：Add an air pulse at the top of catalyst reduction activated reactor, catalyst is pushed to downwards
Carburizing reagent is carried out in fluidized bed carbonization reactor, is by the control of the temperature of one section of circulation fluidized bed and two sections of circulation fluidized beds
550~750 DEG C, carbon-source gas and inert gas are passed through in the inner cylinder distributor of two sections of circulation fluidized beds and annular space distributor respectively
Mixed gas, gas mixing ratio control be carbon-source gas：Inert gas=0.5~2.0：1, the carburizing reagent time be 40~
Solids product is discharged from discharge port after the reaction was completed in 90min..
Preferably, the process conditions of the catalysis reduction are：In carbon nanotube preparation process, catalyst is sent to by leading
In reduction activation fluidized-bed reactor made of the good metal material of hot property, the temperature of fluidized bed is 350~650 DEG C, is led to
In the mixed gas to reactor for entering hydrogen and inert gas, wherein the proportion of hydrogen and inert gas is 0.5~2.0：1, dimension
Reduction activation 5~20min of process is held, the void tower linear speed flow velocity of gas is 0.05~2.0m/s.
Preferably, the inner/outer tube radius ratio of two sections of circulation fluidized beds of carbonization reactor 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.
Preferably, the reduction activation fluidized-bed reactor can be with top half by the good metal material of heating conduction
Material is made, and lower half portion is made of the powder of stainless steel agglomerated material for capableing of filtration, and the pneumatically unlatching of bottom is board-like close
Envelope valve valve plate be also thus powder of stainless steel agglomerated material be made；Using carbon nanotube preparation process generate containing 20~
The cracking gas of 50% hydrogen carries out the reduction activation of catalyst as reducing agent.
Preferably, the carbon source is hydrocarbon, methanol, ethyl alcohol or propyl alcohol.
Preferably, the catalyst is single-phase transition metal or its alloy, or contains the organic of above-mentioned metal or alloy
Compound.
Beneficial effects of the present invention：The present invention is carried out using the cracking gas that carbon nanotube preparation process generates as reducing agent
The reduction activation of catalyst both can save the operating time, improve work efficiency under the premise of not changing operating process,
Hydrogen and the usage amount of other inert medias can be saved again, reduced costs；Catalyst is effectively avoided to spray due to air pulse
Catalyst granules caused by the mode of penetrating is fed is broken；Fluidized bed group of the carbon nano tube growth reactor by two sections with circulation
At effectively improving inside reactor heat and mass efficiency, reinforce gas-solid contacting efficiency, avoid caused by carbon pipe fast-growth anti-
The problem of answering regional temperature distribution and reactant concentration to be unevenly distributed, additionally it is possible to prevent due to carbon nanotube or graphene bulky grain
The problem of fluidized status caused by the formation of aggregation deteriorates.The reaction unit can be used for single-walled carbon nanotube, multi-wall carbon nano-tube
The production of pipe.
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.
Fig. 2 is the schematic diagram of the embodiment of the present invention 2.
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
A kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one, includes the following steps, process is as schemed
1：
(1) catalyst reduction activates：In the normal flow fluidized bed reactor 101 made of heating conduction good metal material
Interior progress, catalyst reduction activated reactor 101 are placed in carbon nanotube reactor 103, specifically in carbon nanotube reactor
In the settling section 1033 on 103 tops.In carbon nanotube preparation process, the carbonization by means of carbon nano tube growth reaction process is anti-
The cracked gas waste heat on device top is answered, catalyst reduction activation process is completed.
Carbon nanotube reactor 103 is made of three parts, one section of circulation fluidized bed 1031, two sections of circulation fluidized beds 1032,
And settling section 1033.
In carbon nanotube preparation growth course, catalyst 1 is sent to made of the good metal material of heating conduction
In reduction activation fluidized-bed reactor 101, fluidized-bed temperature control is 350~650 DEG C, is passed through the mixed gas of hydrogen and nitrogen
2 arrive in the reactor 101, and gas mixing ratio is hydrogen：Nitrogen or argon gas=0.5~2.0, maintenance reduction activation process 5~
20min, linear gas velocity control are 0.05~2.0m/s.
(2) carburizing reagent：The board-like sealing valve pneumatically opened is set in the bottom of catalyst reduction activated reactor 101
102, after catalyst 1 completes reduction activation, just carbon nanotube preparation process terminates, and completes to produce from discharge port discharge solid phase
Product open board-like sealing valve 102, while adding an air pulse 3 at the top of catalyst reduction activated reactor 101, by catalyst
It is pushed in fluidized bed carbon nanotube reactor 103 downwards.
The temperature for maintaining circulation fluidized bed 1031 and 1032 is 550~750 DEG C.Then, respectively in one section of circulation fluidized bed
Inner cylinder distributor 10311, annular space distributor 10312, inner cylinder distributor 10321, the annular space distributor of two sections of circulation fluidized beds
10322 are 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：Nitrogen or argon gas
=0.5~2.0, carry out 40~90min of carburizing reagent.
One section of circulation fluidized bed 1031 of carbon nanotube reactor 103 and the inner/outer tube radius of two sections of circulation fluidized beds 1032
Than controlling 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) solids product 5 is discharged from discharge port 104 after the reaction was completed, carburizing reagent cracking gas 6 is from carbonization reactor 103
Top discharge.
Embodiment 2
A kind of carbon nanotube high efficiency preparation method of reduction activation-reaction coupling one, includes the following steps, process is as schemed
2：
(1) catalyst reduction activates：In the normal flow fluidized bed reactor 101 made of heating conduction good metal material
Interior progress, catalyst reduction activated reactor 101 are placed in carbon nanotube reactor 103, specifically in carbon nanotube reactor
In the settling section 1033 on 103 tops.101 top half 1011 of reduction activation fluidized-bed reactor of catalyst is good by heating conduction
Good metal material is made, and lower half portion 1012 is made of the powder of stainless steel agglomerated material for capableing of filtration, bottom
Pneumatically open board-like sealing valve 102 valve plate be also thus powder of stainless steel agglomerated material be made.
In carbon nanotube preparation process, by means of the cracking on the carbonization reactor top of carbon nano tube growth reaction process
Hydrogen in gas waste-heat and cracking gas completes catalyst reduction activation process.
Carbon nanotube reactor 103 is made of three parts, one section of circulation fluidized bed 1031, two sections of circulation fluidized beds 1032,
And settling section 1033.
In carbon nanotube preparation growth course, catalyst 1 is sent to being made of the good metal material of heating conduction and
In reduction activation fluidized-bed reactor 101 made of powder of stainless steel agglomerated material, fluidized-bed temperature control is 350~650 DEG C.
The cracking gas of carburizing reagent is sintered filter plate by 102 and 1012 powder of stainless steel and fluidizes to catalyst 1, with catalyst
Contact carries out the reduction activation of catalyst, maintains 5~20min of reduction activation process, and linear gas velocity control is 0.05~2.0m/
s。
(2) carburizing reagent：The board-like sealing valve pneumatically opened is set in the bottom of catalyst reduction activated reactor 101
102, after catalyst 1 completes reduction activation, just carbon nanotube preparation process terminates, and completes to produce from discharge port discharge solid phase
Product open board-like sealing valve 102, while adding an air pulse 3 at the top of catalyst reduction activated reactor 101, by catalyst
It is pushed in fluidized bed carbon nanotube reactor 103 downwards.
The temperature for maintaining circulation fluidized bed 1031 and 1032 is 550~750 DEG C.Then, respectively in one section of circulation fluidized bed
Inner cylinder distributor 10311, annular space distributor 10312, inner cylinder distributor 10321, the annular space distributor of two sections of circulation fluidized beds
10322 are 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：Nitrogen or argon gas
=0.5~2.0, carry out 40~90min of carburizing reagent.
One section of circulation fluidized bed 1031 of carbon nanotube reactor 103 and the inner/outer tube radius of two sections of circulation fluidized beds 1032
Than controlling 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.
Solids product 5 is discharged from discharge port 104 after the reaction was completed.Carburizing reagent cracking gas 6 is from reduction activation fluidized bed 101
Top discharge.
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 (6)
1. a kind of reduction activation-reaction coupling one carbon nanotube high efficiency preparation method, it is characterised in that：Including following step
Suddenly：
(1) it is catalyzed reduction activation：The catalyst reduction activated reactor that will be made of a metallic material is placed on carbon nanotube reaction
In device, by means of the cracked gas waste heat on the carbonization reactor top of carbon nano tube growth reaction process, catalyst reduction is completed
Activation process, the carbon nanotube carbonization growth reactor is by one section of circulation fluidized bed, two sections of circulation fluidized beds and settling section
Composition；
(2) carburizing reagent：Add an air pulse at the top of catalyst reduction activated reactor, catalyst is pushed to downwards to fluidisation
Carry out carburizing reagent in bed carbonization reactor, by the control of the temperature of one section of circulation fluidized bed and two sections of circulation fluidized beds for 550~
750 DEG C, the mixed of carbon-source gas and inert gas is passed through in the inner cylinder distributor of two sections of circulation fluidized beds and annular space distributor respectively
Gas is closed, gas mixing ratio control is carbon-source gas：Inert gas=0.5~2.0：1, the carburizing reagent time is that 40~90min. is anti-
Solids product is discharged from discharge port after the completion of answering.
2. a kind of reduction activation according to claim 1-reaction coupling one carbon nanotube high efficiency preparation method, special
Sign is：It is described catalysis reduction process conditions be：In carbon nanotube preparation process, catalyst is sent to good by heating conduction
In reduction activation fluidized-bed reactor made of good metal material, the temperature of fluidized bed is 350~650 DEG C, be passed through hydrogen with
In the mixed gas to reactor of inert gas, wherein the proportion of hydrogen and inert gas is 0.5~2.0：1, maintain reduction to live
Change 5~20min of process, the void tower linear speed flow velocity of gas are 0.05~2.0m/s.
3. a kind of reduction activation according to claim 1-reaction coupling one carbon nanotube high efficiency preparation method, special
Sign is：The inner/outer tube radius ratio of two sections of circulation fluidized beds of carbonization reactor controls r/R=0.3~0.8；Inner cylinder ratio of height to diameter control
L/r=4~9 processed；Inner/outer tube gas line Transmission Ratio Control 2~4.
4. a kind of reduction activation according to claim 1-reaction coupling one carbon nanotube high efficiency preparation method, special
Sign is：The reduction activation fluidized-bed reactor top half is made of the good metal material of heating conduction, lower half
Divide and be made of the powder of stainless steel agglomerated material for capableing of filtration, the valve plate for pneumatically opening board-like sealing valve of bottom is also
Thus powder of stainless steel agglomerated material is made；Using carbon nanotube preparation process generate containing 20~50% hydrogen cracking
Gas carries out the reduction activation of catalyst as reducing agent.
5. a kind of reduction activation according to claim 1-reaction coupling one carbon nanotube high efficiency preparation method, special
Sign is：The carbon source is hydrocarbon, methanol, ethyl alcohol or propyl alcohol.
6. a kind of reduction activation according to claim 1-reaction coupling one carbon nanotube high efficiency preparation method, special
Sign is：The catalyst is single-phase transition metal or its alloy, or the organic compound containing above-mentioned metal or alloy.
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| 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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| 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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