CN104591128B - A kind of basalt fibre does the method that CNT prepared by catalyst - Google Patents
A kind of basalt fibre does the method that CNT prepared by catalyst Download PDFInfo
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- CN104591128B CN104591128B CN201510012041.7A CN201510012041A CN104591128B CN 104591128 B CN104591128 B CN 104591128B CN 201510012041 A CN201510012041 A CN 201510012041A CN 104591128 B CN104591128 B CN 104591128B
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Abstract
The invention discloses the preparation method of a kind of CNT, be specifically related to a kind of basalt fibre and do the method that CNT prepared by catalyst.By basalt fibre being cut into high-temperature calcination after flakelet, putting in fluidized-bed reactor, with low-carbon alkene as carbon source, using chemical vapour deposition technique to prepare CNT.The method low cost, technique are simple, easily operated, have both widened the application of basalt fibre, can solve again the problem that carbon nano-tube catalyst cost is high, it is adaptable to industrialization large-scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of CNT, be specifically related to a kind of basalt fibre and do the method that CNT prepared by catalyst.
Background technology
CNT the most always with structure and the excellent properties of its uniqueness, has attract the attention of domestic and international researcher since coming out.CNT has good mechanical property, heat stability, special electrical properties, heat conduction, hydrogen storage, absorption and catalytic performance etc..The most universal preparation method is chemical vapour deposition technique, the catalyst activity component wherein applied is based on metal Fe, Co, Ni, Mg, Al or its alloy, the most also have and Cu, Mo, Sn etc. are introduced catalytic component, the catalyst of different activities component and structure can affect the growth pattern of gained CNT, structure, yield and performance, and therefore researcher continuously improves component and the structure of catalyst or directly selects the catalyst containing suitable activity metal center and reach to prepare the purpose of CNT.Although carbon nano-tube catalyst is reported a lot, catalytic effect is more and more higher, but still does not overcome the shortcoming that the cost of traditional catalyst is high.
Basalt fibre, be specifically basalt endless fibers (EBF) be in fusion process prepare.Method of smelting complicated for the basalt with specified chemical characteristic is refined into basalt fibre.They are to be prepared by the Basalt melt of liquid at about 1400 DEG C.Its chemical composition is mainly SiO2、Al2O3、Fe2O3、TiO2Deng, wherein SiO2Content is at 44-52%, Al2O3Content is at 12-18%, FeO and Fe2O3Content is 9-14%, various places geology difference slightly deviation.In recent years, along with the maturation of basalt fibre preparation technology, its field of reinforcement, concrete field, field of compound material development and application more and more wider.
Chemical composition based on basalt fibre, exactly contain the metal active constituent of catalyzing carbon nanotube growth, if able to utilize basalt fibre to do carbon nano-tube catalyst, both can widen the application of basalt fibre, the problem that carbon nano-tube catalyst cost is high can be solved again.
Summary of the invention
It is an object of the invention to provide a kind of basalt fibre and do the method that CNT prepared by catalyst.By basalt fibre being cut into high-temperature calcination after flakelet, putting in fluidized-bed reactor, with low-carbon alkene as carbon source, using chemical vapor deposition for carbon nanotubes.The method low cost, technique are simple, easily operated, it is adaptable to industrialization large-scale production.
Containing the active component needed for the carbon nano-tube catalysts such as Fe, Al in basalt fibre, therefore can make catalyst with basalt fibre and prepare CNT.Fluidized-bed reactor is fast due to its reaction, and the features such as yield is high, easy operation are widely used in the preparation of CNT.The present inventor completes the present invention based on above-mentioned.By by basalt fibre cutting growth 0.01-0.5cm, the thin slice of wide 0.01-0.2cm, putting into after 600-900 DEG C of high-temperature calcination in fluidized-bed reactor, be passed through N2, reaction temperature is 600-1000 DEG C, and the carbon-source gas of low-carbon (LC) hydro carbons and the mixed gas of nitrogen that are passed through below 7 carbon are reacted to reactor, generates CNT.
A kind of basalt fibre does the method that CNT prepared by catalyst, and it concretely comprises the following steps:
1) by basalt fibre cutting growth 0.01-0.5cm, the thin slice of wide 0.01-0.2cm；
2) above-mentioned basalt fibre thin slice is put into 600-900 DEG C of calcining 1-4h in Muffle furnace；
3) treated basalt thin slice is put in fluidized-bed reactor, be passed through noble gas 20-60min, be warming up to 600-1000 DEG C, be passed through hydrogen reducing 10-20min；
4) being passed through the carbon-source gas of low-carbon (LC) hydro carbons of below 7 carbon after having reduced with in the mixed gas of noble gas to reactor, catalyst is blown out fluidized state by air-flow, and carbon-source gas adheres at catalyst surface, and is progressively cracked to form CNT.
In one preferred embodiment of the invention, described noble gas is nitrogen or argon.
In one preferred embodiment of the invention, the flow velocity of described hydrogen is 0.05-0.8m/s.
In one preferred embodiment of the invention, mixed gas volume proportion is noble gas: carbon-source gas=1:0.5-1.
In one preferred embodiment of the invention, the flow velocity of described mixed gas is 0.05-1m/s.
Accompanying drawing explanation
Below, in conjunction with accompanying drawing, the present invention will be described:
Fig. 1 is the scanning electron microscopic picture using basalt fibre to do CNT prepared by catalyst, and scale is 5 μm.
Fig. 2 is the scanning electron microscopic picture using basalt fibre to do CNT prepared by catalyst, and scale is 2 μm.
Fig. 3 is the scanning electron microscopic picture using basalt fibre to do CNT prepared by catalyst, and scale is 500 μm.
Detailed description of the invention
Prepare the method for CNT and be described using basalt fibre to make catalyst below:
In the present invention, term " noble gas " refers to that, without interference with carbon source and the gas of basalt fibre catalyst reaction, its not limiting example has, such as nitrogen, helium, argon etc..
In the present invention, term " CNT " represents a kind of One-dimensional Quantum material with special construction, and its radial dimension is nanometer scale, and axial dimension is micron dimension.CNT is mainly made up of the coaxial pipe of several layers to tens of layers the carbon atom of hexagonal arrangement.Keeping fixing distance, about 0.34nm between layers, diameter is generally 2 ~ 20 nm.
In the present invention, term " fluidized state " refers to that basalt fibre and CNT are suspended among the noble gas of motion, so that basalt fibre and CNT have some appearance features of fluid.
In one embodiment of the invention, utilize noble gas (such as nitrogen) to carry basalt fibre in the reactor, basalt fibre is blown out suspended state, basalt fibre is cut into flakelet, can be easier to realize fluidized state.
In the present invention, 600-900 DEG C of high-temperature calcination of Muffle furnace can burn impurity and the organic carbon on basalt fibre surface, is conducive to improving catalytic efficiency.
In the present invention, it is passed through hydrogen reducing and refers under inert gas shielding, with hydrogen by the reactive metal oxides in basalt fibre (such as FeO, Fe2O3、Al2O3Deng) it being reduced into metal, carbon-source gas only can crack in metal surface, generates CNT.
In one preferred embodiment of the invention, described noble gas is nitrogen or argon.
In one preferred embodiment of the invention, the flow velocity of described hydrogen is 0.05-0.8m/s.
In one preferred embodiment of the invention, mixed gas volume proportion is noble gas: carbon-source gas=1:0.5-1.
In one preferred embodiment of the invention, the flow velocity of described mixed gas is 0.05-1m/s.
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.For the experimental technique of actual conditions unreceipted in the following example, generally according to normal condition, or according to the condition proposed by manufacturer.Ratio and percentage ratio are based on mole, unless stated otherwise.
Raw material sources:
(1) source of the gas:
Propylene: purchased from Shandong Qilu Petrochemical Company, purity: > 99.9%；
Methane: purchased from Dongying China National Petroleum company limited, purity: > 99.9%；
Hydrogen: purchased from Anze, Zibo Te Qi company limited, purity: > 99.9%；
Nitrogen: purchased from Anze, Zibo Te Qi company limited, purity: > 99.99%；
(2) basalt fibre: purchased from Mudanjiang basalt fibre company limited.
Properties of product are tested:
(1) purity test:
Fluidized reaction obtains the weight of product by weighing after completing, amount (m based on the basalt catalyst usedCatalyst) and the weight (m of productAlways), the purity of definition product:
Purity=[(mAlways-mCatalyst)/mAlways]×100%。
(2) microscopic appearance test:
The caliber of CNT is determined by scanning electron microscope (SEM).
Embodiment
1
:
By 2g basalt fibre cutting growth 0.3cm, wide 0.1cm thin slice after put in Muffle furnace 700 DEG C of calcining 2h；Putting in fluidized-bed reactor by the basalt thin slice processed, be passed through nitrogen 30min, reactor is warming up to 700 DEG C, be passed through hydrogen reducing 15min, the flow velocity of hydrogen is 0.1m/s；Being passed through the mixed gas of propylene and nitrogen after having reduced in reactor, the flow velocity of mixed gas is 0.5m/s, and catalyst is blown out fluidized state by air-flow, and propylene adheres at catalyst surface, and is progressively cracked to form CNT, cools down blowing after having reacted.
By calculating of weighing, the purity of CNT is 62.8%, and by accompanying drawing 1 it can be seen that generating product is CNT really, caliber is at about 30nm.
Embodiment
2
:
By 2g basalt fibre cutting growth 0.5cm, wide 0.2cm thin slice after put in Muffle furnace 900 DEG C of calcining 4h；Putting in fluidized-bed reactor by the basalt thin slice processed, be passed through nitrogen 50min, reactor is warming up to 800 DEG C, be passed through hydrogen reducing 20min, the flow velocity of hydrogen is 0.2m/s；Being passed through the mixed gas of methane and nitrogen after having reduced in reactor, the flow velocity of mixed gas is 0.3m/s, and catalyst is blown out fluidized state by air-flow, and methane adheres at catalyst surface, and is progressively cracked to form CNT, cools down blowing after having reacted.By calculating of weighing, the purity of CNT is 77.3%.
The present invention uses basalt fibre to make catalyst to prepare the process of CNT, and its raw material dosage and technological parameter are not limited to the above-mentioned embodiment enumerated.After the above-mentioned teachings having read the present invention, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Claims (4)
1. basalt fibre does the method that CNT prepared by catalyst, and it concretely comprises the following steps:
1) by basalt fibre cutting growth 0.01-0.5cm, the thin slice of wide 0.01-0.2cm；
2) above-mentioned basalt fibre thin slice is put into 600-900 DEG C of calcining 1-4h in Muffle furnace；
3) treated basalt thin slice is put in fluidized-bed reactor, be passed through noble gas 20-60min, be warming up to 600-1000 DEG C, be passed through hydrogen reducing 10-20min；Described noble gas is nitrogen or argon；
4) being passed through the carbon-source gas of low-carbon (LC) hydro carbons of below 7 carbon after having reduced with in the mixed gas of noble gas to reactor, catalyst is blown out fluidized state by air-flow, and carbon-source gas adheres at catalyst surface, and is progressively cracked to form CNT.
2. the method for claim 1, it is characterised in that the flow velocity of described hydrogen is 0.05-0.8m/s.
3. the method for claim 1, it is characterised in that mixed gas volume proportion is noble gas: carbon-source gas=1:0.5-1.
4. the method for claim 1, it is characterised in that the flow velocity of described mixed gas is 0.05-1m/s.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412592A (en) * | 2008-11-12 | 2009-04-22 | 东华大学 | Surface modification method for basalt fibre by using plasma treatment and carbon nano-tube coating |
| CN102199872A (en) * | 2011-03-29 | 2011-09-28 | 北京航空航天大学 | Method for in-situ growing carbon nanotubes on fiber surfaces |
| CN103420359A (en) * | 2013-08-08 | 2013-12-04 | 山东大展纳米材料有限公司 | Method for preparing carbon nanotube under catalysis of red mud, reaction device and application |
| CN104085873A (en) * | 2014-06-03 | 2014-10-08 | 张映波 | Method for preparing carbon nanotube on fiber surface in high density |
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2015
- 2015-01-09 CN CN201510012041.7A patent/CN104591128B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412592A (en) * | 2008-11-12 | 2009-04-22 | 东华大学 | Surface modification method for basalt fibre by using plasma treatment and carbon nano-tube coating |
| CN102199872A (en) * | 2011-03-29 | 2011-09-28 | 北京航空航天大学 | Method for in-situ growing carbon nanotubes on fiber surfaces |
| CN103420359A (en) * | 2013-08-08 | 2013-12-04 | 山东大展纳米材料有限公司 | Method for preparing carbon nanotube under catalysis of red mud, reaction device and application |
| CN104085873A (en) * | 2014-06-03 | 2014-10-08 | 张映波 | Method for preparing carbon nanotube on fiber surface in high density |
Non-Patent Citations (1)
| Title |
|---|
| "Natural Lavas as Catalysts for Efficient Production of Carbon Nanotubes and Nanofibers";Dang Sheng Su et al.;《Angewandte Chemie International Edition》;20070130;第46卷;第1823-1824页 * |
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Denomination of invention: A method for preparing carbon nanotubes using basalt fiber as catalyst Effective date of registration: 20230227 Granted publication date: 20160824 Pledgee: China Construction Bank Corporation Zouping sub branch Pledgor: Shandong Dazhan Nano Materials Co.,Ltd. Registration number: Y2023980033537 |
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