CN105174244B - A kind of preparation method of CNT - Google Patents
A kind of preparation method of CNT Download PDFInfo
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- CN105174244B CN105174244B CN201510549461.9A CN201510549461A CN105174244B CN 105174244 B CN105174244 B CN 105174244B CN 201510549461 A CN201510549461 A CN 201510549461A CN 105174244 B CN105174244 B CN 105174244B
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Abstract
The invention discloses a kind of preparation method of CNT, the preparation method of CNT is comprised the following steps：Nitrate or acetate with tri- kinds of materials of Fe, Al, Mg, using citric acid as complexing agent and pore creating material, solution is mixed into after adding water as raw material；By the roasting of above-mentioned solution, catalyst is made, the general structure of the catalyst is FeAlxMgyO, x=1~3, y=0.1~1；Using any one in catalyst cracking methane, ethene or propylene, CNT is obtained.A kind of preparation method of CNT of the present invention has raising CNT bulk density, improves yield, reduces production cost.
Description
Technical field
The present invention relates to CNT manufacturing technology field, more particularly to a kind of preparation method of CNT.
Background technology
The main flow of industrialization carbon nanotube product is multi-walled carbon nano-tubes at present, and its principle for preparing is using high-power
Energy input so that it is regularly arranged pipe that the carbon in carbon raw material is organized themselves into.According to energy input form and carbon source material
Etc. factor, there are three class main flow preparation methods at present：Graphite acr method, laser evaporization method and chemical vapour deposition technique.Graphite arc
Method and laser evaporization method are all locally to introduce high power using physical means such as electric arc or laser so that the atom of carbon
Structure is reset.Because local temperature can be up to 3000~4000 DEG C in mechanism, be conducive to the arrangement of graphite linings whole
Together, thus this kind of method obtain CNT typically have more perfect structure and purity higher.But this kind of method can
Governing factor is few, especially lasting, large area introducing and keep reaction required for high-energy input it is extremely difficult, this makes
Handy these methods are large-scale continuous, and to prepare CNT relatively difficult.Chemical vapour deposition technique, refers in catalyst action
Under, carbonaceous gas is cracked in certain temperature conditionss, and the carbon for depositing is organized into graphite due to the presence of catalyst
The cylinder of piece.By selecting more active carbon source, the temperature conditionss required for cracking can be relatively gentleer, low cost,
Controllability is good, is more suitable for being prepared on a large scale for CNT.Carbon is grown for CVD on the metallic catalysts such as iron, cobalt, nickel to receive
Mitron, after being adsorbed onto on metallic catalyst, reaction cracking produces metal carbides to carbon-source gas, when the concentration of wherein carbon reaches
Supersaturation is separated out after to a certain degree, the graphite linings of formation rule arrangement.The diameter of CNT is related to the diameter of metallic particles,
Spread by metal catalyst particles by carbon during the continuous production of CNT and driven.To sum up state institute, the shortcoming of the above method
Mainly：1st, mainly with transition metal ions (Ni, Co, Mo) as catalyst, it is related to various noxious materials to use；2nd, need with lanthanum
Series rare earth element simultaneously easily causes environmental disruption as dispersant, high cost；3rd, CNT caliber is uneven, Diameter distribution
Width, contains substantial amounts of amorphous carbon；4th, CNT oxidation resistance is poor, and degree of graphitization is low；5th, length of carbon nanotube can not
Control；6th, CNT ash content is high, and purity is low；7th, CNT contains the indissoluble catalyst carrier such as silicon salt, purification difficult；8th, carbon is received
Mitron bulk density is small, and production cost is high, is unfavorable for industrialized production.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of CNT, solves the above problems.
In order to solve the above technical problems, the present invention provides a kind of preparation method of CNT, comprise the following steps：
(1) nitrate or acetate with tri- kinds of materials of Fe, Al, Mg is as raw material, using citric acid as complexing agent and pore-creating
Agent, solution is mixed into after adding water；
(2) above-mentioned solution is calcined, is made catalyst, the general structure of the catalyst is FeAlxMgyO, x=0.1~
3, y=0.1~3；
(3) using any one in catalyst cracking methane, ethene or propylene, CNT is obtained.
As a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, Fe described in step (1)
Nitrate or acetate, the nitrate of Al or acetate, the nitrate of Mg or acetate, citric acid this four classes material mole
Ratio is Fe:Al:Mg=1:x:Y, 0.1≤x≤3,0.1≤y≤3；Citric acid/(Fe+Al+Mg)=z, 1≤z≤3.
As a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, roasted described in step (2)
The temperature of burning is 400~700 DEG C, and the time of roasting is 1~4 hour.
As a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, first described in step (3)
Any one ratio between catalyst in alkane, ethene or propylene is 40~90:1.
Used as a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, step is urged described in (3)
The time for changing cracking is 20~60min.
Used as a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, step is urged described in (3)
The temperature for changing cracking is 500~800 DEG C.
Used as a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, step is additionally added in (3)
Hydrogen participates in any one in catalyst cracking methane, ethene or propylene.
As a kind of a kind of preferred scheme of the preparation method of CNT of the present invention, first described in step (3)
The ratio of the flow of the flow of any one and hydrogen in alkane, ethene or propylene is 1：1~6:1.
The preparation method of CNT of the present invention, using Fe as active component, with Al2O3, MgO be active component
Dispersant, Fe-Al-Mg metal complexs are formed using citric acid complex method.Specifically, in the preparation, with the nitre of respective element
Hydrochlorate or acetate are raw material, using citric acid as complexing agent and pore creating material, solution are calcined 1~4 hour in 400~700 DEG C
Prepare catalyst.The catalyst has spinelle or spinel-like structural, and general structure is FeAlxMgyO, x=0.1~3, y=
0.1~3.Optimal Fe-Al-Mg ratios are determined by Orthogonal Optimization.Using the catalyst crack methane, ethene,
Propylene can obtain the CNT of different tube diameters scope, by controlling pyrolysis time, be capable of achieving CNT length it is controllable
Prepare.This catalyst can make the CNT of preparation have the yield of caliber and Geng Gao evenly.Specifically, being characterized in：1、
Avoid introducing high cost, the toxic heavy-metal elements such as Ni, Co, Mo in catalyst；2nd, catalyst activity component and dispersant make
With conventional alkali earth metal, it is to avoid environment is damaged；3rd, make CNT pipe diameter size controllable within the specific limits,
Caliber is more uniform；4th, CNT oxidation resistance and degree of graphitization are improved, electric conductivity is improved；5th, make CNT long
Degree is controllable within the specific limits；6th, CNT yield is improved, yield is reached more than 9 times；7th, avoid being urged using slightly solubility
Agent carrier, is easy to purify the CNT for obtaining high-purity；8th, CNT bulk density is improved, yield is improved, life is reduced
Produce cost.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will use needed for embodiment description
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill of field, without having to pay creative labor, other can also be obtained according to these accompanying drawings
Accompanying drawing.Wherein,
Fig. 1 is by FeAl1.7Mg0.1O4.15Cracking of ethylene is catalyzed in 700 DEG C prepare the scanning that CNT amplifies 100,000 times
Electromicroscopic photograph；
Fig. 2 is by FeAl1.7Mg0.1O4.15Cracking of ethylene is catalyzed in 700 DEG C and prepares the scanning electricity that CNT amplifies 50,000 times
Mirror photo；With,
Fig. 3 is by FeAl1.7Mg0.1O4.15Cracking of ethylene is catalyzed in 700 DEG C and prepares the scanning electricity that CNT amplifies 10,000 times
Mirror photo.
Specific embodiment
To enable the above objects, features and advantages of the present invention more obvious understandable, with reference to specific embodiment
The present invention is further detailed explanation.
A kind of preparation method of CNT proposed by the present invention, it comprises the following steps or operates.
Step 1, the nitrate or acetate with tri- kinds of materials of Fe, Al, Mg as raw material, using citric acid as complexing agent and making
Hole agent, solution is mixed into after adding water.
In one embodiment, the step can be with execution specific as follows：With the nitrate or second of tri- kinds of materials of Fe, Al, Mg
Hydrochlorate is raw material, using citric acid as complexing agent and pore creating material, solution is mixed into after adding water, wherein, the nitrate of the Fe
Or the molar ratio of the nitrate or acetate of acetate, Al, the nitrate of Mg or acetate, citric acid this four classes material is
Fe:Al:Mg=1:x:Y, 0.1≤x≤3,0.1≤y≤3；Citric acid/(Fe+Al+Mg)=z, 1≤z≤3.
Step 2, by the roasting of above-mentioned solution, is made catalyst, and the general structure of the catalyst is FeAlxMgyO, x=
0.1~3, y=0.1~3.
In one embodiment, the step can be with execution specific as follows：By above-mentioned solution temperature be 400~700 DEG C, when
Between to be calcined under conditions of 1~4 hour, be made catalyst, the general structure of the catalyst is FeAlxMgyO, x=0.1~
3, y=0.1~3.
Step 3, using any one in catalyst cracking methane, ethene or propylene, obtains CNT.
In one embodiment, the step can be with execution specific as follows：The use of the catalyst and hydrogen is 20 in the time
~60min, temperature are that under conditions of 500~800 DEG C, any one in catalytic cracking methane, ethene or propylene obtains carbon and receive
Mitron, wherein, any one ratio between catalyst in the methane, ethene or propylene is 40~90:1, the first
The ratio of the flow of the flow of any one and hydrogen in alkane, ethene or propylene is 1：1~6:1.
Production method of the present invention is described in detail in conjunction with specific embodiments below.
Embodiment one
202kg Fe (NO are weighed respectively3)3·9H2O, 318.86kg Al (NO3)3·9H2O, 12.82kg Mg (NO3)2·
9H2O, 537.99kg anhydrous citric acid, 720kg deionized waters pour into stirring in reactor and are allowed to fully dissolving.100 DEG C of oil baths
Heating, 85r/min mechanical agitations.Agitating heating is evaporated to solution viscosity and reaches 100mPas, by solution 500 DEG C in tunnel cave
It is calcined 3 hours with air atmosphere, obtains FeAl1.7Mg0.1O4.15Catalyst.
The crucible of each filling 6g catalyst fines is used into automatic feed system, the 700 DEG C of tube furnace reactions of continuous push-in
Area, regulation ethene flow 5m3/ h, hydrogen flowing quantity 1m3/ h, setting program makes each crucible be in the residence time of reaction zone
30min, releases crucible and is cooled down under nitrogen atmosphere protection.Fig. 1-Fig. 3 is referred to, Fig. 1 is by FeAl1.7Mg0.1O4.15In 700 DEG C
Catalysis cracking of ethylene prepares the stereoscan photograph that CNT amplifies 100,000 times；Fig. 2 is by FeAl1.7Mg0.1O4.15In 700 DEG C
Catalysis cracking of ethylene prepares the stereoscan photograph that CNT amplifies 50,000 times；With Fig. 3 is by FeAl1.7Mg0.1O4.15In 700
DEG C catalysis cracking of ethylene prepares the stereoscan photograph that CNT amplifies 10,000 times, and such as Fig. 1-Fig. 3 understands that the present embodiment can be obtained
To CNT yield 1100%, caliber 10-15nm, than 220~265 ㎡ of table/g.
Feature is：1st, CNT is prepared using the Fe-Al-Mg catalyst systems of spinelle or spinel-like structural；2、
10~15nm of caliber can be prepared using FeAl1.7Mg0.1O4.15 catalytic pyrolysis ethene, the carbon of specific surface area 200-265 ㎡/g is received
Mitron；3rd, by changing the controllable catalyst activity metallic particles size of the ratio of Fe in Fe-AlMgO catalyst systems, and then
Control the pipe diameter size of CNT；4th, the cracking reaction temperature of ethene is catalyzed by adjusting Fe-AlMgO, carbon nanometer is can control
The caliber and specific surface area size of pipe.
Embodiment two
202kg Fe (NO are weighed respectively3)3·9H2O, 93.78kg Al (NO3)3·9H2O, 192.11kg Mg (NO3)2·
9H2O, 288.21kg anhydrous citric acid, 1620kg deionized waters pour into stirring in reactor and are allowed to fully dissolving.100 DEG C of oil baths
Heating, 85r/min mechanical agitations.Agitating heating is evaporated to solution viscosity and reaches 100mPas, by solution 400 DEG C in tunnel cave
It is calcined 1 hour with air atmosphere, obtains FeAl0.1Mg1.5O3.15Catalyst.
The crucible of each filling 6g catalyst fines is used into automatic feed system, the 500 DEG C of tube furnace reactions of continuous push-in
Area, regulation ethene flow 1m3/ h, hydrogen flowing quantity 1m3/ h, setting program makes each crucible be in the residence time of reaction zone
20min, releases crucible and is cooled down under nitrogen atmosphere protection.CNT yield 2400% is can obtain, 15~20nm of caliber compares table
201~223 ㎡/g.
Embodiment three
202kg Fe (NO are weighed respectively3)3·9H2O, 37.51kg Al (NO3)3·9H2O, 358.60kg Mg (NO3)2·
9H2O, 384.28kg anhydrous citric acid, 2160kg deionized waters pour into stirring in reactor and are allowed to fully dissolving.100 DEG C of oil baths
Heating, 85r/min mechanical agitations.Agitating heating is evaporated to solution viscosity and reaches 100mPas, by solution 700 DEG C in tunnel cave
It is calcined 4 hours with air atmosphere, obtains FeAl0.2Mg2.8O4.6Catalyst.
The crucible of each filling 6g catalyst fines is used into automatic feed system, the 800 DEG C of tube furnace reactions of continuous push-in
Area, regulation ethene flow 6m3/ h, hydrogen flowing quantity 1m3/ h, setting program makes each crucible be in the residence time of reaction zone
60min, releases crucible and is cooled down under nitrogen atmosphere protection.CNT yield 3300% is can obtain, 15~20nm of caliber compares table
178~210 ㎡/g.
Example IV
202kg Fe (NO are weighed respectively3)3·9H2O, 318.86kg Al (NO3)3·9H2O, 12.82kg Mg (NO3)2·
9H2O, 537.99kg anhydrous citric acid, 720kg deionized waters pour into stirring in reactor and are allowed to fully dissolving.100 DEG C of oil baths
Heating, 85r/min mechanical agitations.Agitating heating is evaporated to solution viscosity and reaches 100mPas, by solution 580 DEG C in tunnel cave
It is calcined 3 hours with air atmosphere, obtains FeAl1.7Mg0.1O4.15Catalyst.
The crucible of each filling 6g catalyst fines is used into automatic feed system, the 700 DEG C of tube furnace reactions of continuous push-in
Area, regulation methane flow 5m3/ h, hydrogen flowing quantity 1m3/ h, setting program makes each crucible be in the residence time of reaction zone
60min, releases crucible and is cooled down under nitrogen atmosphere protection.CNT yield 1100% is can obtain, 20~25nm of caliber compares table
97~135 ㎡/g.
In sum, a kind of preparation method of CNT of the present invention, is characterized in：1st, catalyst is made using Fe
It is active component, the toxic heavy-metal elements such as Ni, Co, Mo is not used, raw material is nuisanceless；2nd, catalyst activity component is single, easily
The high degree of dispersion of active component is realized, the stability of catalyst is high；3rd, Catalyst Production is used cost of material is low, equipment is simple
It is single, it is adapted to industrialized production；4th, CNT pipe diameter size is in the range of 10~25nm, the carbon pipe uniform diameter for preparing；
5th, CNT oxidation resistance is good, and oxidizing temperature is 650~700 DEG C, and degree of graphitization is high, conducts electricity very well；6th, carbon nanometer
Pipe yield is high, and yield can reach 10~33g/g catalyst；7th, length of carbon nanotube is in 1~10 μ m；8th, CNT ash
Divide low, be easily purified the high-purity CNT for obtaining content of carbon nanotubes >=99%；9th, CNT bulk density>0.05g/cm3,
And low production cost.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferably
Embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to technology of the invention
Scheme is modified or equivalent, and without deviating from the spirit and scope of technical solution of the present invention, it all should cover in this hair
In the middle of bright right.
Claims (7)
1. a kind of preparation method of CNT, it includes：
(1) nitrate or acetate with tri- kinds of materials of Fe, Al, Mg is as raw material, using citric acid as complexing agent and pore creating material, plus
Solution is mixed into after entering water；
(2) above-mentioned solution is calcined, is made catalyst, the general structure of the catalyst is (FeO1.5)(AlO1.5)x(MgO)y, x
=0.1~3, y=0.1~3；
(3) using any one in catalyst cracking methane, ethene or propylene, CNT is obtained.
2. a kind of preparation method of CNT as claimed in claim 1, it is characterised in that：The nitre of Fe described in step (1)
The molar ratio of hydrochlorate or acetate, the nitrate of Al or acetate, the nitrate of Mg or acetate, citric acid this four classes material
It is Fe:Al:Mg=1:x:Y, 0.1≤x≤3,0.1≤y≤3；Citric acid/(Fe+Al+Mg)=z, 1≤z≤3.
3. a kind of preparation method of CNT as claimed in claim 1, it is characterised in that：It is calcined described in step (2)
Temperature is 400~700 DEG C, and the time of roasting is 1~4 hour.
4. a kind of preparation method of CNT as claimed in claim 1, it is characterised in that：It is catalyzed described in step (3) and is split
The time of solution is 20~60min.
5. a kind of preparation method of CNT as claimed in claim 1, it is characterised in that：It is catalyzed described in step (3) and is split
The temperature of solution is 500~800 DEG C.
6. a kind of preparation method of CNT as claimed in claim 1, it is characterised in that：Step is additionally added hydrogen in (3)
Participate in any one in catalyst cracking methane, ethene or propylene.
7. a kind of preparation method of CNT as claimed in claim 6, it is characterised in that：Methane, second described in step (3)
The flow of any one and the volume ratio of the flow of hydrogen in alkene or propylene are 1：1~6:1.
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| CN106221560A (en) * | 2016-08-03 | 2016-12-14 | 代长华 | A kind of electrochemical sensor electrodes coating material and preparation method thereof |
| CN107500268A (en) * | 2017-10-19 | 2017-12-22 | 焦作集越纳米材料技术有限公司 | A kind of preparation method of CNT |
| CN111514903A (en) * | 2019-12-25 | 2020-08-11 | 江西悦安新材料股份有限公司 | Method for preparing iron-based array carbon tube catalyst in large scale |
| CN112290021B (en) * | 2020-09-28 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube conductive agent for lithium ion battery |
| CN114558583B (en) * | 2022-02-23 | 2023-06-30 | 无锡东恒新能源科技有限公司 | Method for synthesizing superfine catalyst powder |
| CN114643061B (en) * | 2022-03-17 | 2023-06-02 | 无锡东恒新能源科技有限公司 | Reduction method of catalyst for preparing carbon nano tube |
| CN114618516B (en) * | 2022-03-17 | 2023-06-02 | 无锡东恒新能源科技有限公司 | Synthesis method of microspherical catalyst |
| CN114538417B (en) * | 2022-03-17 | 2023-06-30 | 无锡东恒新能源科技有限公司 | Method for preparing carbon nano tube by catalytic cracking of methanol or propylene |
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