CN105217599A - A kind of system and method for synthesizing carbon nanotubes - Google Patents
A kind of system and method for synthesizing carbon nanotubes Download PDFInfo
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Abstract
The invention discloses a kind of system and method for synthesizing carbon nanotubes, described system comprises circulation flame territory, carbon source pyrolysis territory, carbon nanotube composite field, finished product collecting unit and chemical reaction raw material supply unit; And core reaction chamber, circulation flame room, flammenwerfer, top umbrella; It is indoor that described circulation flame territory is positioned at circulation flame, described core reaction chamber is positioned at the center of circulation flame room, described carbon source pyrolysis territory is positioned at bottom, core reaction chamber, described carbon nanotube composite field is positioned at core reaction chamber internal upper part, the jet orifice of described flammenwerfer is positioned at the sidewall of circulation flame room, described top umbrella is positioned at the top in core reaction chamber, described finished product collecting unit is positioned at above the umbrella of top, and described chemical reaction raw material supply unit is to feed in circulation flame room and core reaction chamber.
Description
Technical field
The invention belongs to carbon nanotube synthesis technical field, be specifically related to a kind of system and method for synthesizing carbon nanotubes.
Background technology
Carbon nanotube is a kind of allotropic substance of carbon in itself, can regard as by the seamless hollow tubular structures of the curling nano-scale of single or multiple lift graphite flake.Be rolled into by individual layer, be called Single Walled Carbon Nanotube; The coaxial valve be rolled into by multilayer, is called multi-walled carbon nano-tubes, and interlamellar spacing is about 0.34nm.As the typical one-dimensional carbon nano material of one, carbon nanotube has unique electronic structure and physics-chem characteristic.Such as: greatly length-to-diameter ratio and specific surface area, high Young's modulus and bending strength, can resistance to strong acid and highly basic, heat transfer and conductivity splendid, and self lubricity, give birth to a series of over-all propertieies such as compatability.Therefore, the application of carbon nanotube in every field causes the common concern of scientific circles, and prospect is considerable.Most important Application Areas comprises: super capacitor, hydrogen storage material, field emission device, atomic force microscope probe, lithium ion battery, chemical sensor, support of the catalyst, reinforced composite etc.The multiple good characteristic shown in view of carbon nanotube and the huge applications that derives thus are worth, how can high-level efficiency, low cost, can control, on a large scale synthesizing carbon nanotubes just become the target that lot of domestic and foreign scholar pursues.In line with this aim, the synthetic method of carbon nanotube is also constantly being weeded out the old and bring forth the new.The method of synthesizing carbon nanotubes is very many, mainly contains: arc discharge method, laser evaporization method, chemical Vapor deposition process (CVD) and flame method comparatively novel at present.The research comparative maturity of first three methods, but they are all subject to very large restriction in scale, cost, equipment, operation and continuity etc.Now known various flame method all achieve simple, with low cost, the easy to operate target of equipment substantially, but the output of the overwhelming majority is all on the low side, and the utilization ratio of carbon source is not high yet, and be difficult to meet controlled, in batches, quantity-produced requirement.
In sum, develop a kind of can efficiently, cheap, controlled, in batches, the method for synthesizing carbon nanotubes continuously, be still the primary difficult problem that the art is urgently captured.The present invention is just for a kind of brand-new solution that this thorny problem proposes.
Summary of the invention
The object of the invention is to provide a kind of brand-new scheme to solve the problem, i.e. a kind of system of efficient controlledly synthesis carbon nanotube.
A system for synthesizing carbon nanotubes, comprises circulation flame territory, carbon source pyrolysis territory, carbon nanotube composite field, finished product collecting unit and chemical reaction raw material supply unit; And core reaction chamber, circulation flame room, flammenwerfer, top umbrella; It is indoor that described circulation flame territory is positioned at circulation flame, described core reaction chamber is positioned at the center of circulation flame room, described carbon source pyrolysis territory is positioned at bottom, core reaction chamber, described carbon nanotube composite field is positioned at core reaction chamber internal upper part, the jet orifice of described flammenwerfer is positioned at the sidewall of circulation flame room, described top umbrella is positioned at the top in core reaction chamber, described finished product collecting unit is positioned at above the umbrella of top, and described chemical reaction raw material supply unit is to feed in circulation flame room and core reaction chamber.
Further, described finished product collecting unit comprises flip-over type finished product acquisition probe and travelling belt.
Further, described chemical reaction raw material supply unit comprises carbon source supply equipment, assist gas supply equipment, catalyzer supply equipment, fuel facility, oxygenant supply equipment.
Further, described core reaction chamber is tubular, and the profile of circulation flame room is prismatic, and its external wall cross-section is Polygons, and the jet orifice of flammenwerfer is arranged on each end points polygonal or on each bar limit.
Further, described flammenwerfer installs one group or install many groups at different heights place at the sustained height place of circulation flame room sidewall, and each in same group of flammenwerfer is installed in the sustained height place on the sidewall of circulation flame room.
Further, described fuel and oxygenant first spray after the inner premix of flammenwerfer, or spray respectively from respective passage in flammenwerfer, meet subsequently in circulation flame indoor.
Further, the exit flow of described flammenwerfer is direct jet, or rotating jet, and the geometric axis of air-flow is all tangent with the outer wall in tubular core reaction chamber; After the air-flow of each flammenwerfer ejection converges, the central zone in circulation flame room is formed vigorous combustion and around the flame of the rapid rotational flow of core reaction cavity outer wall.
Further, automatic spring when described flip-over type finished product acquisition probe arrives directly over carbon nanotube composite field, extend into the predetermined position in carbon nanotube composite field, meanwhile, travelling belt is out of service immediately, to gather obtained finished product carbon nanotube; After the residence time of probe reaches default finished product acquisition time, probe just can reply position by appliance for releasing single, and travelling belt also can continue to run immediately.
Further, the carbon source of described carbon source supply equipment supply is the carbon raw material of gas, liquid, solid or plasma body.
The assist gas of described assist gas supply equipment supply refers to hydrogen and rare gas element or low activity gas.
The catalyzer of described catalyzer supply equipment supply is the mixture that the compound of transition metal simple substance or alloy or transition metal or above-mentioned simple substance, alloy or compound are formed.
The fuel of described fuel facility supply is the higher calorific value inflammable substance of gas, liquid or solid.
The oxygenant of described oxygenant supply equipment supply is air, pure oxygen or oxygen-nitrogen gas mixture.
Further, described system also comprises:
(1) bypath system, described bypath system needs change operation condition or system go wrong need to shut down time, can by the gas with refrigerating function direct input coefficient, described gas is rare gas element or low activity gas;
(2) temperature sensor and coupled digital instrument: in order to monitor the temperature of carbon source pyrolysis territory and carbon nanotube composite field;
(3) digital timer: with temperature sensor with the use of, automatic spring and the homing action of finished product acquisition probe can be realized, and travelling belt out of service and continue run action;
(4) lighter for ignition: when system brings into operation, lights by it the fuel sprayed from flammenwerfer;
(5) impeller and the director of Swirl Condition can be provided, make the exit flow of flammenwerfer form rotating jet, to coordinate the combustioncharacteristics controlling flame;
(6) furnace hopper: in the system taking coal as fuel, installs, in order to collect ashes in the bottom of circulation flame room.
The present invention also provides the method utilizing said system synthesizing carbon nanotubes, comprises the following steps:
(1) starting fluid supply equipment and oxygenant supply equipment, transfer the fuel and oxygenant in flammenwerfer, for igniting is prepared;
(2) start assist gas supply equipment, in core reaction chamber, carry cooling gas (such as helium, nitrogen etc., in order to cost-saving, also directly can use air), in order to avoid after catching fire, core reaction chamber burns out by the flame of high temperature;
(3) initial igniter, lights the mixture of fuel and the oxygenant sprayed from flammenwerfer;
(4), after the circulation flame formation of indoor to be combusted, the consumption of fuel metering and oxygenant is to desirable value; ;
(5) burn with treating circulation flame stabilization, and after the circulation flame temperature at the indoor different heights place of circulation flame all reaches design load, start carbon source supply equipment and catalyzer supply equipment, in core reaction chamber, carry carbon source and catalyzer;
(6) consumption of carbon source and catalyzer is tuned up to design variable, make carbon source start pyrolysis occurs;
(7) after the temperature of carbon source pyrolysis territory and carbon nanotube composite field all reaches design load, finished product collecting unit is started;
(8) when first flip-over type finished product acquisition probe arrives directly over carbon nanotube composite field with travelling belt, it just can automatic spring, extend into the predetermined position in carbon nanotube composite field, starts the carbon nanotube gathering synthesis; Meanwhile, travelling belt can be out of service immediately;
(9) after first residence time of probe in carbon nanotube composite field reaches default finished product acquisition time, probe just can reply position by appliance for releasing single, and travelling belt also can continue to run immediately;
(10) the flip-over type finished product acquisition probe continued repeats the step of (8), (9) two steps successively, until system is out of service;
When needs change operation condition or system go wrong need to shut down time, then carry out according to following steps:
(11) close fuel facility and oxygenant supply equipment, stop transfer the fuel and oxygenant in flammenwerfer, make in combustion chamber flame-out;
(12) close carbon source supply equipment and catalyzer supply equipment, stop carrying carbon source and catalyzer in core reaction chamber, avoid wasting raw material;
(13) close finished product collecting unit, make it out of service;
(14) bypath system is opened, cooling gas (such as helium, nitrogen etc. is carried in flammenwerfer and core reaction chamber, in order to cost-saving, also directly air can be used), and cooling gas is sprayed in combustion chamber, so that cooling flame injector, combustion chamber and core reaction chamber, the remaining high temperature after stopping working in combustion chamber is avoided they to be damaged;
(15) indoor to be combusted temperature everywhere is all down to after below 200 DEG C, closes assist gas supply equipment.
The technology and system of synthesizing carbon nanotubes in application the present invention, can efficiently, cheap, controlled, the carbon nanotube and the array thereof that synthesize good quality in batches, continuously.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of carbon nanotube synthesis system of the present invention.
Fig. 2 is three kinds of reference example of flammenwerfer decoration form.
Fig. 3 for after having carried out numerical simulation to the reference example in Fig. 2 (a), the roughly profiling temperatures in circulation flame territory on a certain cross section.
Fig. 4 is the high power transmission electron microscope photo of the Single Walled Carbon Nanotube prepared by embodiment 1.
Fig. 5 is that the Single Walled Carbon Nanotube that prepared by embodiment 1 is at 0-2500cm
-1raman spectrogram in Raman shift range.
Fig. 6 is the stereoscan photograph of the carbon nano pipe array prepared by embodiment 2.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in more detail.
Fig. 1 is the schematic diagram of carbon nanotube synthesis system of the present invention.It is described with the preferred specific embodiment of one of the present invention.For ease of distinguishing, in Fig. 1, theoretical integral part numeral 1 beginning of system is marked, and the structural member numeral 2 in kind beginning of system is marked.
In Fig. 1, circulation flame territory represents with 101, and carbon source pyrolysis territory represents with 102, and carbon nanotube composite field represents with 103.This method for expressing, only in order to explain carbon source pyrolysis territory and the approximate location of carbon nanotube composite field in core reaction chamber, in fact, not clear and definite boundary between carbon source pyrolysis territory and carbon nanotube composite field.In addition, 104 represent finished product collecting unit, and 105 represent chemical reaction raw material supply unit.
In Fig. 1,201 represent core reaction chamber, 202 representative ring filariasis flame combustion chambers, and 203 represent flame spraying mouth, 204 represent top umbrella, 205 represent finished product acquisition probe, and 206 represent flip-over type probe travelling belt, and 207 represent carbon source supply equipment, 208 represent assist gas supply equipment, 209 represent catalyzer supply equipment, and 210 represent fuel facility, and 211 represent oxygenant supply equipment.Wherein, flame spraying mouth (203) refers to the outlet of flammenwerfer, i.e. the interface of flammenwerfer and circulation flame room.
Fig. 2 is three kinds of reference example of flammenwerfer decoration form.Wherein, a () is positive corner decoration form, b () is positive hexagonal decoration form, c () is a kind of special decoration form, in this decoration form, core reaction chamber is square-tube-shaped, and the cross section of its outer wall is rectangle, the cross section of combustion chamber is circular, and flammenwerfer is arranged on four end points of round any two mutually perpendicular diameters.
A system for circulation flame synthesis synthesizing carbon nanotubes, comprising: circulation flame territory, carbon source pyrolysis territory, carbon nanotube composite field, finished product collecting unit and chemical reaction raw material supply unit, the relation between them as shown in Figure 1.
In addition, this system can also comprise some other attached integral parts.Such as, when needs change operation condition or system go wrong need to shut down time, in order to timely cooling flame injector, combustion chamber and core reaction chamber, ensure the safety of equipment and the bypath system that arranges.
Textural at material object, the major parts of this system has: core reaction chamber, circulation flame room, flammenwerfer, top umbrella, finished product collecting device and chemical reaction raw material supply equipment.
In addition, this system can also comprise some other attached structural members.Such as, the furnace hopper of ashes is collected; The impeller, the director that arrange to make the exit flow of flammenwerfer form rotating jet.
Described circulation flame territory is the distribution range of circulation flame in space.The combustion processes of circulation flame mainly concentrates on circulation flame indoor and carries out.
Described carbon source pyrolysis territory is that carbon source under the high temperature conditions pyrolysis occurs and produces the spatial dimension of carbon atom.The pyrolytic process of carbon source mainly in core reaction chamber, bottom carries out.
Described carbon nanotube composite field is the spatial dimension of carbon atom synthesizing carbon nanotubes under suitable condition (as temperature, catalyzer etc.).The building-up process of carbon nanotube mainly in core reaction chamber, top and outlet periphery carry out, in some case study on implementation, the building-up process of carbon nanotube even can be carried out in the umbrella of top.
Described finished product collecting unit is used to a module of the carbon nanotube gathering synthesis, and wherein comprise a series of equipment, concrete equipment will be introduced later.
Described chemical reaction raw material supply unit is used to as the series of chemical of synthesizing carbon nanotubes and the combustion processes of circulation flame provide a module of required various chemical feedstockss (as carbon source, catalyzer, fuel etc.), wherein comprise a series of equipment, concrete equipment will be introduced later.
Described core reaction chamber, from the angle of engineering thermodynamics, can regard that have material and energy exchange with the external world, to comprise a chemical reaction open loop system as, for a series of successive processess of synthesizing from carbon source pyrolysis to carbon nanotube provide required space.Synthesis from the pyrolysis of carbon source to carbon nanotube is a series of continuous print processes, and this series of continuous print process is all carried out in core reaction chamber, boundary not clear and definite between carbon source pyrolysis territory and carbon nanotube composite field.Usually, in core reaction chamber, bottom provides carbon source pyrolysis territory, and in, top and outlet periphery provide carbon nanotube composite field.
In order to coordinate the hydrodynamic characteristics of external rings filariasis flame, pipe should be made in core reaction chamber, can obtain best heats like this.Certainly, other shape is made in core reaction chamber also to should be all right.
The bottom in core reaction chamber is connected with chemical reaction raw material supply unit, and it is inner that the chemical reaction raw materials such as the carbon source needed for synthesizing carbon nanotubes, catalyzer, assist gas input core reaction chamber thus.
In order to monitor the temperature of carbon source pyrolysis territory and carbon nanotube composite field, should arrange many places point for measuring temperature near core reaction cavity wall along short transverse, this just needs at this several places set temperature sensor, and is connected on outside digital instrument.
The burning that described circulation flame room is circulation flame provides required space.It also can regard that have material and energy exchange with the external world, to comprise a chemical reaction open loop system as.
The pattern that the profile of circulation flame room is not completely fixed, can make cylindrical, prismatic, conical, pyramid etc. according to concrete working conditions.For non-special occasion, for the ease of installing flammenwerfer, prismatic circulation flame room should be used.
In order to monitor the temperature of different heights place circulation flame in combustion chamber, should arrange many places point for measuring temperature near core reaction cavity outer wall along short transverse, this just needs at this several places set temperature sensor, and is connected on outside digital instrument.
Described flammenwerfer is used for burner oil and oxygenant in combustion chamber, to form the circulation flame around core reaction chamber in combustion chamber, thus provides required energy for the series of chemical of synthesizing carbon nanotubes.The import of flammenwerfer is connected with chemical reaction raw material supply unit, and the chemical feedstockss such as the fuel needed for the combustion processes of circulation flame, oxygenant input thus, then spray into combustion chamber by outlet.Fuel and oxygenant just take fire after flammenwerfer sprays, and form the most violent circulation flame of burning at the center (namely around core reaction cavity outer wall) of combustion chamber.
Flammenwerfer is arranged on the sidewall of combustion chamber.Only can install one group (individual layer layout) at a certain At The Height of combustion chamber, also can install many groups (multilayer layouts) along the short transverse of combustion chamber, determine according to the needs of embodiment.
Fuel, oxygenant both can first spray after the inner premix of flammenwerfer, also can spray respectively from respective passage in flammenwerfer, meet subsequently in combustion chamber.Different hybrid modes can be selected in different case study on implementation.
In order to control the combustioncharacteristics of flame, the exit flow of flammenwerfer both can be direct jet, also can be rotating jet, can select different mode of jet in different case study on implementation.Realize rotating jet, the appurtenances that some can provide Swirl Condition should be installed, such as impeller, director etc.
In addition, at appurtenances such as the exit layout points firearms of certain (or multiple) flammenwerfer, when system brings into operation, the fuel sprayed from flammenwerfer must be lighted by lighter for ignition.
Described top umbrella is mounted in the parts of core reaction top of chamber, and its sectional area is comparatively large, even can the top of cover ring filariasis flame combustion chamber, so gain the name.By it, multiple object can be realized, reach multi-effect.
The pattern that the profile of top umbrella is not completely fixed, can make disc, fan-like pattern, bowl-type, fin shape, splayed, herringbone, two splayed, two herringbone, petal etc. according to concrete working conditions.
Described finished product collecting unit is used to the general name of a series of equipment of the carbon nanotube gathering synthesis.Mainly comprise: finished product acquisition probe, flip-over type probe travelling belt.
The finished product that carbon nanotube composite field obtains is taken out by acquisition probe, and finished product acquisition probe both can have been goed deep into inside, core reaction chamber and gather carbon nanotube, also can gather carbon nanotube in the umbrella of top.
Flip-over type probe travelling belt is in order to batch, quantity-produced requirement and arranging, and finished product acquisition probe is arranged on a moving belt with order by the interval of design.
Just can automatic spring when finished product acquisition probe on travelling belt arrives directly over carbon nanotube composite field, extend into the predetermined position in carbon nanotube composite field, meanwhile, travelling belt can be out of service immediately, to gather obtained finished product carbon nanotube.After the residence time of probe reaches default finished product acquisition time, probe just can reply position by appliance for releasing single, and travelling belt also can continue to run immediately.
The automatic spring of finished product acquisition probe and homing action, and the out of service and continuation run action of travelling belt relies on the appurtenances such as temperature sensor and digital timer to realize.
Described chemical reaction raw material supply equipment is used to as the series of chemical of synthesizing carbon nanotubes and the combustion processes of circulation flame provide the general name of all devices of required various chemical feedstockss.Mainly comprise: carbon source supply equipment, catalyzer supply equipment, assist gas supply equipment, fuel facility, oxygenant supply equipment etc.
Described carbon source supply equipment is in order to provide synthesizing carbon nanotubes essential carbon source to system.Carbon source can be gas, liquid or solid, or even plasma body, such as: carbon monoxide, methane, ethanol, benzene, coke, carbon nano plasma.
Described catalyzer supply equipment is in order to provide the catalyzer corresponding to the carbon nanotube synthesizing required kind to system.Catalyzer can be the simple substance (or alloy) that forms of the transition metals such as Fe, Co, Ni, Mo, Cr, Cu, Pt and compound thereof or mixture.Such as: iron simple substance, nickel simple substance, ferrocene, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, ferric oxide, pentacarbonyl iron etc.Suitable catalyzer can be selected according to technical requirementss such as the thickness of required carbon nanotube, wall numbers.
Described assist gas supply equipment is in order to provide the various assist gass needed for synthesizing carbon nanotubes to system.Assist gas is of great advantage to synthesizing carbon nanotubes, and often kind of gas wherein all plays respective not same-action.Such as: hydrogen can play and promotes carbon source to adsorb and dissociate, clean carbon tube-surface impurity, make catalyzer keep the effects such as activity; Rare gas element or low activity gas (such as helium, neon, argon gas, nitrogen etc.) can dilute catalysts, the effect into local cooling can also be played, carbon nanotube is avoided to be burnt at too high a temperature, in addition, at use pentacarbonyl iron etc. as under the operating mode of catalyzer, also can be used as the carrier carrying catalyzer.
Described fuel facility is in order to provide the fuel needed for burning to system.Described fuel can be gas, liquid or solid, such as: acetylene, hydrogen, methane, gasoline, diesel oil, coal dust, wood chip, sulphur etc.
Described oxygenant supply equipment is in order to provide the ignition dope needed for burning to system.In order to cost-saving, first oxygenant is considered to use air, and in the example needing higher Heating temperature, oxygenant also can use the oxygen-nitrogen gas mixture of 21: 79,3: 7 or 1: 1 equal proportion, even pure oxygen.
All attached integral part in native system and attached structural member are all for above-mentioned integral part and structural member in kind are served.Such as: lighter for ignition is used for lighting the fuel from flammenwerfer ejection when system starts; Temperature sensor and digital timer are used for automatic spring and the homing action of finished product acquisition probe.Be arranged on the bottom of combustion chamber in order to collect the furnace hopper of ashes; The impeller, the director that arrange to make the exit flow of flammenwerfer form rotating jet.
The decoration form of flammenwerfer has multiple, gives several reference example in Fig. 2.Be easy to most manufacture, install and use positive corner to arrange (as Suo Shi Fig. 2 (a)), in this decoration form, the cross section of combustion chamber is square, flammenwerfer is arranged on foursquare four angles, and the geometric axis of these four flammenwerfer exit flows is all tangent with the outer wall in tubular core reaction chamber.Carried out numerical simulation to the flame of this decoration form, the roughly profiling temperatures in circulation flame territory on a certain cross section as shown in Figure 3.
Arrange in (as Suo Shi Fig. 2 (b)) mode in positive hexagonal, the cross section of combustion chamber is regular hexagon, flammenwerfer is arranged on orthohexagonal six angles, and the geometric axis of these six flammenwerfer exit flows is all tangent with the outer wall in tubular core reaction chamber.
Shown in Fig. 2 (c) is a kind of special decoration form, in this decoration form, core reaction chamber is square-tube-shaped, the cross section of its outer wall is rectangle, the cross section of combustion chamber is circular, flammenwerfer is arranged on four end points of round any two mutually perpendicular diameters, and the geometric axis of these four flammenwerfer exit flows is all tangent with the imaginary circle being diameter with the diagonal lines of this rectangle.
The present invention utilizes the method for said system synthesizing carbon nanotubes to comprise the following steps:
S1. starting fluid supply equipment and oxygenant supply equipment, transfer the fuel and oxygenant in flammenwerfer, for igniting is prepared;
S2. start assist gas supply equipment, in core reaction chamber, carry cooling gas (such as helium, nitrogen etc., in order to cost-saving, also directly can use air), in order to avoid after catching fire, core reaction chamber burns out by the flame of high temperature;
S3. initial igniter, lights the mixture of fuel and the oxygenant sprayed from flammenwerfer;
After the circulation flame formation of S4. indoor to be combusted, the consumption of fuel metering and oxygenant is to desirable value;
S5. burn with treating circulation flame stabilization, and after the circulation flame temperature at different heights place all reaches design load in combustion chamber, start carbon source supply equipment and catalyzer supply equipment, in core reaction chamber, carry carbon source and catalyzer;
S6. the consumption of carbon source and catalyzer is tuned up to design variable, make carbon source start pyrolysis occurs;
S7., after the temperature of carbon source pyrolysis territory and carbon nanotube composite field all reaches design load, finished product collecting unit is started;
S8., when the finished product acquisition probe of first on travelling belt arrives directly over carbon nanotube composite field, it just can automatic spring, extend into the predetermined position in carbon nanotube composite field, starts the carbon nanotube gathering synthesis; Meanwhile, travelling belt can be out of service immediately;
S9., after first residence time of probe in carbon nanotube composite field reaches default finished product acquisition time, probe just can reply position by appliance for releasing single, and travelling belt also can continue to run immediately;
S10. all finished product acquisition probe below all will repeat the step of S8, S9, successively until system is out of service;
When needs change operation condition or system go wrong need to shut down time, then carry out according to following steps:
S11. close fuel facility and oxygenant supply equipment, stop transfer the fuel and oxygenant in flammenwerfer, make in combustion chamber flame-out;
S12. close carbon source supply equipment and catalyzer supply equipment, stop carrying carbon source and catalyzer in core reaction chamber, avoid wasting raw material;
S13. close finished product collecting unit, make it out of service;
S14. bypass valve is opened, in flammenwerfer and core reaction chamber, carry cooling gas (as helium, nitrogen etc., in order to cost-saving, also directly air can be used), and cooling gas is sprayed in combustion chamber, so that cooling flame injector, combustion chamber and core reaction chamber, the remaining high temperature after stopping working in combustion chamber is avoided they to be damaged;
S15. indoor to be combusted temperature everywhere is all down to after below 200 DEG C, closes assist gas supply equipment.
Below with reference to the accompanying drawings with preferred embodiment, content of the present invention is described further.It must be noted that, the present invention can be realized by many different specific forms, and not will be understood that the present invention is only confined to the embodiments described herein.On the contrary, provide these embodiments will make content of the present invention clearly, complete, and give full expression to scope of the present invention to those skilled in the art, and other object still NM before passing on.
In following two preferred embodiments, system of the present invention is utilized to carry out the roughly Methods and steps of synthesizing carbon nanotubes as previously mentioned, and the preparation method of catalyzer and the operation steps of some routines are as well known to those skilled in the art, therefore repeat no more, only wherein crucial technical parameter is described here.
Embodiment 1
The present embodiment provides a kind of preparation method of Single Walled Carbon Nanotube, and its technical parameter is as follows:
(1) profile of circulation flame room is four prism type, and its cross section is square; Flammenwerfer is arranged on foursquare four angles, and installs three groups (multilayer layouts) along the short transverse of combustion chamber; Core reaction chamber is tubular; Top umbrella is bowl-type;
(2) adopt sol-gel method to prepare Co/Mo/MgO catalyzer in advance, wherein the ratio of the amount of substance of Co, Mo, Mg is 1: 2: 30, and maturing temperature is 850 DEG C;
(3) using methane gas as carbon source, using hydrogen, helium as assist gas, wherein CH
4, H
2, He the ratio of volumetric flow rate be 3: 4: 5;
(4) using acetylene gas as fuel, the oxygen-nitrogen gas mixture using 21: 79 is as oxygenant, and its volume flow ratio is 1: 13; Fuel, oxygenant spray respectively from respective passage in flammenwerfer, meet subsequently in combustion chamber, and the exit flow of flammenwerfer is direct jet;
(5) finished product acquisition time is 6 minutes.
Fig. 4 is the high power transmission electron microscope photo of the carbon nanotube prepared by embodiment 1.Can be clear that many Single Walled Carbon Nanotube from Fig. 4, its length-to-diameter ratio is very large, and diameter Distribution is even, and purity is also very high, only has few decolorizing carbon to exist.
Fig. 5 is that the carbon nanotube that prepared by embodiment 1 is at 0-2500cm
-1raman spectrogram in Raman shift range.As can be seen from Figure 5, at 1550-1600cm
-1near occurred that G mould (G-band) composes peak, its spectrum peak is very strong, shows that the degree of graphitization of product is very high; And at 1250-1450cm
-1near occurred that D mould (D-band) composes peak, its spectrum peak quite weak, show that in product, the content of decolorizing carbon is very little.In addition, at 180cm
-1near there is fairly obvious radial climacteric (RBM), this shows to there is a large amount of high-quality Single Walled Carbon Nanotube in product.
Embodiment 2
The present embodiment provides a kind of preparation method of carbon nano pipe array, and its technical parameter is as follows:
(1) profile of circulation flame room is cylindrical, and its cross section is circular; Flammenwerfer is arranged on four end points of two round mutually perpendicular diameters, and installs three groups (multilayer layouts) along the short transverse of combustion chamber; Core reaction chamber is tubular; Top umbrella is petal;
(2) sol-gel method is adopted to prepare Fe/Mo/Al in advance
2o
3catalyzer, wherein the ratio of the amount of substance of Fe, Mo, Al is 5: 1: 60, and maturing temperature is 900 DEG C;
(3) using CO (carbon monoxide converter) gas as carbon source, using hydrogen, helium as assist gas, wherein CO, H
2, He the ratio of volumetric flow rate be 2: 3: 3;
(4) using acetylene gas as fuel, using air as oxygenant, its volume flow ratio is 1: 13; Fuel and oxygenant first spray after the inner premix of flammenwerfer, and the exit flow of flammenwerfer is rotating jet;
(5) along the short transverse in core reaction chamber, the electric field that a potential difference is not less than 60V is applied to inside, core reaction chamber;
(6) finished product acquisition time is 5 minutes.
Fig. 6 is the stereoscan photograph of the carbon nano pipe array prepared by embodiment 2.As can be seen from Figure 6, carbon nanotube cluster ground oriented growth, lines up neat array, and caliber is comparatively thin, and pipeline is comparatively straight, and impurity is few.
Above embodiment is only preferred embodiment of the present invention, is not limited to the present invention, all make within spirit of the present invention and principle any amendment, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a system for synthesizing carbon nanotubes, is characterized in that, comprises circulation flame territory, carbon source pyrolysis territory, carbon nanotube composite field, finished product collecting unit and chemical reaction raw material supply unit; And core reaction chamber, circulation flame room, flammenwerfer, top umbrella; It is indoor that described circulation flame territory is positioned at circulation flame, described core reaction chamber is positioned at the center of circulation flame room, described carbon source pyrolysis territory is positioned at bottom, core reaction chamber, described carbon nanotube composite field is positioned at core reaction chamber internal upper part, the jet orifice of described flammenwerfer is positioned at the sidewall of circulation flame room, described top umbrella is positioned at the top in core reaction chamber, described finished product collecting unit is positioned at above the umbrella of top, and described chemical reaction raw material supply unit is to feed in circulation flame room and core reaction chamber.
2. system according to claim 1, is characterized in that, described finished product collecting unit comprises flip-over type finished product acquisition probe and travelling belt.
3. system according to claim 1, is characterized in that, described chemical reaction raw material supply unit comprises carbon source supply equipment, assist gas supply equipment, catalyzer supply equipment, fuel facility, oxygenant supply equipment.
4. system according to claim 1, it is characterized in that, described core reaction chamber is tubular, and the profile of circulation flame room is prismatic, its external wall cross-section is Polygons, and the jet orifice of flammenwerfer is arranged on each end points polygonal or on each bar limit.
5. system according to claim 1, it is characterized in that, described flammenwerfer installs one group or install many groups at different heights place at the sustained height place of circulation flame room sidewall, each in same group of flammenwerfer is installed in the sustained height place on the sidewall of circulation flame room.
6. system according to claim 5, is characterized in that, the exit flow of described flammenwerfer is direct jet, or rotating jet, and the geometric axis of air-flow is all tangent with the outer wall in tubular core reaction chamber; After the air-flow of each flammenwerfer ejection converges, the central zone in circulation flame room is formed vigorous combustion and around the flame of the rapid rotational flow of core reaction cavity outer wall.
7. system according to claim 2, it is characterized in that, automatic spring when described flip-over type finished product acquisition probe arrives directly over carbon nanotube composite field, extend into the predetermined position in carbon nanotube composite field, meanwhile, travelling belt is out of service immediately, to gather obtained finished product carbon nanotube; After the residence time of probe reaches default finished product acquisition time, probe just can reply position by appliance for releasing single, and travelling belt also can continue to run immediately.
8. system according to claim 3, is characterized in that, the carbon source of described carbon source supply equipment supply is the carbon raw material of gas, liquid, solid or plasma body;
The assist gas of described assist gas supply equipment supply refers to hydrogen and rare gas element or low activity gas;
The catalyzer of described catalyzer supply equipment supply is the mixture that the compound of transition metal simple substance or alloy or transition metal or above-mentioned simple substance, alloy or compound are formed;
The fuel of described fuel facility supply is the higher calorific value inflammable substance of gas, liquid or solid;
The oxygenant of described oxygenant supply equipment supply is air, pure oxygen or oxygen-nitrogen gas mixture.
9. system according to claim 1, is characterized in that, described system also comprises:
(1) bypath system, described bypath system needs change operation condition or system go wrong need to shut down time, can by the gas with refrigerating function direct input coefficient, described gas is rare gas element or low activity gas;
(2) temperature sensor and coupled digital instrument: in order to monitor the temperature of carbon source pyrolysis territory and carbon nanotube composite field;
(3) digital timer: with temperature sensor with the use of, automatic spring and the homing action of finished product acquisition probe can be realized, and travelling belt out of service and continue run action;
(4) lighter for ignition: when system brings into operation, lights by it the fuel sprayed from flammenwerfer;
(5) impeller and the director of Swirl Condition can be provided, make the exit flow of flammenwerfer form rotating jet, to coordinate the combustioncharacteristics controlling flame;
(6) furnace hopper: be in the system of fuel with solid, installs furnace hopper in the bottom of circulation flame room, is used for collecting ashes.
10. utilize the method for the system synthesis carbon nanotube described in any one in claim 1-9, comprise the following steps:
(1) starting fluid supply equipment and oxygenant supply equipment, transfer the fuel and oxygenant in flammenwerfer, for igniting is prepared;
(2) start assist gas supply equipment, in core reaction chamber, carry cooling gas;
(3) initial igniter, lights the mixture of fuel and the oxygenant sprayed from flammenwerfer;
(4) after the circulation flame formation of circulation flame indoor, the consumption of fuel metering and oxygenant is to desirable value;
(5) burn with treating circulation flame stabilization, and after the circulation flame temperature at the indoor different heights place of circulation flame all reaches design load, start carbon source supply equipment and catalyzer supply equipment, in core reaction chamber, carry carbon source and catalyzer;
(6) consumption of carbon source and catalyzer is tuned up to design variable, make carbon source start pyrolysis occurs;
(7) after the temperature of carbon source pyrolysis territory and carbon nanotube composite field all reaches design load, finished product collecting unit is started;
(8) when first flip-over type finished product acquisition probe arrives directly over carbon nanotube composite field with travelling belt, automatic spring, extend into the predetermined position in carbon nanotube composite field, starts the carbon nanotube gathering synthesis; Meanwhile, travelling belt is out of service;
(9) after first residence time of flip-over type finished product acquisition probe in carbon nanotube composite field reaches default finished product acquisition time, appliance for releasing single replys position, and travelling belt continues to run;
(10) the flip-over type finished product acquisition probe continued repeats the step of (8), (9) two steps successively, until system is out of service;
When needs change operation condition or system go wrong need to shut down time, then carry out according to following steps:
(11) close fuel facility and oxygenant supply equipment, stop transfer the fuel and oxygenant in flammenwerfer, make in combustion chamber flame-out;
(12) close carbon source supply equipment and catalyzer supply equipment, stop carrying carbon source and catalyzer in core reaction chamber;
(13) close finished product collecting unit, make it out of service;
(14) open bypath system, in flammenwerfer and core reaction chamber, carry cooling gas, and cooling gas is sprayed in combustion chamber;
(15) indoor to be combusted temperature everywhere is all down to 200 DEG C, closes assist gas supply equipment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675282A (en) * | 2018-04-19 | 2018-10-19 | 华北电力大学 | Plasma reinforces flame method and prepares carbon nanotube industrial production device |
| CN114162806A (en) * | 2022-01-07 | 2022-03-11 | 北京石油化工学院 | Flame-controllable symmetrically-distributed combustor and method for synthesizing carbon nano tube by using same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050077168A1 (en) * | 2003-06-24 | 2005-04-14 | Little Reginald B. | Neutron activated and laser stimulated chemical luminescence and condensation for the mass production of diamond, carbon nanotube and other carbonaceous articles |
| CN2723423Y (en) * | 2004-03-15 | 2005-09-07 | 西安交通大学 | Plasma reinforced photo-thermal chemical gas phase depositing device for preparing carbon nano tube film |
| CN1923677A (en) * | 2005-09-02 | 2007-03-07 | 鸿富锦精密工业（深圳）有限公司 | Carbon nano-tube growth apparatus and method |
| CN104787747A (en) * | 2015-04-10 | 2015-07-22 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
-
2015
- 2015-10-22 CN CN201510691230.1A patent/CN105217599B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050077168A1 (en) * | 2003-06-24 | 2005-04-14 | Little Reginald B. | Neutron activated and laser stimulated chemical luminescence and condensation for the mass production of diamond, carbon nanotube and other carbonaceous articles |
| CN2723423Y (en) * | 2004-03-15 | 2005-09-07 | 西安交通大学 | Plasma reinforced photo-thermal chemical gas phase depositing device for preparing carbon nano tube film |
| CN1923677A (en) * | 2005-09-02 | 2007-03-07 | 鸿富锦精密工业（深圳）有限公司 | Carbon nano-tube growth apparatus and method |
| CN104787747A (en) * | 2015-04-10 | 2015-07-22 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675282A (en) * | 2018-04-19 | 2018-10-19 | 华北电力大学 | Plasma reinforces flame method and prepares carbon nanotube industrial production device |
| CN114162806A (en) * | 2022-01-07 | 2022-03-11 | 北京石油化工学院 | Flame-controllable symmetrically-distributed combustor and method for synthesizing carbon nano tube by using same |
| CN114162806B (en) * | 2022-01-07 | 2023-05-16 | 北京石油化工学院 | Burner with controllable flame and symmetrical distribution and method for synthesizing carbon nano tube by burner |
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