CN1317446A - Moving-bed catalytic cracking process for continuously preparing nm carbon tubes - Google Patents
Moving-bed catalytic cracking process for continuously preparing nm carbon tubes Download PDFInfo
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- CN1317446A CN1317446A CN 01111561 CN01111561A CN1317446A CN 1317446 A CN1317446 A CN 1317446A CN 01111561 CN01111561 CN 01111561 CN 01111561 A CN01111561 A CN 01111561A CN 1317446 A CN1317446 A CN 1317446A
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Abstract
A process for continuously preparing nm carbon tubes by moving-bed catalytic cracking method includes arranging moving bed in tunnel kiln, continuously spreading catalyst onto convaying belt of moving bed, reaction between the raw gas of carbon-contained compound and the catalyst on said conveying belt to generate nm carbon tubes, and conveying them to collector. Its advantage is continuous production.
Description
The invention provides a kind of continuous method for preparing carbon nanotube (CNTs), belong to the synthetic field of nano material, relate to carbon compound particularly Sweet natural gas, liquefied gas, methane, acetylene, dme or carbon monoxide etc. be raw material, pass through catalytic cracking process for continuously preparing nm carbon tubes.
Carbon nanotube is since 1991 are found, and its preparation technology has obtained broad research.Now existing multiple preparation method is as arc discharge method, laser ablation, electrolysis, cryogenic solid cracking, hydrocarbon oxidation catalyst decomposition or chemical Vapor deposition process etc.But main method has only three kinds, and a kind of is arc discharge method, and another kind is a laser ablation method, in the product that these two kinds of methods make, carbon nanotube all with the coexistence of the carbon product of other forms, the separation and purification difficulty, yield is lower, and is difficult to mass-producing.The third method is a catalystic pyrolysis, with hydrocarbon gas (as Sweet natural gas, methane, ethane, ethene, acetylene etc.), oxygenatedchemicals (as methyl alcohol, dme, methyl-formiate etc.) or carbon monoxide is raw material, to support or the non-Fe that supports, Co or Ni are catalyzer, preparation high-purity C NTs under proper temperature.This method technology is easy, CNTs yield height, and specification is easy to control, and is the most rising.
Present catalystic pyrolysis prepares CNTs and comprises fixed-bed catalytic cracking technology and ebullated bed Deep Catalytic Cracking process (United States Patent (USP) 5,578,543).
Cracking generated CNTs when catalyzer transfixion in reactor in the fixed-bed catalytic cracking technology, unstripped gas were passed through on catalyzer.Catalyzer is only with the formal expansion of thin layer in this technology, the effect that just has, otherwise the utilization ratio of catalyzer is just low, thereby the preparation amount of CNTs is difficult to enlarge.
In the ebullated bed Deep Catalytic Cracking process, gas (unstripped gas) solid (catalyzer) contact is good, even add a large amount of catalyzer, also can obtain high catalyst utilization.The ebullated bed Deep Catalytic Cracking process can roll up because of the amount of catalyzer, thereby can prepare CNTs in a large number.The problem that this technology exists is operation easier big (with the growth of CNTs, bed weight constantly increases, and for keeping " boiling " state, must constantly adjust feed gas flow rates and heat supply), the energy consumption height, and the unstripped gas transformation efficiency is low, thereby CNTs production cost height.
The objective of the invention is to adopt the tunnel furnace moving-bed catalytic cracking process for continuously preparing nm carbon tubes, a kind of synthesis technique of sophisticated extensive, cheap preparation high-purity carbon nano tube is provided.
The preparation of carbon nanotube comprises catalyst activation and two processes of carbon nano tube growth.These two processes are divided successively in time in the prior art, and do not change on the locus, and promptly catalyzer is used unstripped gas carbon nano-tube on catalyst activated instead then through overactivation before this.Variation has all taken place in these two processes of catalyst activation and carbon nano tube growth among the present invention on time and space, and promptly the at a time a certain position of catalyzer is activated, and at another moment another location carbon nano-tube.
The objective of the invention is to realize: in tunnel furnace moving-bed catalytic cracking reactor by following principle, nm-class catalyst is spread across on the moving-bed by the continuously uniform cloth of disperser nozzle, moving-bed moves with certain speed, and the residence time of catalyzer on moving-bed can be regulated by the movement velocity of control moving-bed.The flow direction of unstripped gas can be consistent with the direction of motion of catalyzer also can be opposite.Unstripped gas generates carbon nanotube in the catalyst surface cracking.When the residence time of catalyzer on moving-bed reached set(ting)value, catalyzer deviate to enter collector together with the carbon nanotube that generates from moving-bed thereon, and reaction end gas is discharged through the tail gas outlet.
Catalyzer can directly utilize the reaction atmosphere reduction activation.The reduction activation of catalyzer has just begun at 400 ℃, and the temperature of catalyzer carbon nano-tube is more than 650 ℃.So can utilize reaction end gas at the thermograde section reduction activation catalyzer of catalyzer release position to reaction zone.Be under the situation of unstripped gas with the hydrocarbon gas, the content of hydrogen has reached very high concentration in the reaction end gas, generally can reach 80 (v/v) more than the %.If the flow direction of unstripped gas is opposite with the direction of motion of catalyzer, then in described thermograde section, catalyzer can fully be activated fully.Even the flow direction of unstripped gas is identical with the direction of motion of catalyzer, also owing to the counter diffusion of split product hydrogen, can make in this thermograde section reaction atmosphere has the hydrogen of enough concentration that catalyzer is fully activated.The reduction activation catalyzer can keep catalyzer than the primary particle state in this way, easily generates the carbon nanotube of design specification.
The flow direction of unstripped gas is opposite with the direction of motion of catalyzer not only to help generating highly purified carbon nanotube, also helps improving the transformation efficiency of unstripped gas.Because under this processing condition, highly active catalyzer at first contacts with the lower concentration unstripped gas of remnants, easily generate the carbon nanotube rather than the nano-sized carbon of high-crystallinity at catalyst surface, and the lower concentration unstripped gas more is tending towards transforming fully on highly active catalyzer, and the catalyzer (the existing reduction of catalytic activity this moment) that has generated carbon nanotube on the surface contacts with the unstripped gas of high density, more help the growth of surface carbon nanotube, increase the output of unit catalyzer synthesizing carbon nanotubes.
Catalyzer also can pass through activation treatment among the present invention before cloth is spread across on the moving-bed, the activation in advance of catalyzer is just very necessary when particularly being unstripped gas with oxygenatedchemicals such as dme or carbon monoxide, because reducing gas is not enough to deactivated catalyst in the reaction end gas.
For preparation process uninterruptedly being carried out continuously, being preferably in two catalyzer dispensers are set on the reaction unit.The catalyzer dispenser preferably also has the function of deactivated catalyst within it having on moving-bed when cloth spills catalyst function continuously, certainly and do not require that these two functions play a role simultaneously.When continuously cloth spilt catalyzer on moving-bed, second catalyzer dispenser can cover the reactivation of catalyst catalyzer at first catalyzer dispenser.Wait when catalyzer exhausts in first catalyzer dispenser, second catalyzer dispenser continuous cloth on moving-bed spills catalyzer.So by turns, can realize the input of catalyzer successive, thereby realize the continuous preparation of carbon nanotube.
The activation temperature of catalyzer directly has influence on the specification of the carbon nanotube that is generated.Generalized case is, activation temperature is high more, and the particle of catalyzer (being actually the metallics that is scattered in carrier surface) will become big more, and the carbon nanotube diameter of generation is just big more, and the carbon nanotube output of every gram catalyzer is just low more.On the contrary, if activation temperature is low, granules of catalyst is smaller relatively, and the carbon nanotube diameter of generation is also corresponding smaller, and the carbon nanotube output of every gram catalyzer is just more.This is because catalyst activity point is many at this moment, and the quantity of every gram catalyzer generation carbon nanotube is just much bigger, thereby output can increase.If but activation temperature is low excessively, catalyzer just might fully not activated, and directly influences the output and the quality of carbon nanotube.
In view of the These characteristics of catalyzer, can adopt two sections stoves to realize the serialization preparation of design specification carbon nanotube.Primary reformer is used for deactivated catalyst, and secondary reformer is used for preparing carbon nanotube.The atmosphere of these two sections stoves is wanted strict control, and the atmosphere that particularly is used for preparing the secondary reformer of carbon nanotube can not enter primary reformer, otherwise just might grow carbon nanotube in primary reformer, does not reach the purpose for preparing the design specification carbon nanotube.
The present invention is a catalyzer with the composite oxides of Ni, Co or Fe and rare earth element, reduction activation in 400～1000 ℃ of following nitrogen atmosphere.Transferring under hydrogen or the protection of inert gas among the catalyzer dispenser.For guaranteeing the nm-class catalyst particle, it is suitable adopting citric acid complex method to prepare composite oxide catalysts, and it can effectively prevent catalyzer melting knot and generate large granular catalyst between the particle in reactivation process.
Catalyzer can be thrown on moving-bed by modes such as bolting, spraying or negative pressure.Also can adopt stone mill abrasive dust principle to throw in catalyzer.Also available material distribution cartridge cloth spills catalyzer.
Below in conjunction with description of drawings specific embodiment of the present invention.
Fig. 1 is a tunnel furnace moving-bed catalytic cracking device diagrammatic cross-section of the present invention.
Fig. 2 is a catalyzer dispenser synoptic diagram.
The catalyzer that activation treatment is good joins under rare gas element or hydrogen shield in the catalyzer dispenser (200), and tunnel furnace (101) is heated to preset temperature, and temperature is by thermocouple measurement, SCR control.Material distribution cartridge (203) is rendered to catalyzer (108) on the travelling belt (109) of moving-bed (104) in the catalyzer dispenser (200), the catalyzer that scraper (107) will be rendered on the travelling belt is organized into thin and uniform one deck, carbon compound enters tunnel furnace inside through unstripped gas inlet (102), have an effect with catalyzer on the travelling belt, cracking generates carbon nanotube.The tail gas of scission reaction is discharged through tail gas relief outlet (106).Because travelling belt is at the uniform velocity mobile under the drive of rotating shaft (110), catalyzer on the travelling belt is also simultaneously at the uniform velocity mobile forward, when catalyzer moves to second rotating shaft (111) position, because the steering-effecting of rotating shaft (111), catalyzer and the carbon nanotube that generates on it split away off from travelling belt, enter product collector (105).Catalyzer can be added at any time in the catalyzer dispenser.When the product collector is filled, close end switch on the product collector (112), take out prepared carbon nanotube.After connecting product collector (105), open and vacuumize switch (113), the product collector is vacuumized, filling with inert gas or fill the tail gas that this cracker is discharged then beats that end switch (112) continues to collect product on the Ji product collector.
The effect of catalyzer dispenser (200) is to go up cloth to travelling belt (109) equably continuously to spill catalyzer, it is made up of rotating shaft (201), material distribution cartridge (203) and catalyst container etc., be uniform-distribution with dome-type pit (205) on the material distribution cartridge (203), with the cloth amount of spilling of control catalyst.Material distribution cartridge (203) is driven by rotating shaft (204), and rotating shaft (204) can be driven by stepping or stepless speed-regulating motor.The add-on of catalyzer can be regulated by the quantity of design dome-type pit (205) and the rotating speed of size and rotating shaft (204).Can be at material distribution cartridge (203) positioned beneath one hairbrush with under the catalyzer in the dome-type pit (205) brush, and catalyzer is evenly fallen on the travelling belt (109).
For making catalyzer can fall into the dome-type pit (205) of material distribution cartridge (203) with comparalive ease, preferably add a flexible whipping appts (202) in the rotating shaft (201), stick on the container wall to stop catalyzer.Flexible whipping appts (202) available resistance wire etc. is made.
For rotating shaft and the power set that makes moving-bed is in lesser temps, the heating zone of tunnel furnace will be as far as possible away from rotating shaft and power set.So both can guarantee that rotating shaft and power set worked under relatively mild condition, also can prevent from rotating shaft and power set, to tie carbon, guarantee that rotating shaft and power set can works better.
Moving-bed is made up of travelling belt, rotating shaft and power set.Power set drives rotating shaft and rotates, and travelling belt moves towards the direction of setting under the drive of rotating shaft.Be the ulking thickness of control catalyst on travelling belt, adding a scraper near above the travelling belt of catalyzer dispensing port one end, the distance between the edge of a knife and the travelling belt upper surface is the maximum ulking thickness of catalyzer.
Travelling belt can be that a series of flaky materials interconnect by hook, also the side and the chain of travelling belt can be combined, and moves thereby drive travelling belt by the gear driven chain movement in the rotating shaft.Travelling belt also can be that a successive band is formed by connecting.
The conveyor materials of moving-bed can be used quartz, carbon cloth, stainless steel, copper and alloy, titanium and alloy thereof, molybdenum and alloy thereof or other refractory metal or stupalith manufacturing, and the travelling belt surface that high temperature material is made can copper facing, plating molybdenum or form corundum layer to prevent to tie carbon thereon.
The power set of moving-bed can be a motor, obtains appropriate conveyer belt speed by gear combination.The required power of moving-bed also can be provided by the outer electro-magnet that rotates of tunnel furnace, and electro-magnet rotates in the outer electro-magnet drive moving-bed rotating shaft of rotating of tunnel furnace, thereby drives conveyer belt.
The moving-bed travelling belt also axle rod (103) of available a pair of reverse rotation drives.The axle rod (103) of reverse rotation compresses travelling belt (109) on one side, moves towards direction initialization Yi Bian drag travelling belt (109).The axle rod makes into mutual counter-rotating by two gear mesh.Axle rod available silicon rubber or General Purpose Rubber are made.
As a simplification device of the present invention, moving-bed can be replaced by push pedal.Catalyzer at first is sprinkled upon in the push pedal by cloth, moves in tunnel furnace by pushing away pole promotion push pedal.After growing the maximum carbon nanotube on the catalyzer, tunnel furnace is shifted out in push pedal.This device also can divide two sections, and first section is used for deactivated catalyst, and second section is used for preparing carbon nanotube, thereby the control that realizes the design specification carbon nanotube is synthetic.A transition section can be arranged between first section and second section, do not enter in first section with the reaction atmosphere of controlling second section.
Said tunnel furnace can be a laboratory tubes formula stove among the present invention.
The present invention can operate under normal pressure, malleation or negative pressure.
Claims (10)
1. method for preparing carbon nanotube, particularly Sweet natural gas, methane, acetylene or carbon monoxide are raw material with carbon compound, prepare carbon nanotube by catalytic cracking method, it is characterized in that adopting tunnel furnace moving-bed catalytic cracking reaction unit to realize the continuous preparation of carbon nanotube.
2. method according to claim 1 is characterized in that described tunnel furnace moving-bed catalytic cracking reaction unit is made up of tunnel furnace (101), unstripped gas inlet (102), catalyzer dispenser (200), moving-bed (104), product collector (105) and tail gas relief outlet (106).
3. method according to claim 2 is characterized in that described moving-bed is the one or more push pedals that can move in tunnel furnace.
4. method according to claim 2, it is characterized in that moving-bed (104) is by travelling belt (109), rotating shaft (110,111) and power set form, travelling belt (109) material is quartz material, red copper and alloy thereof, molybdenum and alloy, carbon cloth etc.
5. method according to claim 2 is characterized in that the flow direction of unstripped gas is consistent or opposite with travelling belt (109) direction of motion of moving-bed (104).
6. method according to claim 1 is characterized in that described catalyzer can use the reaction end gas direct activation.
7. method according to claim 1 is characterized in that described tunnel furnace moving-bed catalytic cracking reaction unit forms by two sections; First section is used for deactivated catalyst, and second section is used for preparing carbon nanotube; A transition section can be arranged between first section and second section, do not enter in the first stage activation atmosphere with the reaction atmosphere of controlling second section.
8. method according to claim 2 is characterized in that the axle rod (103) of the available a pair of reverse rotation of moving-bed (104) travelling belt (109) drives.
9. method according to claim 2 is characterized in that moving-bed (104) is driven by step down gear by stepless speed-regulating motor, stepper-motor or common electric machine.
10. method according to claim 2 is characterized in that a material distribution cartridge (203) being arranged, the size of first ball-type pit (205) of material distribution cartridge (203) and the add-on of controllable number controlling catalyst in the catalyzer dispenser (200).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011115610A CN1168656C (en) | 2000-04-13 | 2001-03-21 | Moving-bed catalytic cracking process for continuously preparing nm carbon tubes |
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| CN00112845.0 | 2000-04-13 | ||
| CN00112845 | 2000-04-13 | ||
| CNB011115610A CN1168656C (en) | 2000-04-13 | 2001-03-21 | Moving-bed catalytic cracking process for continuously preparing nm carbon tubes |
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| CN1317446A true CN1317446A (en) | 2001-10-17 |
| CN1168656C CN1168656C (en) | 2004-09-29 |
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| CNB011115610A Expired - Fee Related CN1168656C (en) | 2000-04-13 | 2001-03-21 | Moving-bed catalytic cracking process for continuously preparing nm carbon tubes |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393616C (en) * | 2003-02-05 | 2008-06-11 | 列日大学 | Method and installation for making carbon nanotubes |
| WO2012068781A1 (en) * | 2010-11-25 | 2012-05-31 | Bestrong International Limited | System and method for producing hydrogen gas |
| CN104936894A (en) * | 2013-01-17 | 2015-09-23 | 沙特基础工业公司 | Carbon nano-tube production from carbon dioxide |
| CN106185863A (en) * | 2016-07-06 | 2016-12-07 | 上海绿人生态经济环境保护研究所 | The technique that CNT prepared by the combustible gas utilizing junked tire thermal cracking to produce |
| CN110937592A (en) * | 2019-11-08 | 2020-03-31 | 深圳烯湾科技有限公司 | Batch continuous production equipment for carbon nanotubes and preparation method thereof |
| CN111632461A (en) * | 2020-06-03 | 2020-09-08 | 龙永南 | Rubber banburying tail gas treatment system and method |
| CN114558521A (en) * | 2022-03-10 | 2022-05-31 | 无锡碳谷科技有限公司 | Layered material distribution moving bed reaction device and use method |
| WO2023207044A1 (en) * | 2022-04-27 | 2023-11-02 | 东南大学 | System and method for continuously preparing carbon material and co-producing hydrogen from organic solid waste polymer |
-
2001
- 2001-03-21 CN CNB011115610A patent/CN1168656C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393616C (en) * | 2003-02-05 | 2008-06-11 | 列日大学 | Method and installation for making carbon nanotubes |
| WO2012068781A1 (en) * | 2010-11-25 | 2012-05-31 | Bestrong International Limited | System and method for producing hydrogen gas |
| CN104936894A (en) * | 2013-01-17 | 2015-09-23 | 沙特基础工业公司 | Carbon nano-tube production from carbon dioxide |
| CN106185863A (en) * | 2016-07-06 | 2016-12-07 | 上海绿人生态经济环境保护研究所 | The technique that CNT prepared by the combustible gas utilizing junked tire thermal cracking to produce |
| CN110937592A (en) * | 2019-11-08 | 2020-03-31 | 深圳烯湾科技有限公司 | Batch continuous production equipment for carbon nanotubes and preparation method thereof |
| CN111632461A (en) * | 2020-06-03 | 2020-09-08 | 龙永南 | Rubber banburying tail gas treatment system and method |
| CN114558521A (en) * | 2022-03-10 | 2022-05-31 | 无锡碳谷科技有限公司 | Layered material distribution moving bed reaction device and use method |
| CN114558521B (en) * | 2022-03-10 | 2023-01-10 | 无锡碳谷科技有限公司 | Layered material distribution moving bed reaction device and use method |
| WO2023207044A1 (en) * | 2022-04-27 | 2023-11-02 | 东南大学 | System and method for continuously preparing carbon material and co-producing hydrogen from organic solid waste polymer |
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