CN102530921A - Reactor for semi-continuous production of carbon nano tube - Google Patents
Reactor for semi-continuous production of carbon nano tube Download PDFInfo
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- CN102530921A CN102530921A CN2012100432453A CN201210043245A CN102530921A CN 102530921 A CN102530921 A CN 102530921A CN 2012100432453 A CN2012100432453 A CN 2012100432453A CN 201210043245 A CN201210043245 A CN 201210043245A CN 102530921 A CN102530921 A CN 102530921A
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Abstract
The invention discloses a reactor for semi-continuous production of a carbon nano tube, and relates to a reactor for producing a carbon nano tube. The reactor for semi-continuous production of the carbon nano tube has the advantages of simple structure, short operation cycle, low energy consumption, high space-time utilization rate of the equipment and the like, is convenient to operate and can enable a solid product to be quickly removed out of the reactor in high-temperature working condition. The reactor is provided with a reactor body, a saggar, a carbon nano tube bed layer, a gas preheater, a cooler and a saggar lifting air pump, wherein the top of the reactor body is provided with a thermocouple lead-out point and a tail gas outlet; the upper part of the reactor body is provided with a heating layer; the saggar is arranged in the reactor body; the carbon nano tube bed layer is arranged in the saggar; a raw gas inlet is arranged on one side of the gas preheater; a heating galvanic couple rod is arranged in the gas preheater; the gas preheater is arranged on one side of the lower part of the reactor body and connected with the reactor body; the cooler is arranged at the lower part of the reactor body and forms a vertical trapezoidal structure with the reactor body and the gas preheater; and the saggar lifting air pump is arranged in the cooler.
Description
Technical field
The present invention relates to a kind of production carbon nanotube reactor drum, especially relate to a kind of semicontinuous production carbon nanotube reactor drum.
Background technology
Carbon nanotube is a kind of One-dimensional Quantum material with unique texture, and being curled by the graphite carbon atomic shell forms, and the pipe diameter is generally several nanometers to tens nanometers, and thickness of pipe is merely several nanometers, and length can reach several microns.1991; Professor Iijima of Japan NEC Corporation has found multi-wall carbon nano-tube carbon pipe for the first time in the cathode deposit that the discharge of stone mill rod forms; Owing to have the potential high-performance; Carbon nanotube still all will have the major application prospect at material science at physics, chemistry, cause numerous scientists' very big concern, become one of research object the most popular in the nanotechnology at present.In recent years, countries such as the U.S., Japan, Germany and China have set up nano materials research mechanism in succession, and the progress of carbon nanotube is accelerated thereupon, and have obtained breakthrough in preparation and application facet.Global carbon nanotube market demand surpassed 1,900,000,000 dollars in 2010, and average growth rate surpasses 80%, estimates that Asian-Pacific market demand in 2012 will break through 2,500,000,000 dollars.
The preparation method of carbon nanotube mainly contains arc discharge method, laser evaporation method and catalytic pyrolysis method etc.; Wherein catalytic pyrolysis method is chemical Vapor deposition process (chemical vapour deposition again; CVD); Be the preparation method of the carbon nanotube that gets up of development in recent years, its cost is low, output is high, is the prefered method of producing carbon nanotube in enormous quantities.At present, the CVD method mainly contains 3 kinds of technologies, is respectively fixed-bed process, moving bed process and fluidized-bed process, and corresponding reactor drum mainly contains 3 kinds: moving-bed, fixed bed and fluidized-bed.Moving-bed is mobile fixed bed, has the problem of thermograde and translational speed aspect.Fluidized-bed process is present high quality, produce one of the most promising technology of CNTs in batches.The fixed-bed process device is simple, flexible and convenient operation, and facility investment is few, but has temperature and mass transfer gradient, and can only periodical operation, the suitable CNTs that produces in batches.Gas-solid contacts in the fluidized-bed, and thermograde and resistance to mass transfer are little, and catalyst utilization is high, and can carry out shifting out and the continuous interpolation of catalyzer of product as required, but but also continuous production of periodical operation.As being method and the device that discloses a kind of producing Nano carbon tubes continuously in the one Chinese patent application of CN101049927A at publication number, provide a kind of multi-stage countercurrent tank reactor, but continuous production CNTs, but technology controlling and process is difficult.Because catalytic pyrolysis prepares in this type of carbon nanotube solid vapor phase deposition process; Monodimension nanometer material can occur and be prone to produce bonding; Very easily cause the fluidisation difficulty in the production process; Caking appears in the bed thereby make, local temperature, density unevenness is even or because of carbon deposits between particle can't normal running.Therefore, do not see as yet that so far the relevant fluidized-bed that utilizes carries out the bibliographical information that the serialization industry test is produced carbon nanomaterial in batches.Zavarukhin in 2004, (Zavarukhin, S.G, Kuvshinov G.G.The kinetic model of formation ofnanofibrous carbon fromCH such as S.G
4-H
2Mixture over ahigh-loaded nickel catalyst with consideration for the catalyst [J] .AppliedCatalysis; 2004; 272 (1-2): 219-227) reported vibrations tubular type fluidized-bed reactor, equipment is simple, and output is high; But be periodical operation, be difficult to realize producing in batches.Above-mentioned fluidized-bed reactor is all the lab scale stage.Philippe; R (AuroreMorancais; Massimiliano CorriasCatalytic, et al.Production of carbon nanotubes by fluidized-BedCVD [J] .Midi-Pyrenees Chemical Vapor Deposition, 2007; 13 (9): 447-457) reported the fluidized-bed tubular reactor of pilot scale, but be periodical operation.
Summary of the invention
The objective of the invention is to overcome the technology controlling and process difficulty of existing made of carbon nanotubes continuous fluidized bed; The batch fluidized bed process cycle is long, operation is difficult for; Be difficult to realize the difficult point of carbon nanotube production in enormous quantities; Provide a kind of not only have easy to operate, simple in structure, the operational cycle is short, energy consumption is low, equipment time and space utilization rate advantages of higher, and can solve solid phase prod shifts out reactor drum fast under worst hot case semicontinuous production carbon nanotube reactor drum.
The present invention is provided with reactor body, saggar, carbon nanotube bed, gas preheater, water cooler and saggar up-down air pump; The top of said reactor body is provided with the derivation point and the tail gas outlet of thermopair, and the top of reactor body is provided with zone of heating; Saggar is located in the reactor body; The carbon nanotube bed is located in the saggar; One side of gas preheater is provided with the virgin gas inlet, is placed with in the gas preheater to add the thermopair rod, and gas preheater is located at bottom one side of reactor body and is connected as a single entity with reactor body; Water cooler is located at the reactor body bottom and is constituted cat ladder shape structure with reactor body and gas preheater; Saggar up-down air pump is located in the water cooler.
Said saggar liftable in reactor body moves; The carbon nanotube bed is located in the saggar and is constituted the reaction vitellarium of carbon nanotube.Said gas preheater and reactor body are L-shaped.But said water cooler translation breaks away from reactor body, is convenient to the saggar loading and unloading.
Said reactor body can adopt catalytic cracker.
Compare with existing production carbon nanotube reactor drum, the present invention has following outstanding advantage:
1) because reactor body of the present invention adopts perpendicular T type structure design; Said perpendicular T type structure utilizes fluid to be prone to the adjustment flow direction, solid keeps vertical service performance; Different reactants gets into reactive moieties (catalytic cracker) from different directions; Special furnace binding shape guarantees that the solid materials turnover is convenient, is easy to realize.In addition; Said perpendicular T type structure makes the cyclical operation of the operation of charging, blow-on intensification, reaction, cooling, discharging and charging, blow-on intensification, reaction, cooling, discharging again keep body of heater operation operating mode (hot conditions etc.) in process; Therefore can be implemented under the not blowing out condition; Pack into smoothly and draw off carbon nanometer tube material and finished product, realize semi continuous operation.Simultaneously; Said perpendicular T type structure keeps the body of heater working condition to realize the operation of loading and unloading solid material down; Need necessary reactor drum blowing out cooling, the temperature-rise period in following cycle because of the turnover material after having avoided the monocycle reaction to accomplish; Thereby realize not changing the semi continuous operation process of turnover material target under the furnace body temperature condition, gradient of temperature causes the energy additive decrementation that causes.
2) owing to adopting march-past, preheating, hot spots arrange; Therefore can guarantee to reach predetermined temperature of reaction into bed gas; Make the outer heating of equipment reaction section be merely reaction consumes heat energy, avoided the fluctuation of bed temperature, the reaction process heat effect is tended to be steady.Said preheating, heating march-past are arranged heating, preheating section can be controlled respectively, realize carrying out as required the heat adjustment, cut down the consumption of energy.
3) reactive moieties (catalytic cracker) of preparation CNTs and attached water cooler adopt split-type structural, and the process of cooling of the CNTs product after reaction is accomplished is realized by split type water cooler, adopts protection of inert gas.Realized that the main body catalytic cracker only carries out reaction process in the production cycle, the main body catalytic cracker need not the heating and cooling operation in system's cycle of operation.The material process of cooling is carried out in the march-past water cooler, has shortened the operational cycle greatly, and single furnace operating loop cycle is 1/3 of a former periodical operation process.In addition, said attached water cooler split-type structural is implemented protection of inert gas, and chilled product cooling whole process places rare gas element, prevents the oxidation of initial stage high-temperature product in gas phase.
In sum, CNTs of the present invention prepares process and comprises reactive moieties (catalytic cracker) preheating, catalyst activation, CNTs preparation and cooling.For periodical operation, these processes are all accomplished in catalytic cracker, and energy-output ratio is big, and the production cycle is long, and especially product is cooled to normal temperature (～50 ℃) from high temperature (～650 ℃), need the long time.For operate continuously, having only made of carbon nanotubes is in reactor drum, to accomplish, and reactor drum time and space utilization rate is high, but made of carbon nanotubes realizes that fluidized-bed prepares difficulty continuously, and the experimental size report is only arranged at present.Because in the carbon nanotube production process, very easily " sintering " and can't discharge product continuously.And particular design of the present invention adopts " integration " input and output material mode.When the one-period reaction is accomplished, under not blowing out operating mode, can inner member be moved into the water cooler cooling in company with product, place inertia protection gas; Again in reactor drum, add the saggar that raw material is housed then, proceed carbon nanotube production.Solved product refrigerative problem, shortened reaction time, cut down the consumption of energy, product in time shifts out the difficult problem of reactor drum when having solved continuous the preparation again.
The present invention is different from the fixed bed of periodical operation, also is different from the fluidized-bed of operate continuously, has realized semicontinuous batch process carbon nanotube.Technological adaptability of the present invention is strong, because the kind of carbon nanotube is relevant with catalyst type and kind, can produce different carbon nanotubes through changing different catalyst with the present invention.
Description of drawings
Fig. 1 is that the structure of the embodiment of the invention is formed synoptic diagram.
Fig. 2 is JEM-2100 (HR) the type transmission electron microscope figure of the product of embodiment of the invention production.As can be seen from Figure 2, the carbon nanotube external diameter is 30～60nm, and wall thickness is about 10nm; Scale is 200nm.
Fig. 3 is the part enlarged view among Fig. 2.In Fig. 3, scale is 50nm.
Embodiment
Below in conjunction with accompanying drawing the present invention is elaborated.
Referring to Fig. 1, the embodiment of the invention is provided with reactor body 4, saggar 5, carbon nanotube bed 6, gas preheater 8, water cooler 9 and saggar up-down air pump 10; The top of said reactor body 4 is provided with the derivation point and the tail gas outlet 2 of thermopair 1, and the top of reactor body 4 is provided with zone of heating 3; Saggar 5 is located in the reactor body 4, and saggar 5 liftable in reactor body 4 moves; Carbon nanotube bed 6 is located in the saggar 5, is the reaction vitellarium of carbon nanotube; One side of gas preheater 8 is provided with virgin gas inlet 7; Be placed with in the gas preheater 8 and add the thermopair rod, gas preheater 8 is located at bottom one side of reactor body 4 and is connected as a single entity with reactor body 4, and gas preheater 8 is L-shaped with reactor body 4; Water cooler 9 is located at reactor body 4 bottoms and is constituted cat ladder shape structure with reactor body 4 and gas preheater 8; But water cooler 9 translations break away from reactor body 4, are convenient to saggar 5 loading and unloading, and saggar up-down air pump 10 is located in the water cooler 9.
Said thermopair 1 can be established 3.
Said saggar 5 is main on-board components, and saggar 5 main bodys are a hollow tube 51, and reaction bed 6 places in the hollow tube 51 of saggar 5, supports reaction mass by card 52, card 52 aperture 1.5mm, and the hole between centers is 2.5mm, is laser punching.Gas flow guiding hole 53 is offered in hollow tube 51 bottoms, and virgin gas gets into from preheater 8, carries out catalytic cracking reaction through pod apertures 53 rising reaction beds, and the bottom is airtight flange 54.When saggar 5 is in place, utilize the airtight flange 54 of saggar 5 bottoms and the flange in the bottom locking of reactor body 4, play support saggar 4 and airtight.
Thermopair 1 is used for measuring interior each the interval temperature of reactor drum, is provided with 3 points for measuring temperature altogether.Point derived by thermopair 1 and tail gas outlet 2 is positioned at the reactor top location; Zone of heating is external electrically heated, is wrapped in the reactor drum outside with lagging material; Reactor body 4 is that a hollow ketoboidies and gas preheater 8 are connected as a single entity, and is the L type, and the gas preheater 8 built-in thermopair rods that add, virgin gas inlet 7 import from gas preheater 8 sides; Saggar 5 is positioned at reactor body 4, is that a liftable moves on-board components, and reaction bed 6 places in the saggar 5, is the reaction vitellarium of carbon nanotube.Water cooler 9 is arranged at reactor lower part, forms perpendicular T type structure with reactor body 4, preheater 8.But water cooler 9 translations break away from reactor body 4, are convenient to packing into and taking out water cooler 9 built-in up-down air pumps 10 of saggar 5.When water cooler 9 and reactor body 4 are in the plumb position each other; Start saggar up-down air pump 10; Saggar 5 is risen to desired location in the reactor body 4 from water cooler 9, and when locking the lower flange of reactor body 4 and saggar 5, reactive system has been in and can have carried out the scission reaction state; When the reaction completion, the lower flange of release reactor body 4 and saggar 5 starts saggar up-down air pump 10, and saggar 5 is dropped to desired location in the water cooler 9 from reactor body 4 interior verticals, carries out protection of inert gas and cools off.
The system pressure of device is by the pressure reduction control that is communicated with atmospheric vent gas treatment part, and full device is except the input and output gas pipe, and the System and Surroundings hermetic unit is reactor body 4 upper flanges, following end flanges and preheater end flanges.
Below provide application example of the present invention.
A certain amount of raw material places in the saggar 5, and saggar 5 gets into reactor body 4 (employing pyrolyzer) from the bottom.Feed inertia protection gas from virgin gas inlet 9, the resistance to air loss of inspection units, after the passed examination, the electrothermal stove of opening in the zone of heating 3 that adds heats reactor drum, feeds controlled atmosphere simultaneously.When treating that temperature is elevated to catalyst activation temperature, feed reducing gas, guarantee that rare gas element and reducing gas flow proportional are field planting from virgin gas inlet 9.Activation finishes, and stops to feed rare gas element and reducing gas, feeds virgin gas CH from virgin gas inlet 9
4, after gas preheater 8 preheatings, virgin gas gets into carbon nano tube growth bed 6, carries out catalytic cracking reaction, CH
4Catalytic pyrolysis generates carbon nanotube and is deposited on the metal catalyst.Reaction does not change reactor body 4 furnace temperature after finishing, and under protection of inert gas, saggar 5 and on-board components is vertically shifted out entering water cooler 9 and translation disengaging reactor body 4 from reactor body 4, feeds rare gas element and is cooled to normal temperature.Take out saggar 5, be inverted saggar 5 and take out product, get into postprocessing working procedures.
New catalyzer places in the saggar 5, gets into the reactor body 4 under the operating mode from the bottom.Carry out the next cycle reaction, so circulation.
Get a certain amount of catalyzer and put into the saggar 5 of reactor drum, saggar is fit into reactor body 4.
The setting program temperature controller, the Heating temperature that makes pyrolyzer is 650 ℃, preheating temperature is 450 ℃, the protection gas N of feeding
2, catalyst reduction gas H
2, virgin gas CH
4Flow proportional be about 12: 2: 1.
Behind the reaction 4h, stop to feed CH
4, at N
2Under the protection, product is the fs cooling in reactor drum, when temperature of reactor is reduced to 400 ℃, at N
2Protection under general who has surrendered's saggar 5 move into water coolers 9 and cool off.
When product temperature is cooled to room temperature, take out product, it is 177.5gh that weighing obtains the carbon nanotube productive rate
-1, through JEM-2100 (HR) type transmission electron microscope (TEM) photo (referring to Fig. 2 and 3), observe the carbon nanotube O.D.T. between 30～60nm, wall thickness is about 10nm, the hollow structure of pipe is high-visible, belongs to multi-walled carbon nano-tubes (MWCNTs).
Claims (3)
1. semicontinuous production carbon nanotube reactor drum is characterized in that being provided with reactor body, saggar, carbon nanotube bed, gas preheater, water cooler and saggar up-down air pump; The top of said reactor body is provided with the derivation point and the tail gas outlet of thermopair, and the top of reactor body is provided with zone of heating; Saggar is located in the reactor body; The carbon nanotube bed is located in the saggar; One side of gas preheater is provided with the virgin gas inlet, is placed with in the gas preheater to add the thermopair rod, and gas preheater is located at bottom one side of reactor body and is connected as a single entity with reactor body; Water cooler is located at the reactor body bottom and is constituted cat ladder shape structure with reactor body and gas preheater; Saggar up-down air pump is located in the water cooler.
2. semicontinuous production carbon nanotube reactor drum as claimed in claim 1 is characterized in that said gas preheater and reactor body are L-shaped.
3. semicontinuous production carbon nanotube reactor drum as claimed in claim 1 is characterized in that said reactor body adopts catalytic cracker.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922310A (en) * | 2014-04-09 | 2014-07-16 | 中国科学院金属研究所 | Method and device for low-temperature gas-phase macro growth of high-quality straight carbon nanotube |
| CN114572961A (en) * | 2022-01-14 | 2022-06-03 | 深圳市飞墨科技有限公司 | Carbon nanotube production equipment and method for preparing carbon nanotubes by using same |
| CN114604856A (en) * | 2022-01-21 | 2022-06-10 | 成都铭川新材料科技有限公司 | Purification furnace for preparing carbon nano tube |
| CN116395673A (en) * | 2023-03-07 | 2023-07-07 | 青岛昊鑫新能源科技有限公司 | Carbon nanotube production reactor |
-
2012
- 2012-02-24 CN CN2012100432453A patent/CN102530921A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 朱丽等: "半连续碳纳米管反应器中试开发及流态化模拟", 《化工进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922310A (en) * | 2014-04-09 | 2014-07-16 | 中国科学院金属研究所 | Method and device for low-temperature gas-phase macro growth of high-quality straight carbon nanotube |
| CN103922310B (en) * | 2014-04-09 | 2016-01-13 | 中国科学院金属研究所 | The method of low-temperature gaseous phase magnanimity growing high-quality, straight carbon nanotubes and device |
| CN114572961A (en) * | 2022-01-14 | 2022-06-03 | 深圳市飞墨科技有限公司 | Carbon nanotube production equipment and method for preparing carbon nanotubes by using same |
| CN114604856A (en) * | 2022-01-21 | 2022-06-10 | 成都铭川新材料科技有限公司 | Purification furnace for preparing carbon nano tube |
| CN116395673A (en) * | 2023-03-07 | 2023-07-07 | 青岛昊鑫新能源科技有限公司 | Carbon nanotube production reactor |
| CN116395673B (en) * | 2023-03-07 | 2023-09-15 | 青岛昊鑫新能源科技有限公司 | Carbon nanotube production reactor |
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Application publication date: 20120704 |