CN103395774A - Reaction device and method for producing graphene or carbon nanotubes - Google Patents
Reaction device and method for producing graphene or carbon nanotubes Download PDFInfo
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- CN103395774A CN103395774A CN2013103139774A CN201310313977A CN103395774A CN 103395774 A CN103395774 A CN 103395774A CN 2013103139774 A CN2013103139774 A CN 2013103139774A CN 201310313977 A CN201310313977 A CN 201310313977A CN 103395774 A CN103395774 A CN 103395774A
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Abstract
The invention provides a reaction device and method for producing graphene or carbon nanotubes. The reaction device comprises an enlarging section, a reaction section and a plurality of bins, wherein the upper end of the enlarging section is connected with a catalyst feeding device, the reaction section is connected to the lower end of the enlarging section, gas distribution boards can axially move and pass in the reaction section, a plurality of vent holes are formed in the gas distribution boards, an electric furnace surrounds the reaction section externally, the lower end of the reaction section is connected with a first gas inlet pipe, the bins are connected with the reaction section through inlet pipes, valves are arranged on the inlet pipes, and protection gas inlets are formed in the bins. According to the reaction device and method for producing the graphene or carbon nanotubes, continuous addition of a catalyst and continuous extraction of a solid-phase product can be realized, the production can be carried out continuously, and the production process efficiency is greatly improved.
Description
Technical field
The present invention is relevant for a kind of reaction unit and method, especially relevant in a kind of technical field of chemical for the production of reaction unit and the method for Graphene or carbon nanotube.
Background technology
The carbon nanomaterial such as carbon nanotube and Graphene is the study hotspot that last decade comes the carbon material field, because it has good electroconductibility, physical and chemical stability and higher physical strength, they have a good application prospect at aspects such as conductive additive, catalysis and composite strengthening toughening materials.
The prerequisite that carbon nanomaterial is used widely is development and the maturation of low-cost batch techniques, adopting the chemical vapor deposition method aspect carbon nanotube production at present more, the employing fluidized-bed that proposes in prior art is produced flow process and the reactor of carbon nanotube, can not realize totally continuous production process, catalyzer add or removing in batches of the finished product carried out.And the process of the standby Graphene of chemical vapor deposition legal system unrealized industrializing implementation also, but the report of efficient quantity-produced device and technical process is arranged not yet.
Therefore, be necessary to provide a kind of new reaction unit and method, overcome above-mentioned defect.
Summary of the invention
The purpose of this invention is to provide a kind of reaction unit of producing Graphene or carbon nanotube, what it can realize catalyzer constantly adds continuous extraction with the solid phase product, can uninterruptedly produce, and has greatly improved Production Flow Chart efficiency.
Another object of the present invention is to provide a kind of method of producing Graphene or carbon nanotube, and that adopts that the method can realize catalyzer constantly adds continuous extraction with the solid phase product, can uninterruptedly produce, and has greatly improved Production Flow Chart efficiency.
Above-mentioned purpose of the present invention can adopt following technical proposal to realize:
The invention provides a kind of reaction unit of producing Graphene or carbon nanotube, the reaction unit of described production Graphene or carbon nanotube comprises:
Expanding reach, its upper end is connected with the catalyst charge device;
Conversion zone, it is connected to the lower end of described expanding reach, can be equipped with gas distribution grid in described conversion zone with moving axially, offers a plurality of ventilating pits on described gas distribution grid, the outer peripheral of described conversion zone is provided with electric furnace, and the lower end of described conversion zone is connected with the first inlet pipe;
A plurality of feed bins, it is connected with described conversion zone by inlet tube, and described inlet tube is provided with valve, offers protection gas entrance on described feed bin.
In a preferred embodiment, described feed bin is two, and the inlet tube of two described feed bins is connected to first location and the second position of described conversion zone, and described first location is positioned at the top of the described second position.
In a preferred embodiment, described conversion zone comprises the first conversion zone and the second conversion zone, and described the first conversion zone is connected to the upper end of described the second conversion zone, and the diameter of described the first conversion zone is greater than the diameter of described the second conversion zone.
In a preferred embodiment, be connected with the second inlet pipe on described expanding reach, described the second inlet pipe stretches into the bottom of the first conversion zone of described conversion zone, and described gas distribution grid can be located in the second conversion zone of described conversion zone with moving axially.
The present invention also provides a kind of method of producing Graphene or carbon nanotube, and the method for described production Graphene or carbon nanotube adopts the reaction unit of above-mentioned production Graphene or carbon nanotube, and the method for described production Graphene or carbon nanotube comprises the steps:
A) provide catalyzer, described catalyzer is put into the catalyst charge device;
B) the first inlet pipe that certainly is connected to the conversion zone lower end is injected argon gas or nitrogen, a plurality of ventilating pits of offering on described argon gas or the nitrogen gas distribution grid in described conversion zone inject in described conversion zone, simultaneously, open the electric furnace that is around in described conversion zone outside;
C) after electric furnace is complete to described conversion zone heating, catalyzer in described catalyst charge device is injected and is connected in the described conversion zone of described expanding reach lower end by the expanding reach that is connected with described catalyst charge device, at this moment, inject the hydro carbons carbon-source gas in described conversion zone, described catalyzer, described argon gas or nitrogen and described hydro carbons carbon-source gas prepare the solid phase product through chemical vapour deposition in described conversion zone;
D) described solid phase product is entered in a plurality of feed bins that are connected to described conversion zone bottom.
In a preferred embodiment, also comprise step e) after described step d): the solid phase product in described a plurality of feed bins is carried out purification process.
In a preferred embodiment, described feed bin is two, and the inlet tube of two described feed bins is connected to first location and the second position of described conversion zone, and described first location is positioned at the top of the described second position.
In a preferred embodiment, in described step c), the gas distribution grid in described conversion zone is positioned at the first location top of described conversion zone.
In a preferred embodiment, in described step d), gas distribution grid in described conversion zone is moved to respectively the below of the described second position, or move between described first location and the described second position, described solid phase product enters respectively in corresponding described feed bin.
In a preferred embodiment, the argon gas that injects in described conversion zone or the gas speed of nitrogen are 0.01～10m/s.
The reaction unit of production Graphene of the present invention or carbon nanotube and characteristics and the advantage of method are:
One, reaction unit and the method for production Graphene of the present invention or carbon nanotube, in whole production process, the catalyst charge device of reaction unit can be constantly to charging in conversion zone, in addition, be connected to the feed bin of conversion zone bottom, the solid phase product for preparing in conversion zone constantly is plucked out of, and the present invention can uninterruptedly produce, and has greatly improved Production Flow Chart efficiency.
Two, reaction unit and the method for production Graphene of the present invention or carbon nanotube, the density of catalyst less due to not carbon deposit or carbon deposit is less, and can be located in the gas distribution grid in conversion zone with moving axially, thereunder under the effect of stream pressure, guaranteed that further the catalyzer in conversion zone does not fall into the below of gas distribution grid, thereby can not be used as the final product extraction; When the catalyst carbon deposit in conversion zone was fully completed, its tap density increased, and will enter in feed bin through the conversion zone bottom, as the finished product, was plucked out of.In addition, the conveying that the nitrogen that passes into from a plurality of ventilating pits of gas distribution grid or argon stream also help the solid phase product is carried out smoothly, makes the solid phase product have good mobility, avoids the generation of coking phenomenon.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, in below describing embodiment, the accompanying drawing of required use is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the front view of a reaction unit embodiment of production Graphene of the present invention or carbon nanotube.
Fig. 2 is the front view of another reaction unit embodiment of production Graphene of the present invention or carbon nanotube.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment that obtains, belong to the scope of protection of the invention.
The present embodiment provides a kind of reaction unit of producing Graphene or carbon nanotube, and the applicable cases of this device in Graphene or carbon nanotube production.
As shown in Figure 1, the invention provides a kind of reaction unit of producing Graphene or carbon nanotube, it comprises expanding reach 1, conversion zone 2 and a plurality of feed bin 3.Wherein: the upper end of expanding reach 1 is connected with catalyst charge device 4; Conversion zone 2 is connected to the lower end of described expanding reach 1, can be equipped with gas distribution grid 21 in described conversion zone 2 with moving axially, offer a plurality of ventilating pit (not shown)s on described gas distribution grid 21, the outer peripheral of described conversion zone 2 is provided with electric furnace 5, and the lower end of described conversion zone 2 is connected with the first inlet pipe 22; A plurality of feed bins 3 are connected with described conversion zone 2 by inlet tube 31, and described inlet tube 31 is provided with valve 32, offer protection gas entrance 33 on described feed bin 3.
Specifically, catalyst charge device 4 is connected to the upper end of expanding reach 1 and stretches in expanding reach 1, catalyst charge device 4 is used for holding catalyst, in the present invention, this catalyst charge device 4 is realized continuously or intermittent feeding for the mode that adopts screw conveyer or air pulse to spray, adopting the catalyst charge device 4 of screw conveyer or the charging of air pulse spray regime has been prior art, does not repeat them here its concrete structure.The upper end of expanding reach 1 offers tail gas outlet 11, and its underpart forms an inverted round stage bodily form, facilitates like this catalyzer in catalyst charge device 4 to pour into smoothly in the conversion zone 2 that is connected to expanding reach 1 lower end.
Conversion zone 2 is used for catalyzer is carried out chemical vapour deposition reaction, to prepare required Graphene or carbon nanotube.The electric furnace 5 that is around in conversion zone 2 outsides is used for conversion zone 2 is carried out heat treated.In the present invention, be located in movably the gas distribution grid 21 in conversion zone 2, be to control by the motor 23 that is connected to gas distribution grid 21 lower ends, according to needs of production, motor 23 can drive gas distribution grid 21 in the interior axial upper and lower displacement of conversion zone 2.A plurality of ventilating pits of offering on this gas distribution grid 21 are used for making the gas that passes in the first inlet pipe 22 that is connected to conversion zone 2 lower ends in those ventilating pits inject conversion zone 2.In the present embodiment, distance between the inwall of the outer rim of gas distribution grid 21 and conversion zone 2 is 0～0.5mm, can guarantee that like this gas distribution grid 21 is carrying out good coordinating under 400～950 ℃ with between conversion zone 2 inwalls, fall to the conversion zone 2 of gas distribution grid 21 belows with the pulverulent material of avoiding being positioned at gas distribution grid 21 tops, and as the finished product, be plucked out of; In addition, the gas that passes in conversion zone 2 from the first inlet pipe 22 can form certain air pressure below gas distribution grid 21, guaranteed further that also pulverulent material does not spill.
A plurality of feed bins 3 are connected on the lower outside wall of conversion zone 2, and feed bin 3 is used for the interior solid phase product that obtains after chemical vapour deposition reaction of splendid attire conversion zone 2.In the present invention, feed bin 3 is connected with conversion zone 2 by an inlet tube 31, and this inlet tube 31 is provided with valve 32, and valve 32 is used for opening or closing inlet tube 31; In addition, also offer protection gas entrance 33 on feed bin 3, this protection gas entrance 33 is used for passing into shielding gas such as nitrogen or argon gas to feed bin 3, prevents that air from entering.In the present embodiment, the inlet tube 31 that the reaction unit of production Graphene or carbon nanotube has 3, two feed bins 3 of two feed bins is connected on the first location 24 and the second position 25 of conversion zone 2, and described first location 24 is positioned at the top of the second position 25.Prepare Graphene or carbon nanotube solid phase product in conversion zone 2, and gas distribution grid 21 moves between the first location 24 and the second position 25 of conversion zone 2, be also, during B position in Fig. 1, open the valve 32 that is positioned on conversion zone 2 left side feed bin 3 inlet tubes 31 this moment, the solid phase product in conversion zone 2 will fall in the feed bin 3 in conversion zone 2 left sides; Move to the below of the second position 25 of conversion zone 2 when gas distribution grid 21, be also, during C position in Fig. 1, open the valve 32 that is positioned on conversion zone 2 right side feed bin 3 inlet tubes 31 this moment, the solid phase products in conversion zone 2 will fall into the feed bin 3 that is positioned at conversion zone 2 right sides.
it is as follows that the reaction unit of the present invention by this production Graphene or carbon nanotube prepares the Production Flow Chart of Graphene: at first, the first inlet pipe 22 of autoreaction section 2 belows passes into argon gas, argon gas injects in conversion zone 2 through a plurality of ventilating pits of gas distribution grid 21, open the electric furnace 5 that is around in conversion zone 2 outsides this moment, makes electric furnace 5 be warming up to 900 ℃, afterwards, from the first inlet pipe 22, pass into methane in conversion zone 2, starter motor 23, move to gas distribution grid 21 top of the first location 24 of conversion zone 2, also, and A position shown in Figure 1, then, the MgO template that catalyst charge device 4 is interior is in expanding reach 1 is poured conversion zone 2 into, during this, interior argon gas and the methane of constantly passing into of the first inlet pipe 22, reinforced when adding the MgO template approximately to suspend after 100g, make the MgO template, methane and argon gas were conversion zone 2 internal reaction 20 minutes, then starter motor 23, gas distribution grid 21 is displaced downwardly between the first location 24 and the second position 25 of conversion zone 2, be also, B position shown in Figure 1, make the solid phase product for preparing in conversion zone 2 enter the feed bin 3 that is positioned at conversion zone 2 left sides, during this, pass into argon gas from these protection gas entrance 33 places that are positioned at the feed bin 3 in conversion zone 2 left sides as protection gas, afterwards, starter motor 23, the top of the first location 24 of conversion zone 2 will be moved on on gas distribution grid 21, be also, A position shown in Figure 1, continuation adds approximately 100g of MgO template in catalyst charge device 4, react after 20 minutes mobile gas grid distributor 21 to B position discharging shown in Figure 1, so cyclical operation again, when the feed bin 3 that is positioned at conversion zone 2 left sides is soon filled, valve 32 on feed bin 3 inlet tubes 31 in off-response section 2 left sides, gas distribution grid 21 is moved to the below of the second position 25 of conversion zone 2, be also, C position shown in Figure 1, make the solid phase product for preparing in conversion zone 2 enter the feed bin 3 that is positioned at conversion zone 2 right sides, during this, these protection gas entrance 33 places that are positioned at the feed bin 3 on conversion zone 2 right sides pass into argon gas as protection gas certainly.Finally, the solid phase product in two feed bins 3 is taken out and to carry out purification process, also, with excessive hydrochloric acid and solid phase Product mix, stirring, then suction filtration, oven dry, obtain the Graphene product.
It is as follows that the reaction unit of the present invention by this production Graphene or carbon nanotube prepares the Production Flow Chart of single wall or double-walled carbon nano-tube: at first, the first inlet pipe 22 of autoreaction section 2 belows passes into argon gas, this argon gas injects in conversion zone 2 through a plurality of ventilating pits of gas distribution grid 21, open the electric furnace 5 that is around in conversion zone 2 outsides this moment, makes electric furnace 5 be warming up to 900 ℃; Afterwards, from the first inlet pipe 22, pass into methane in conversion zone 2, starter motor 23, move to gas distribution grid 21 between the first location 24 and the second position 25 of conversion zone 2, also, and B position shown in Figure 1; Then, the FeMo/MgO catalyzer that catalyst charge device 4 is interior is in expanding reach 1 is poured conversion zone 2 into, during this, interior argon gas and the methane of constantly passing into of the first inlet pipe 22, the FeMo/MgO catalyzer directly falls into the feed bin 3 that is arranged in conversion zone 2 left sides after entering the interior generation single wall of conversion zone 2 or double-walled carbon nano-tube, during this, these protection gas entrance 33 places that are positioned at the feed bin 3 in conversion zone 2 left sides pass into argon gas as protection gas certainly; When the feed bin 3 that is positioned at conversion zone 2 left sides is filled soon, valve 32 on feed bin 3 inlet tubes 31 in off-response section 2 left sides, gas distribution grid 21 is displaced downwardly to the below of the second position 25 of conversion zone 2, be also, C position shown in Figure 1, the solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 right sides; At this moment, take out the solid phase product in conversion zone 2 left side feed bins 3, and the protection gas entrance 33 of this feed bin 3 passes into argon gas with the emptying air that is arranged in conversion zone 2 left side feed bins 3 certainly; When the feed bin 3 that is positioned at conversion zone 2 right sides is filled soon, gas distribution grid 21 is moved between the first location 24 and the second position 25 of conversion zone 2, also, B position shown in Figure 1, solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 left sides, so loop.Finally, the solid phase product in two feed bins 3 is taken out and to carry out purification process, that is, with excessive hydrochloric acid and Product mix, stirring, then suction filtration, oven dry, obtain single wall or double-walled carbon nano-tube product.
it is as follows that the reaction unit of the present invention by this production Graphene or carbon nanotube prepares the Production Flow Chart of multi-walled carbon nano-tubes: at first, the first inlet pipe 22 of autoreaction section 2 belows passes into nitrogen, this nitrogen injects in conversion zone 2 through a plurality of ventilating pits of gas distribution grid 21, open the electric furnace 5 that is around in conversion zone 2 outsides this moment, makes electric furnace 5 be warming up to 1000 ℃, afterwards, from the first inlet pipe 22, pass into methane in conversion zone 2, starter motor 23, move to gas distribution grid 21 top of the first location 24 of conversion zone 2, also, and A position shown in Figure 1, then, the NiMo/MgO catalyzer that catalyst charge device 4 is interior is in expanding reach 1 is poured conversion zone 2 into, during this, interior nitrogen and the methane of constantly passing into of the first inlet pipe 22, the NiMo/MgO catalyzer, methane and nitrogen are at conversion zone 2 internal reactions after 30 minutes, gas distribution grid 21 is displaced downwardly between the first location 24 and the second position 25 of conversion zone 2, be also, B position shown in Figure 1, make the solid phase product for preparing in conversion zone 2 enter the feed bin 3 that is positioned at conversion zone 2 left sides, during this, pass into argon gas from these protection gas entrance 33 places that are positioned at the feed bin 3 in conversion zone 2 left sides as protection gas, when the feed bin 3 in question response section 2 left sides is filled soon, feed bin 3 valves 32 in off-response section 2 left sides, gas distribution grid 21 is displaced downwardly to the below of the second position 25 of conversion zone 2, be also, C position shown in Figure 1, the solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 right sides, at this moment, take out the solid phase product in conversion zone 2 left side feed bins 3, and the protection gas entrance 33 of this feed bin 3 passes into argon gas with emptying air in it certainly, when the feed bin 3 that is positioned at conversion zone 2 right sides is filled soon, gas distribution grid 21 is moved between the first location 24 and the second position 25 of conversion zone 2, also, B position shown in Figure 1, solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 left sides, so loop.Finally, the solid phase product in two feed bins 3 is taken out and to carry out purification process, that is, with excessive hydrochloric acid and Product mix, stirring, then suction filtration, oven dry, obtain single wall or double-walled carbon nano-tube product.
The reaction unit of production Graphene of the present invention or carbon nanotube, in whole production process, its catalyst charge device 4 can be constantly to the interior charging of conversion zone 2, in addition, be connected to the feed bin 3 of conversion zone 2 bottoms, the solid phase product for preparing in conversion zone 2 constantly is plucked out of, and the present invention can uninterruptedly produce, and has greatly improved Production Flow Chart efficiency.Have again, the density of catalyst less due to not carbon deposit or carbon deposit is less, and can be located in the gas distribution grid 21 in conversion zone 2 with moving axially, thereunder under the effect of stream pressure, guaranteed that further the catalyzer in conversion zone 2 does not fall into the below of gas distribution grid 21, thereby can not be used as the final product extraction; When the catalyst carbon deposit in conversion zone 2 was fully completed, its tap density increased, and will enter in feed bin 3 through conversion zone 2 bottoms, as the finished product, was plucked out of.In addition, the conveying that the nitrogen that passes into from a plurality of ventilating pits of gas distribution grid 21 or argon stream also help the solid phase product is carried out smoothly, makes the solid phase product have good mobility, avoids the generation of coking phenomenon.
According to an embodiment of the invention, as shown in Figure 2, described conversion zone 2 comprises the first conversion zone 26 and the second conversion zone 27, and described the first conversion zone 26 is connected to the upper end of described the second conversion zone 27, and the diameter of described the first conversion zone 26 is greater than the diameter of described the second conversion zone 27.The present invention is designed to diameter less than the first conversion zone 26 with the diameter of the second conversion zone 27 of conversion zone 2, like this through the air-flow that gas distribution grid 21 passes into can tap density is less material blow out in the second conversion zone 27, the larger material of tap density is entered in the feed bin 3 of appointment smoothly.
According to an embodiment of the invention, be connected with the second inlet pipe 12 on described expanding reach 1, described the second inlet pipe 12 stretches into the bottom of the first conversion zone 26 of described conversion zone 2, and described gas distribution grid 21 can be located in the second conversion zone 27 of described conversion zone 2 with moving axially.This second inlet pipe 12 is used for passing into methane, can make like this first inlet pipe 21 only pass into nitrogen or argon gas in whole Production Flow Chart process, prevents from follow-up having potential safety hazard in the first inlet pipe 21 passes into the process of methane.
Embodiment 2
The present embodiment provides a kind of processing method of producing Graphene or carbon nanotube.
The present invention also provides a kind of method of producing Graphene or carbon nanotube, the method of described production Graphene or carbon nanotube adopts above-mentioned production Graphene or the reaction unit (as depicted in figs. 1 and 2) of carbon nanotube, and the method for described production Graphene or carbon nanotube comprises the steps:
A) provide catalyzer, described catalyzer is put into catalyst charge device 4;
B) the first inlet pipe 22 that certainly is connected to conversion zone 2 lower ends is injected argon gas or nitrogen, a plurality of ventilating pits of offering on described argon gas or the nitrogen gas distribution grid 21 in described conversion zone 2 inject in described conversion zone 2, simultaneously, open the electric furnace 5 that is around in described conversion zone 2 outsides;
C) after 5 pairs of described conversion zone 2 heating of electric furnace are complete, catalyzer in described catalyst charge device 4 is injected and is connected in the described conversion zone 2 of described expanding reach 1 lower end by the expanding reach 1 that is connected with described catalyst charge device 4, at this moment, to the interior injection hydro carbons of described conversion zone 2 carbon-source gas, described catalyzer, described argon gas or nitrogen and described hydro carbons carbon-source gas prepare the solid phase product through chemical vapour deposition described conversion zone 2 is interior;
D) described solid phase product is entered in a plurality of feed bins 3 that are connected to described conversion zone 2 bottoms.
Specifically, structure, principle of work and the beneficial effect of the production Graphene of the present embodiment 2 or the reaction unit of carbon nanotube is identical with the reaction unit of the production Graphene of embodiment 1 or carbon nanotube, does not repeat them here.
In the present invention, also comprise step e) after described step d): the solid phase product in described a plurality of feed bins 3 is carried out purification process.Also namely, with excessive hydrochloric acid and Product mix, stirring, then suction filtration, oven dry, obtain single wall or double-walled carbon nano-tube product.
In the present embodiment, the gas speed of the argon gas of described conversion zone 2 interior injections or nitrogen is 0.01～10m/s.Described argon gas or nitrogen gas stream are 0.1～100m/s through the gas speed of a plurality of ventilating pits of described gas distribution grid 21.In described step c), the Heating temperature of described electric furnace is 900～1000 ℃.Described hydro carbons carbon-source gas can be methane.
In the present embodiment, the feed bin 3 of producing the reaction unit of Graphene or carbon nanotube is two, and the inlet tube 31 of two feed bins 3 is connected to the first location 24 and the second position 25 of conversion zone 2, and first location 24 is positioned at the top of the second position 25.In described step c), the gas distribution grid 21 in conversion zone 2 is positioned at first location 24 tops of conversion zone 2.
Further, in described step d), the gas distribution grid in described conversion zone is moved to respectively the below of the described second position, or move between described first location and the described second position, described solid phase product enters respectively in corresponding described feed bin.
it is as follows that the reaction unit of the present invention by this production Graphene or carbon nanotube prepares the Production Flow Chart of Graphene: at first, the first inlet pipe 22 of autoreaction section 2 belows passes into argon gas, argon gas injects in conversion zone 2 through a plurality of ventilating pits of gas distribution grid 21, open the electric furnace 5 that is around in conversion zone 2 outsides this moment, makes electric furnace 5 be warming up to 900 ℃, afterwards, from the first inlet pipe 22, pass into methane in conversion zone 2, starter motor 23, move to gas distribution grid 21 top of the first location 24 of conversion zone 2, also, and A position shown in Figure 1, then, the MgO template that catalyst charge device 4 is interior is in expanding reach 1 is poured conversion zone 2 into, during this, interior argon gas and the methane of constantly passing into of the first inlet pipe 22, reinforced when adding the MgO template approximately to suspend after 100g, make the MgO template, methane and argon gas were conversion zone 2 internal reaction 20 minutes, then starter motor 23, gas distribution grid 21 is displaced downwardly between the first location 24 and the second position 25 of conversion zone 2, be also, B position shown in Figure 1, make the solid phase product for preparing in conversion zone 2 enter the feed bin 3 that is positioned at conversion zone 2 left sides, during this, pass into argon gas from these protection gas entrance 33 places that are positioned at the feed bin 3 in conversion zone 2 left sides as protection gas, afterwards, starter motor 23, the top of the first location 24 of conversion zone 2 will be moved on on gas distribution grid 21, be also, A position shown in Figure 1, continuation adds approximately 100g of MgO template in catalyst charge device 4, react after 20 minutes mobile gas grid distributor 21 to B position discharging shown in Figure 1, so cyclical operation again, when the feed bin 3 that is positioned at conversion zone 2 left sides is soon filled, valve 32 on feed bin 3 inlet tubes 31 in off-response section 2 left sides, gas distribution grid 21 is moved to the below of the second position 25 of conversion zone 2, be also, C position shown in Figure 1, make the solid phase product for preparing in conversion zone 2 enter the feed bin 3 that is positioned at conversion zone 2 right sides, during this, these protection gas entrance 33 places that are positioned at the feed bin 3 on conversion zone 2 right sides pass into argon gas as protection gas certainly.Finally, the solid phase product in two feed bins 3 is taken out and to carry out purification process, also, with excessive hydrochloric acid and solid phase Product mix, stirring, then suction filtration, oven dry, obtain the Graphene product.
It is as follows that the reaction unit of the present invention by this production Graphene or carbon nanotube prepares the Production Flow Chart of single wall or double-walled carbon nano-tube: at first, the first inlet pipe 22 of autoreaction section 2 belows passes into argon gas, this argon gas injects in conversion zone 2 through a plurality of ventilating pits of gas distribution grid 21, open the electric furnace 5 that is around in conversion zone 2 outsides this moment, makes electric furnace 5 be warming up to 900 ℃; Afterwards, from the first inlet pipe 22, pass into methane in conversion zone 2, starter motor 23, move to gas distribution grid 21 between the first location 24 and the second position 25 of conversion zone 2, also, and B position shown in Figure 1; Then, the FeMo/MgO catalyzer that catalyst charge device 4 is interior is in expanding reach 1 is poured conversion zone 2 into, during this, interior argon gas and the methane of constantly passing into of the first inlet pipe 22, the FeMo/MgO catalyzer directly falls into the feed bin 3 that is arranged in conversion zone 2 left sides after entering the interior generation single wall of conversion zone 2 or double-walled carbon nano-tube, during this, these protection gas entrance 33 places that are positioned at the feed bin 3 in conversion zone 2 left sides pass into argon gas as protection gas certainly; When the feed bin 3 that is positioned at conversion zone 2 left sides is filled soon, valve 32 on feed bin 3 inlet tubes 31 in off-response section 2 left sides, gas distribution grid 21 is displaced downwardly to the below of the second position 25 of conversion zone 2, be also, C position shown in Figure 1, the solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 right sides; At this moment, take out the solid phase product in conversion zone 2 left side feed bins 3, and the protection gas entrance 33 of this feed bin 3 passes into argon gas with the emptying air that is arranged in conversion zone 2 left side feed bins 3 certainly; When the feed bin 3 that is positioned at conversion zone 2 right sides is filled soon, gas distribution grid 21 is moved between the first location 24 and the second position 25 of conversion zone 2, also, B position shown in Figure 1, solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 left sides, so loop.Finally, the solid phase product in two feed bins 3 is taken out and to carry out purification process, that is, with excessive hydrochloric acid and Product mix, stirring, then suction filtration, oven dry, obtain single wall or double-walled carbon nano-tube product.
it is as follows that the reaction unit of the present invention by this production Graphene or carbon nanotube prepares the Production Flow Chart of multi-walled carbon nano-tubes: at first, the first inlet pipe 22 of autoreaction section 2 belows passes into nitrogen, this nitrogen injects in conversion zone 2 through a plurality of ventilating pits of gas distribution grid 21, open the electric furnace 5 that is around in conversion zone 2 outsides this moment, makes electric furnace 5 be warming up to 1000 ℃, afterwards, from the first inlet pipe 22, pass into methane in conversion zone 2, starter motor 23, move to gas distribution grid 21 top of the first location 24 of conversion zone 2, also, and A position shown in Figure 1, then, the NiMo/MgO catalyzer that catalyst charge device 4 is interior is in expanding reach 1 is poured conversion zone 2 into, during this, interior nitrogen and the methane of constantly passing into of the first inlet pipe 22, the NiMo/MgO catalyzer, methane and nitrogen are at conversion zone 2 internal reactions after 30 minutes, gas distribution grid 21 is displaced downwardly between the first location 24 and the second position 25 of conversion zone 2, be also, B position shown in Figure 1, make the solid phase product for preparing in conversion zone 2 enter the feed bin 3 that is positioned at conversion zone 2 left sides, during this, pass into argon gas from these protection gas entrance 33 places that are positioned at the feed bin 3 in conversion zone 2 left sides as protection gas, when the feed bin 3 in question response section 2 left sides is filled soon, feed bin 3 valves 32 in off-response section 2 left sides, gas distribution grid 21 is displaced downwardly to the below of the second position 25 of conversion zone 2, be also, C position shown in Figure 1, the solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 right sides, at this moment, take out the solid phase product in conversion zone 2 left side feed bins 3, and the protection gas entrance 33 of this feed bin 3 passes into argon gas with emptying air in it certainly, when the feed bin 3 that is positioned at conversion zone 2 right sides is filled soon, gas distribution grid 21 is moved between the first location 24 and the second position 25 of conversion zone 2, also, B position shown in Figure 1, solid phase product in conversion zone 2 will fall into the feed bin 3 that is arranged in conversion zone 2 left sides, so loop.Finally, the solid phase product in two feed bins 3 is taken out and to carry out purification process, that is, with excessive hydrochloric acid and Product mix, stirring, then suction filtration, oven dry, obtain single wall or double-walled carbon nano-tube product.
The method of production Graphene of the present invention or carbon nanotube, in whole production process, the catalyst charge device of the production Graphene that the method adopts or the reaction unit of carbon nanotube can be constantly to charging in conversion zone, in addition, be connected to the feed bin of conversion zone bottom, the solid phase product for preparing in conversion zone constantly is plucked out of, and method of the present invention can uninterruptedly be produced, and has greatly improved Production Flow Chart efficiency.
The foregoing is only several embodiments of the present invention, those skilled in the art can carry out various changes or modification and not break away from the spirit and scope of the present invention the embodiment of the present invention according to the disclosed content of application documents.
Claims (10)
1. a reaction unit of producing Graphene or carbon nanotube, is characterized in that, the reaction unit of described production Graphene or carbon nanotube comprises:
Expanding reach, its upper end is connected with the catalyst charge device;
Conversion zone, it is connected to the lower end of described expanding reach, can be equipped with gas distribution grid in described conversion zone with moving axially, offers a plurality of ventilating pits on described gas distribution grid, the outer peripheral of described conversion zone is provided with electric furnace, and the lower end of described conversion zone is connected with the first inlet pipe;
A plurality of feed bins, it is connected with described conversion zone by inlet tube, and described inlet tube is provided with valve, offers protection gas entrance on described feed bin.
2. the reaction unit of production Graphene as claimed in claim 1 or carbon nanotube, it is characterized in that, described feed bin is two, and the inlet tube of two described feed bins is connected to first location and the second position of described conversion zone, and described first location is positioned at the top of the described second position.
3. the reaction unit of production Graphene as claimed in claim 1 or carbon nanotube, it is characterized in that, described conversion zone comprises the first conversion zone and the second conversion zone, described the first conversion zone is connected to the upper end of described the second conversion zone, and the diameter of described the first conversion zone is greater than the diameter of described the second conversion zone.
4. the reaction unit of production Graphene as claimed in claim 3 or carbon nanotube, it is characterized in that, be connected with the second inlet pipe on described expanding reach, described the second inlet pipe stretches into the bottom of the first conversion zone of described conversion zone, and described gas distribution grid can be located in the second conversion zone of described conversion zone with moving axially.
5. method of producing Graphene or carbon nanotube, it is characterized in that, the method of described production Graphene or carbon nanotube adopts the reaction unit of production Graphene as described in any one in claim 1～4 or carbon nanotube, and the method for described production Graphene or carbon nanotube comprises the steps:
A) provide catalyzer, described catalyzer is put into the catalyst charge device;
B) the first inlet pipe that certainly is connected to the conversion zone lower end is injected argon gas or nitrogen, a plurality of ventilating pits of offering on described argon gas or the nitrogen gas distribution grid in described conversion zone inject in described conversion zone, simultaneously, open the electric furnace that is around in described conversion zone outside;
C) after electric furnace is complete to described conversion zone heating, catalyzer in described catalyst charge device is injected and is connected in the described conversion zone of described expanding reach lower end by the expanding reach that is connected with described catalyst charge device, at this moment, inject the hydro carbons carbon-source gas in described conversion zone, described catalyzer, described argon gas or nitrogen and described hydro carbons carbon-source gas prepare the solid phase product through chemical vapour deposition in described conversion zone;
D) described solid phase product is entered in a plurality of feed bins that are connected to described conversion zone bottom.
6. the method for production Graphene as claimed in claim 5 or carbon nanotube, is characterized in that, also comprises step e) after described step d): the solid phase product in described a plurality of feed bins is carried out purification process.
7. the method for production Graphene as claimed in claim 5 or carbon nanotube, it is characterized in that, described feed bin is two, and the inlet tube of two described feed bins is connected to first location and the second position of described conversion zone, and described first location is positioned at the top of the described second position.
8. the method for production Graphene as claimed in claim 7 or carbon nanotube, is characterized in that, in described step c), the gas distribution grid in described conversion zone is positioned at the first location top of described conversion zone.
9. the method for production Graphene as claimed in claim 7 or carbon nanotube, it is characterized in that, in described step d), gas distribution grid in described conversion zone is moved to respectively the below of the described second position, or move between described first location and the described second position, described solid phase product enters respectively in corresponding described feed bin.
10. the method for production Graphene as claimed in claim 5 or carbon nanotube, is characterized in that, the argon gas that injects in described conversion zone or the gas speed of nitrogen are 0.01～10m/s.
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| CN106379885A (en) * | 2016-08-31 | 2017-02-08 | 潍坊昊晟碳材料有限公司 | Efficient preparation method of carbon nanotubes or graphene |
| WO2018192345A1 (en) * | 2017-04-21 | 2018-10-25 | 山东大展纳米材料有限公司 | Device and method for single-stage continuous preparation of carbon nanotubes |
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| KR20090073346A (en) * | 2007-12-31 | 2009-07-03 | 세메스 주식회사 | Fluidizing bed apparatus and method for prosucting carbon nano tube |
| CN102079519A (en) * | 2009-11-17 | 2011-06-01 | 温州大学 | Preparation method and production equipment for controllably growing carbon nanotubes |
| CN102602912A (en) * | 2012-03-15 | 2012-07-25 | 南昌大学 | Synthesizing device for continuously producing carbon nano pipe with shape of crystal whisker |
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| KR20090073346A (en) * | 2007-12-31 | 2009-07-03 | 세메스 주식회사 | Fluidizing bed apparatus and method for prosucting carbon nano tube |
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| CN106379885A (en) * | 2016-08-31 | 2017-02-08 | 潍坊昊晟碳材料有限公司 | Efficient preparation method of carbon nanotubes or graphene |
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| WO2018192345A1 (en) * | 2017-04-21 | 2018-10-25 | 山东大展纳米材料有限公司 | Device and method for single-stage continuous preparation of carbon nanotubes |
| US11820661B2 (en) | 2017-04-21 | 2023-11-21 | Shandong Dazhan Nano Materials Co., Ltd. | Device and method for single-stage continuous preparation of carbon nanotubes |
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