CN100552105C - Apparatus and method for preparing continuous carbon nanotube fibers by catalytic reaction of liquid-enclosed gas phase flow - Google Patents
Apparatus and method for preparing continuous carbon nanotube fibers by catalytic reaction of liquid-enclosed gas phase flow Download PDFInfo
- Publication number
- CN100552105C CN100552105C CNB2007100594917A CN200710059491A CN100552105C CN 100552105 C CN100552105 C CN 100552105C CN B2007100594917 A CNB2007100594917 A CN B2007100594917A CN 200710059491 A CN200710059491 A CN 200710059491A CN 100552105 C CN100552105 C CN 100552105C
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- quartz ampoule
- carbon nanotube
- fluid box
- tube fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种液封气相流催化反应制备连续碳纳米管纤维的装置和方法。该装置是：液体箱通过法兰与安装在管式炉中的石英管连接，用H2O、10%HCl、10%PVA水溶液等为密封液体；将乙醇、二茂铁、噻吩和水的混合溶液通过微量注射泵注入500～1200ml/min H2的载气气流中，经喷嘴导入石英管中，在900～1200℃高温条件下进行反应，反应区生成筒状的连续碳纳米管纤维，将形成的碳纳米管纤维用密封液体介质处理或直接从反应区对形成的碳纳米管纤维进行操作。本发明实现了对反应区碳纳米管纤维进行直接操作和对形成的纤维进行处理，得到高纯度、高强度的连续碳纳米管纤维，反应条件温和，适宜大规模工业化生产碳纳米管纤维，应用广泛。
The invention discloses a device and a method for preparing continuous carbon nanotube fibers by liquid-sealed gas-phase flow catalytic reaction. The device is: the liquid tank is connected to the quartz tube installed in the tube furnace through the flange, and H 2 O, 10% HCl, 10% PVA aqueous solution, etc. are used as the sealing liquid; ethanol, ferrocene, thiophene and water The mixed solution is injected into the carrier gas flow of 500-1200ml/min H2 through a micro-injection pump, introduced into the quartz tube through the nozzle, and reacted at a high temperature of 900-1200°C, and the reaction zone generates cylindrical continuous carbon nanotube fibers. The formed carbon nanotube fibers are treated with a sealed liquid medium or the formed carbon nanotube fibers are manipulated directly from the reaction zone. The invention realizes the direct operation of the carbon nanotube fiber in the reaction zone and the processing of the formed fiber to obtain the high-purity and high-strength continuous carbon nanotube fiber, the reaction condition is mild, and it is suitable for large-scale industrial production of the carbon nanotube fiber. widely.
Description
Technical field
The present invention relates to the synthetic of carbon nano-tube fibre, a kind of apparatus and method of producing continuous carbon nano-tube fibre by liquid sealed vapor-phase flow catalytic reaction particularly, it is liquid sealed vapor-phase flow catalytic reaction synthesizing continuous carbon nanometer tube fiber and method that fiber is directly handled in high-temperature region, liquid.
Technical background
Carbon nano-tube fibre has superpower and the high conductivity characteristic, and has characteristics such as high heat conduction, air-sensitive, electric field transmitted.This novel high strength multifunctional fiber has important application prospects at aspects such as high-strength composite material, high conducing composite material, novel conductive material, sensor, electrochemical capacitance and artificial-muscles.Chinese patent CN1724346 A discloses the method for making carbon nanotube microfibers with the CNT fragment.
The most promising method of preparation continuous carbon nano-tube fibre is a high temperature vapor phase stream process for catalytic synthesis at present, this method has been used special equipment, adopt reaction carbon source and iron-containing catalysts such as ethanol, the floating catalytic reaction takes place in being higher than 1000 ℃ hydrogen stream, under appropriate reaction conditions, in air-flow, can grow continuous carbon nano-tube fibre (U.S. Pat Patent 2005/006801-A1).Because reaction is the high-temperature hydrogen sealing system, be difficult at present directly obtain continuous accessible carbon nano-tube fibre by reaction.
Summary of the invention
The object of the present invention is to provide a kind of apparatus and method of producing continuous carbon nano-tube fibre by liquid sealed vapor-phase flow catalytic reaction.The present invention can realize the reaction zone carbon nano-tube fibre is carried out direct control and uses the seal fluid medium that carbon nano-tube fibre is handled, obtain high-purity, high-intensity continuous carbon nano-tube fibre, the reaction condition gentleness, suitability for mass industrialized production carbon nano-tube fibre is widely used.
The device of producing continuous carbon nano-tube fibre by liquid sealed vapor-phase flow catalytic reaction provided by the invention mainly comprises the synthesis reactor that tube furnace, quartz ampoule are formed, also comprise the fluid box of containing the seal fluid medium, the seal fluid case is connected by flange with the quartz ampoule outlet side of synthesis reactor, micro-injection pump is positioned at the air inlet position of synthesis reactor, and nozzle is positioned at the inlet end of quartz ampoule.With the liquid phase medium in the fluid box reaction zone and outside air are separated.The basically identical of the synthesis reactor parts of carbon nano-tube fibre and United States Patent (USP) (2005/006801-A1) report.
Described fluid box is a trapezium structure, can adopt vertical type device and horizontal type device.
The vertical type device, the top mid portion sealing of described fluid box, the top both-side opening is for the usefulness of operation carbon nano-tube fibre.Fluid box crown center hermetic unit has the circular hole identical with the quartz ampoule diameter, and this hole is connected by flange with quartz ampoule; Both sides in the crown center sealing are connected with and angled two baffle plates of level, the outside of the right baffle plate is opened aperture and is adorned peephole, at trapezoidal fluid box the inside rigid staybolt rod, support reflective mirror above the rod, reflective mirror can reflex to the pattern of reaction zone on the peephole, can observe the phenomenon of reaction zone by peephole.During experiment when not ventilating body baffle plate inboard identical with outside liquid level, inside pressure is a bit larger tham outside pressure when gas, make inboard liquid level be lower than slightly outside liquid level.
Horizontal type device, fluid box are the containers of splendid attire seal fluid medium, and the global design of fluid box is a right angle trapezium structure.The top left-half sealing of described fluid box, the right half part opening is for the usefulness of operation carbon nano-tube fibre; The fluid box top is connected with and the angled baffle plate of level, and the outside of baffle plate has aperture and adorns peephole, can observe the reacting phenomenon in the quartz ampoule from peephole; Have the circular hole identical with the quartz ampoule diameter on the right angle of right-angled trapezium fluid box face, this hole is connected by flange with quartz ampoule.The inboard of baffle plate is identical with outside liquid level when leading to reacting gas, and the baffle plate inside pressure is a bit larger tham outside pressure when feeding reacting gas, and outer liquid level also just is higher than the medial surface liquid level.
The step that the method for producing continuous carbon nano-tube fibre by liquid sealed vapor-phase flow catalytic reaction provided by the invention comprises:
1) mixed solution of preparation ethanol (carbon source), catalyst ferrocene, promoter thiophene and water injects H with mixed solution with micro-injection pump
2The carrier gas air-flow in.
2) import in the quartz ampoule through nozzle, react under hot conditions, reaction zone generates the continuous carbon nano-tube fibre of tubular.
3) with the carbon nano-tube fibre that forms with the seal fluid media processes or directly the carbon nano-tube fibre of formation is operated from reaction zone.
The mass percent of described ethanol, ferrocene, thiophene and water is formed: 80～96%, 1.0～3.0%, 1.0～3.0%, 1.0～10.0%.
The mixed aqueous solution injection rate of described ethanol, ferrocene and thiophene is 5～10ml/h.
Described H
2The carrier gas air velocity is 500～1200ml/min.
Under the described hot conditions be 900～1200 ℃.
The continuous carbon nano-tube fibre diameter of described tubular is 0.5～1.5cm.
Described liquid medium is: H
2O, 5～20%HCl, 5～30%H
2SO
4, 5～30%HNO
3, one or more the mixing in the ethanol, ethylene glycol, 2～20%PVP liquid, 2～20%PVA liquid, silicone oil, preferable liquid medium is water and silicone oil.
Described carbon source also can be acetone, ethylene glycol or n-hexane; Catalyst also can be iron chloride, nickel oxalate or cobalt acetate.Thiophene is a kind of promoter for preparing carbon nano-tube fibre, can improve the purity and the output of preparation carbon nano-tube fibre with thiophene.
The present invention has realized the reaction zone carbon nano-tube fibre is carried out direct control and uses the seal fluid medium that carbon nano-tube fibre is handled, obtain high-purity, high-intensity continuous carbon nano-tube fibre, the reaction condition gentleness, suitability for mass industrialized production carbon nano-tube fibre is widely used.
Description of drawings
Fig. 1: for vertical type prepares continuous carbon nano-tube fibre device overall structure generalized section.
Fig. 2: for vertical type prepares the continuous carbon nano-tube fibre device fluid box generalized section of bowing.
Fig. 3: be horizontal preparation continuous carbon nano-tube fibre device overall structure generalized section.
Fig. 4: be the horizontal preparation continuous carbon nano-tube fibre device fluid box generalized section of bowing.
Fig. 5: for embodiment 1 obtains fine and close carbon nano-tube fibre uniformly.
The specific embodiment
The method of producing continuous carbon nano-tube fibre by liquid sealed vapor-phase flow catalytic reaction provided by the invention, with reference to specific embodiment, but they are not limitations of the present invention.
As shown in the figure, 1 fluid box, 2 baffle plates, 3 peepholes, the outlet of 4 tail gas, 5 connect the flange of fluid box and quartz ampoule, 6 tube furnaces, 7 carbon nano-tube fibres, 8 quartz ampoules, 9 micro-injection pumps, 10 connect the flange of inlet tube and quartz ampoule, 11 nozzles, 12 seal fluids, 13 support sticks, 14 reflective mirrors.
The device that liquid sealing vapor-phase flow catalytic reaction provided by the invention prepares continuous carbon nano-tube fibre mainly comprises the synthesis reactor that tube furnace 6, quartz ampoule 8 are formed, also comprise the fluid box 1 of containing the seal fluid medium, micro-injection pump 9 is positioned at the air inlet position of synthesis reactor, the flange 10 that connects air inlet pipe and quartz ampoule is positioned at the reaction front end, and nozzle 11 is positioned at the inlet end of quartz ampoule.With the liquid phase medium in the fluid box reaction zone and outside air are separated, the seal fluid case is connected by flange 5 with the quartz ampoule outlet side of synthesis reactor.The basically identical of the synthesis reactor parts of carbon nano-tube fibre and United States Patent (USP) (2005/006801-A1) report.
The vertical type device:
Both sides in the crown center sealing are connected with and angled two baffle plates 2 of level, and the outside of the right baffle plate is opened an aperture and adorned a peephole 3.Fix a support stick 13 in the trapezoidal container the inside, support a reflective mirror 14 above the rod, reflective mirror can reflex to the pattern of reaction zone on the peephole 3, can observe the phenomenon of reaction zone by peephole 3.
During experiment when not ventilating body baffle plate inboard identical with outside liquid level, inside pressure is a bit larger tham outside pressure when gas, make inboard liquid level be lower than slightly outside liquid level.
Horizontal type device:
The specific embodiment that liquid sealing vapor-phase flow catalytic reaction provided by the invention prepares continuous carbon nano-tube fibre is as follows:
Water is the seal fluid medium.Ethanol (carbon source), ferrocene (catalyst), thiophene (promoter), water are pressed 23.70g, 0.45g, the ultrasonic mixing wiring solution-forming of 0.40g, 0.66g, and solution injects 600ml/min H by micro syringe with 7.0ml/h speed
2In the reaction gas flow, synthetic reaction is carried out in quartz ampoule, and the horizontal pipe atmosphere furnace is provided with 1150 ℃ and is reaction temperature.Can be observed from peephole after the reaction beginning, vaporific carbon nano-tube fibre produces in quartz ampoule, and along with flowing of carrier gas stream, fiber becomes the continuous carbon nano-tube fibre of the tubular of 0.5～1.5cm.Can carry out the direct mechanical operation to the carbon nano-tube fibre that forms by the water-stop medium, the carbon pipe fiber that takes out from reaction zone is by behind the aqueous medium, and diameter becomes about 0.1cm, and intensity increases, and fiber surface and water soak into.When the water evaporation back of fiber absorption fiber become fine and close more, diameter is about 0.02cm, it is original 1/75～1/25 that fibre diameter is punctured into, the intensity increase of fiber.
Joining 10% HCl solution is the seal fluid medium.Ethanol, ferrocene, thiophene, water are pressed 23.70g, 0.45g, the ultrasonic mixing wiring solution-forming of 0.40g, 0.66g, and solution injects 600ml/min H by micro syringe with 7.0ml/h speed
2In the reaction gas flow, synthetic reaction is carried out in quartz ampoule, and the horizontal pipe atmosphere furnace is provided with 1150 ℃ and is reaction temperature.Can be observed from peephole after the reaction beginning, vaporific carbon nano-tube fibre produces in quartz ampoule, and along with flowing of carrier gas stream, fiber becomes the continuous carbon nano-tube fibre of the tubular of 0.5～1.5cm.Can carry out the direct mechanical operation to the carbon nano-tube fibre that forms by the water-stop medium, the carbon pipe fiber that takes out from reaction zone is by behind the aqueous medium, and diameter becomes about 0.1cm, and intensity increases, and fiber surface and water soak into.
Join 10%HNO
3Solution is the seal fluid medium.Ethanol, ferrocene, thiophene, water are pressed 23.70g, 0.45g, the ultrasonic mixing wiring solution-forming of 0.40g, 0.66g, and solution injects 600ml/min H by micro syringe with 7.0ml/h speed
2In the reaction gas flow, synthetic reaction is carried out in quartz ampoule, and vertical tubular type atmosphere furnace is provided with 1150 ℃ and is reaction temperature.Can be observed from peephole after the reaction beginning, vaporific carbon nano-tube fibre produces in quartz ampoule, and along with flowing of carrier gas stream, fiber becomes the continuous carbon nano-tube fibre of the tubular of 0.5～1.5cm.Can carry out the direct mechanical operation to the carbon nano-tube fibre that forms by the water-stop medium, the carbon pipe fiber that takes out from reaction zone is by behind the aqueous medium, and diameter becomes about 0.1cm, and intensity increases, and fiber surface and water soak into.
Joining the 10%PVA aqueous solution is the seal fluid medium.Ethanol, ferrocene, thiophene, water are pressed 23.70g, 0.45g, the ultrasonic mixing wiring solution-forming of 0.40g, 0.66g, and solution injects 600ml/min H by micro syringe with 7.0ml/h speed
2In the reaction gas flow, synthetic reaction is carried out in quartz ampoule, and vertical tubular type atmosphere furnace is provided with 1150 ℃ and is reaction temperature.Can be observed from peephole after the reaction beginning, vaporific carbon nano-tube fibre produces in quartz ampoule, and along with flowing of carrier gas stream, fiber becomes the continuous carbon nano-tube fibre of the tubular of 0.5～1.5cm.Can carry out the direct mechanical operation to the carbon nano-tube fibre that forms by the water-stop medium, the carbon pipe fiber that takes out from reaction zone is by behind 10%PVA aqueous medium, and diameter becomes about 0.2cm, and intensity increases.Fiber enters 10%PVA aqueous solution fluid box with air-flow, and the PVA aqueous solution and carbon nano-tube fibre are directly compound, and the fiber after compound can be by direct control.
Claims (8)
1, a kind of liquid sealing vapor-phase flow catalytic reaction prepares the device of continuous carbon nano-tube fibre, mainly comprise the synthesis reactor that tube furnace, quartz ampoule are formed, it is characterized in that also comprising the fluid box of containing the seal fluid medium, the seal fluid case is connected by flange with the quartz ampoule outlet side of synthesis reactor, micro-injection pump is positioned at the air inlet position of synthesis reactor, and nozzle is positioned at the inlet end of quartz ampoule.
2, device according to claim 1 is characterized in that described fluid box is a trapezium structure.
3, device according to claim 2 is characterized in that the top mid portion sealing of described fluid box, the top both-side opening, and fluid box crown center hermetic unit has the circular hole identical with the quartz ampoule diameter, and this hole is connected by flange with quartz ampoule; Both sides in the crown center sealing are connected with and angled two baffle plates of level, and the outside of the right baffle plate is opened aperture and adorned peephole, at trapezoidal fluid box the inside fixed support rod, support reflective mirror above the rod.
4, device according to claim 2 is characterized in that the top left-half sealing of described fluid box, the right half part opening; The fluid box top is connected with and the angled baffle plate of level, and the outside of baffle plate has aperture and adorns peephole; Have the circular hole identical with the quartz ampoule diameter on the right angle of right-angled trapezium fluid box face, this hole is connected by flange with quartz ampoule.
5, a kind of preparation method who utilizes the described device of claim 1 to prepare continuous carbon nano-tube fibre is characterized in that it may further comprise the steps:
1) mixed solution of preparation ethanol, ferrocene, thiophene and water injects H with mixed solution with micro-injection pump
2The carrier gas air-flow in,
2) import in the quartz ampoule through nozzle, react under 900～1200 ℃ of conditions, reaction zone generates the continuous carbon nano-tube fibre of tubular,
3) carbon nano-tube fibre that forms is directly handled by aqueous medium or taken out carbon nano-tube fibre from reaction zone and handle aqueous medium.
6, preparation method according to claim 5 is characterized in that the quality of described ethanol, ferrocene, thiophene and water is respectively: 23.70g, 0.45g, 0.40g and 0.66g.
7, preparation method according to claim 5, the mixed aqueous solution injection rate that it is characterized in that described ethanol, ferrocene and thiophene is 5～10ml/h.
8, preparation method according to claim 5 is characterized in that described H
2The carrier gas air velocity is 500～1200ml/ minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100594917A CN100552105C (en) | 2007-09-04 | 2007-09-04 | Apparatus and method for preparing continuous carbon nanotube fibers by catalytic reaction of liquid-enclosed gas phase flow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100594917A CN100552105C (en) | 2007-09-04 | 2007-09-04 | Apparatus and method for preparing continuous carbon nanotube fibers by catalytic reaction of liquid-enclosed gas phase flow |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101153413A CN101153413A (en) | 2008-04-02 |
| CN100552105C true CN100552105C (en) | 2009-10-21 |
Family
ID=39255292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100594917A Expired - Fee Related CN100552105C (en) | 2007-09-04 | 2007-09-04 | Apparatus and method for preparing continuous carbon nanotube fibers by catalytic reaction of liquid-enclosed gas phase flow |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100552105C (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613895B (en) * | 2009-06-04 | 2011-08-24 | 天津大学 | Process method for preparing carbon nanotube fibers in an inert atmosphere based on chemical vapor flow spinning |
| CN101665997B (en) * | 2009-09-25 | 2013-01-02 | 天津大学 | Lamellar carbon nanofibre and preparation method thereof |
| CN101857986A (en) * | 2010-06-11 | 2010-10-13 | 垦利三合新材料科技有限责任公司 | Method for preparing nano carbon fiber |
| CN103031624A (en) * | 2012-12-03 | 2013-04-10 | 天津大学 | Method for preparing continuous carbon nanotube complex fiber |
| CN104641028B (en) * | 2013-06-18 | 2016-08-31 | Lg化学株式会社 | The device preparing carbon nano-tube fibre and the method utilizing described device to prepare carbon nano-tube fibre |
| CN103435029A (en) * | 2013-09-05 | 2013-12-11 | 武汉博力信纳米科技有限公司 | Device and method for preparing continuous carbon nanotube aggregate by assistance of ultrasonic atomization |
| CN103531753A (en) * | 2013-09-22 | 2014-01-22 | 天津大学 | Continuous carbon nanotube-titanium dioxide composite membrane/fiber for electrode material |
| CN103523768B (en) * | 2013-09-27 | 2018-02-09 | 武汉博力信纳米科技有限公司 | The apparatus and method that box sealing chemical gas phase reaction prepares continuous carbon nano-tube fibre |
| CN103626155B (en) * | 2013-12-06 | 2016-01-06 | 天津大学 | An efficient and environmentally friendly method for preparing carbon nanofibers |
| CN103628183B (en) * | 2013-12-06 | 2016-07-06 | 天津大学 | The method of continuous carbon nano-tube fibre is prepared in a kind of scale |
| CN107002306B (en) * | 2015-07-24 | 2020-05-12 | Lg化学株式会社 | Apparatus for making carbon nanotube fibers |
| CN107824140A (en) * | 2017-11-17 | 2018-03-23 | 河南师范大学 | It is a kind of to produce reactor visual during dibenzoyl methane |
| CN108301109A (en) * | 2018-03-27 | 2018-07-20 | 东华大学 | A kind of carbon nano-tube fibre knitted fabric and preparation method thereof |
| CN108588902A (en) * | 2018-04-18 | 2018-09-28 | 复旦大学 | A kind of extensive continuous preparation device and method of carbon nano tube composite fibre |
| KR102678204B1 (en) * | 2019-09-25 | 2024-06-26 | 주식회사 엘지화학 | Method for manufacturing carbon nanotube fibers with improved tensile strength |
| CN113957568A (en) * | 2020-07-21 | 2022-01-21 | 华东理工大学 | Preparation method of high-orientation carbon nanotube fiber |
| CN113957570B (en) * | 2021-11-23 | 2022-08-05 | 东华大学 | Device and method for preparing multi-wall high-purity carbon nanotube fiber |
| CN118056932B (en) * | 2022-11-18 | 2025-10-10 | 北京石墨烯研究院 | A method for preparing continuous and pure carbon nanotube fibers based on floating catalytic CVD method |
-
2007
- 2007-09-04 CN CNB2007100594917A patent/CN100552105C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101153413A (en) | 2008-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100552105C (en) | Apparatus and method for preparing continuous carbon nanotube fibers by catalytic reaction of liquid-enclosed gas phase flow | |
| CN111020747B (en) | System and method for continuously preparing carbon nanotube fibers based on floating catalytic CVD method | |
| CN101830455B (en) | Method for synthesizing continuous carbon nanometer tube film | |
| CN101613895B (en) | Process method for preparing carbon nanotube fibers in an inert atmosphere based on chemical vapor flow spinning | |
| CN103628183B (en) | The method of continuous carbon nano-tube fibre is prepared in a kind of scale | |
| EP3214212A1 (en) | Device for producing carbon nanotube fibers and method for producing carbon nanotube fibers using same | |
| CN206701242U (en) | A kind of pipeline reactor for fine chemistry industry production | |
| CN101665247A (en) | Method and device for preparing carbon nanotube film | |
| CN110685039B (en) | A method for mass production of carbon nanotube fibers | |
| CN101696519A (en) | Method for preparing carbon nanotube fibers at safe atmosphere | |
| CN103435029A (en) | Device and method for preparing continuous carbon nanotube aggregate by assistance of ultrasonic atomization | |
| CN108588902A (en) | A kind of extensive continuous preparation device and method of carbon nano tube composite fibre | |
| CN103031624A (en) | Method for preparing continuous carbon nanotube complex fiber | |
| CN104843666B (en) | A kind of device for growing carbon nanotube aerogel | |
| CN203558855U (en) | Device for preparing continuous carbon nano tube aggregate under assistance of ultrasonic atomization | |
| CN110385094A (en) | A kind of quick serialization preparation facilities of liquid hydrate | |
| CN114315768B (en) | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by using microwave-microreactor to catalyze fructose | |
| CN115814725A (en) | Method and device for producing carbon nano tube | |
| CN216273120U (en) | A continuous reaction device for synthesizing carbon nanotubes by chemical vapor deposition | |
| CN117324634B (en) | System and method for continuously synthesizing silver nanowires in microwave microreactor | |
| CN208661155U (en) | An oscillating flow reactor | |
| CN208944112U (en) | A kind of adiponitrile cyanation device | |
| CN205340399U (en) | Novel filter and collect device | |
| CN116603488A (en) | Preparation device and method of carbon nanotube tube-shaped object | |
| CN113247879B (en) | Method for preparing carbonized polymer quantum dots by spray pyrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091021 Termination date: 20120904 |