CN104310375B - A kind of method of removing carbon impurity in SWCN - Google Patents
A kind of method of removing carbon impurity in SWCN Download PDFInfo
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- CN104310375B CN104310375B CN201410528149.7A CN201410528149A CN104310375B CN 104310375 B CN104310375 B CN 104310375B CN 201410528149 A CN201410528149 A CN 201410528149A CN 104310375 B CN104310375 B CN 104310375B
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Abstract
The invention discloses a kind of method of removing carbon impurity in SWCN, comprise mechanical lapping, high-temperature hydrogen or middle isothermal plasma hydrogen treat, air current classifying screening and repetition above-mentioned steps two to three times; The method can be onion carbon nano-particle by the carbon impurity in SWCN, and the mass fraction of multi-walled carbon nano-tubes or amorphous carbon is reduced to below 0.05% by 50%; Owing to being complete dry process, can keep the leavening structure of SWCN, for the application such as ultracapacitor energy storage or electrically conducting transparent demonstration provide basis simultaneously; This method have equipment few, simple to operate, easily repeat, process is easily amplified, the advantage that cost is low.
Description
Technical field
The present invention relates to carbon impurity technical field in SWCN, be specifically related to a kind of single wall carbon of removingThe method of carbon impurity in nanotube.
Background technology
SWCN is that a kind of diameter is little, draw ratio is large, and specific area is large, electric conductivity and semiconductorThe nano material that property is adjustable, mechanical strength is excellent, at nanometer circuit, macromolecule intensity composite, softThe fields such as property electronic product, electrically conducting transparent display material, capacitor deposited energy, have extensive and important useOn the way.
The effective method of preparing at present SWCN is chemical vapour deposition technique. Its principle is to makeWith metallic catalyst, cracking carbon source gained under higher temperature. Because diameter of single-wall carbon nano tube is little, instituteMust use the very little metal nano catalyst of particle diameter. But even so, nano metal coalescence under high temperature,Still can inevitably produce the carbon impurity such as onion carbon nano-particle and multi-walled carbon nano-tubes, amorphous carbon.Due to these impurity diameters or size larger, during for electrically conducting transparent display material, can cause material thoroughlyLightness declines. And during for ultracapacitor, because its specific area is low, can cause the electricity of electrode materialCapacity loss. Therefore be necessary very much by the method for subsequent purification processing, it to be removed completely.
The purification process of SWCN has had a lot of reports at present, comprises acidic treatment, or high temperatureOxidation processes. Acid treatment (wet method) has produced much not tractable waste water on the one hand, simultaneously after washingCarbon nanomaterial can reunite, be difficult for disperse, affect serviceability. On the other hand, high-temperature oxidation choosingSelecting property is poor, is difficult for control, in removing onion carbon nano-particle and multi-walled carbon nano-tubes Graphene, and meetingA large amount of loss SWCNs. And the oxidate temperature of onion carbon nano-particle and multi-walled carbon nano-tubesHigher than SWCN, be difficult for removing completely. Above-mentioned condition for SWCN at electrically conducting transparentApplication in demonstration, ultracapacitor is unfavorable.
Summary of the invention
The problem existing in order to solve above-mentioned prior art, the object of the present invention is to provide a kind of list of removingThe method of carbon impurity in wall carbon nano tube, can reduce the loss late of SWCN in purge process,Can keep the leavening structure of SWCN, for ultracapacitor energy storage or electrically conducting transparent demonstration etc. shouldWith provide basis, have employing equipment few, simple to operate, easily repeat, process is easily amplified, cost is lowAdvantage.
For reaching above object, the present invention adopts following technical scheme:
A method of removing carbon impurity in SWCN, comprises the steps:
Step 1: the SWCN product of carbon-containing impurities is ground to 1-24h by the method for mechanical lapping;
Step 2: the SWCN product after mechanical lapping is placed in to reactor, by hydrogenGas is processed in the environment of high temperature or middle isothermal plasma;
Step 3: by the method processing of SWCN product recycling air current classifying after treatment screening,Then be down to room temperature;
Step 4: repeat above-mentioned steps 1-3 mono-to three time;
The gas of the hydrogen described in step 2 refers to the mist of hydrogen and helium or argon gas, wherein hydrogenVolume fraction be 50-100%; Temperature when high-temperature process is 700-850 DEG C, and absolute pressure is0.1-0.3Mpa, the processing time is 1-72h, the weight space velocity of hydrogen is 0.1-10g/g carbon impurity/h; Middle temperatureTemperature when plasma hydrogen treat is 300-550 DEG C, and absolute pressure is 0.1-0.3Mpa, the processing timeFor 1-72h, the weight space velocity of hydrogen is 0.1-10g/g carbon impurity/h;
The method processing that utilizes air current classifying screening described in step 3, is specially: make to pass in reactorOne or more gases in hydrogen, helium or argon gas, controlling gas speed is 0.01-0.1m/s, the processing timeFor 0.1-0.5h, carbon impurity is separated with SWCN.
The mass fraction that the SWCN product of described carbon-containing impurities is SWCN is50-99.7%, carbon impurity be a kind of in multi-walled carbon nano-tubes, onion carbon nano-particle, amorphous carbon orMultiple, its gross mass mark is 0.3-50%.
The carbon-coating number of described multi-walled carbon nano-tubes is greater than 5.
Described in step 1, the method for mechanical lapping refers to and uses corundum, boron carbide or the spherical grinding of zirconiaGrain, the volume ratio of the SWCN product of spherical grinding particle and carbon-containing impurities is 10:1-1:10.
The pattern of described reactor is fixed bed, fluid bed or revolving burner.
Compared to the prior art, tool has the following advantages in the present invention:
1) what the inventive method adopted is to be all to carry out under dry environment in steps, with wet-treating(in liquid) is compared, and has save filtration, drying and other steps, has both shortened the processing time, avoids againIn traditional heat drying process, the volume contraction of the too fast carbon nano-electrode material causing of liquid evaporationProblem, make product keep bulk state, be conducive to subsequent applications. Can reduce processing cost 20%, improveThe ratio 50% of the product of leavening structure.
2) utilizing the method for hydrogen reducing, is the feature of having utilized SWCN good crystallinity, and itsStructural instability of his carbon impurity, can selective removal carbon impurity. Method with oxidizing gas processingCompare, not only easy temperature control, process is easily amplified, and can maximumly reduce single wall carbon nano-tube in purge process simultaneouslyThe loss late of pipe to 0.5%. make processing cost reduce by 30%.
3) mechanical lapping can increase the active face of carbon impurity, improves the efficiency of hydrogen. Simultaneously in mechanical lappingAnd after hydrogen treat diminishes part carbon impurity, it is difficult for forming agglomerate, available air current classifying screening directlyRemove part carbon impurity, can effectively reduce the consumption of hydrogen.
4) the present invention is owing to processing in dry environment, and products obtained therefrom, after cooling, can directly be packed,Reduce again the links such as dry or oven dry, be conducive to keep SWCN product surface clean, rightFavourable in subsequent applications.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
By the SWCN containing 50% multi-walled carbon nano-tubes, use corundum ball to grind, control carbon productsWith the volume of corundum ball be 1:10, grind 20 hours. Proceed to fixed bed reactors, at 850 DEG C, pass intoHydrogen, control hydrogen weight space velocity be under the condition of 0.1g/g carbon impurity/h, at 0.3MPa (definitelyPressure) process 72 hours. Then gas velocity is mentioned to 0.1m/s, the processing time is 0.5 hour, by gasStream sizing screening separates multi-walled carbon nano-tubes with SWCN, be then down to room temperature. Institute for the first timeObtain SWCN mass fraction in product and be increased to 85%. Repeat above-mentioned steps, gained produces for the second timeIn product, SWCN mass fraction is increased to 95%. Repeat above-mentioned steps, for the third time in products obtained therefromSWCN mass fraction is increased to 99%. Repeat above-mentioned steps, single wall in the 4th products obtained therefromCNT mass fraction is increased to 99.97%.
Embodiment 2
By the SWCN containing 50% onion carbon nano-particle, use boron nitride ball to grind, control carbonThe volume of product and boron nitride ball is 10:1, grinds 24 hours. Proceed to fluidized-bed reactor, at 800 DEG CUnder pass into 90% hydrogen and 10% argon gas (volume fraction), controlling the weight space velocity of hydrogen is that 10g/g carbon is assortedUnder the condition of matter/h, process 60 hours at 0.1MPa (absolute pressure). Then gas velocity is mentioned to 0.01m/s,Processing time is 0.5 hour, is screened onion carbon nano-particle and SWCN are divided by air current classifyingFrom, be then down to room temperature. In products obtained therefrom, SWCN mass fraction is increased to 88% for the first time.Repeat above-mentioned steps, in products obtained therefrom, SWCN mass fraction is increased to 96% for the second time. RepeatAbove-mentioned steps, in products obtained therefrom, SWCN mass fraction is increased to 99.95% for the third time.
Embodiment 3
By the SWCN containing 5% onion carbon nano-particle and 1% multi-walled carbon nano-tubes, use nitrogenizeBoron ball grinds, and the volume of controlling carbon products and boron nitride ball is 1:2, grinds 1 hour. Proceed to fluid bed anti-Answer device, pass into 50% hydrogen and 50% helium (volume fraction) at 480 DEG C, plasma atmosphere, controlsThe weight space velocity of hydrogen is under the condition of 5g/g carbon impurity/h, little in 0.2MPa (absolute pressure) processing 48Time. Then gas velocity is mentioned to 0.05m/s, the processing time is 0.3 hour, by onion carbon nano-particle,Multi-walled carbon nano-tubes separates with SWCN, is then down to room temperature. Single wall in products obtained therefrom for the first timeCNT mass fraction is increased to 97%. Repeat above-mentioned steps, in products obtained therefrom, single wall carbon is received for the second timeMitron mass fraction is increased to 99.3%. Repeat above-mentioned steps, for the third time SWCN in products obtained therefromMass fraction is increased to 99.98%.
Embodiment 4
By the SWCN containing 5% amorphous carbon and 5% multi-walled carbon nano-tubes, use zirconia ball to grindMill, the volume of controlling carbon products and zirconia ball is 1:2, grinds 3 hours. Proceed to revolving burner reactor,At 850 DEG C, pass into 50% hydrogen and 50% helium (volume fraction), the weight space velocity of controlling hydrogen is 2g/gUnder the condition of carbon impurity/h, process 1 hour at 0.2MPa (absolute pressure). Then gas velocity is mentioned0.06m/s, the processing time is 0.4 hour, screens amorphous carbon, multi-wall carbon nano-tube by air current classifyingPipe separates with SWCN, is then down to room temperature. SWCN matter in products obtained therefrom for the first timeAmount mark is increased to 98%. Repeat above-mentioned steps, in products obtained therefrom, SWCN quality is divided for the second timeNumber is increased to 99.96%.
Embodiment 5
By the SWCN containing 5% onion carbon nano-particle and 1% multi-walled carbon nano-tubes, use corundumBall grinds, and the volume of controlling carbon products and corundum ball is 1:10, grinds 1 hour. Proceed to fixed bed reactors,At 520 DEG C, pass into 50% hydrogen and 50% helium (volume fraction), under plasma atmosphere, control hydrogenWeight space velocity be under the condition of 5g/g carbon impurity/h, 0.2MPa (absolute pressure) process 30 hours.Then gas velocity is mentioned to 0.05m/s, the processing time is 0.5 hour, screens onion carbon by air current classifyingNano particle, multi-walled carbon nano-tubes separate with SWCN, are then down to room temperature. Gained for the first timeIn product, SWCN mass fraction is increased to 98.5%. Repeat above-mentioned steps, for the second time products obtained therefromMiddle SWCN mass fraction is increased to 99.8%. Repeat above-mentioned steps, single in products obtained therefrom for the third timeWall carbon nano tube mass fraction is increased to 99.99%.
Embodiment 6
By the SWCN containing 20% amorphous carbon and 20% onion carbon nano-particle, use boron nitrideBall grinds, and the volume of controlling carbon products and boron nitride ball is 1:10, grinds 20 hours. Proceed to fixed bed anti-Answer device, at 550 DEG C, pass into hydrogen, under plasma atmosphere, the weight space velocity of controlling hydrogen is 8g/gUnder the condition of carbon impurity/h, process 72 hours at 0.1MPa (absolute pressure). Then gas velocity is mentioned0.1m/s, is screened onion carbon nano-particle, amorphous carbon is separated with SWCN by air current classifying,Then be down to room temperature. In products obtained therefrom, SWCN mass fraction is increased to 90% for the first time. RepeatAbove-mentioned steps, in products obtained therefrom, SWCN mass fraction is increased to 99% for the second time. Repeat above-mentionedStep, in products obtained therefrom, SWCN mass fraction is increased to 99.9% for the third time. Repeat above-mentioned steps,In the 4th products obtained therefrom, SWCN mass fraction is increased to 99.98%.
Embodiment 7
Will be containing 10% onion carbon nano-particle and 20% multi-walled carbon nano-tubes, the single wall carbon of 5% amorphous carbon is receivedMitron, uses zirconia ball to grind, and the volume of controlling carbon products and zirconia ball is 1:10, and grinding 24 is littleTime, proceed to fixed bed reactors, at 300 DEG C, pass into 90% hydrogen and 10% helium (volume fraction), etc.Under gas ions atmosphere, the weight space velocity of controlling hydrogen is under the condition of 10g/g carbon impurity/h, at 0.3MPa (absolutelyTo pressure) process 72 hours. Then gas velocity is mentioned to 0.08m/s, the processing time is 0.5 hour, passes throughAir current classifying screens onion carbon nano-particle, multi-walled carbon nano-tubes, amorphous carbon and SWCNSeparate, be then down to room temperature. In products obtained therefrom, SWCN mass fraction is increased to 95% for the first time.Repeat above-mentioned steps, in products obtained therefrom, SWCN mass fraction is increased to 99% for the second time. RepeatAbove-mentioned steps, in products obtained therefrom, SWCN mass fraction is increased to 99.97% for the third time.
Embodiment 8
By the SWCN containing 0.2% onion carbon nano-particle and 0.1% multi-walled carbon nano-tubes, use justBeautiful ball grinds, and the volume of controlling carbon products and boron nitride ball is 5:1, grinds 2 hours, proceeds to revolving burner reactionDevice passes into 50% hydrogen and 50% argon gas (volume fraction) at 700 DEG C, controls the weight space velocity of hydrogenUnder condition for 0.5g/g carbon impurity/h, process 15 hours at 0.2MPa (absolute pressure). Then by gasFlow velocity is mentioned 0.08m/s, and the processing time is 0.2 hour, screens onion carbon nanometer by air current classifyingGrain, multi-walled carbon nano-tubes separate with SWCN, are then down to room temperature. Single wall carbon in products obtained therefromNanotube mass fraction reaches 99.96%.
Embodiment 9
By the SWCN containing 2% multi-walled carbon nano-tubes, use zirconia ball to grind, control carbon productsWith the volume of zirconia ball be 6:1, grind 1 hour, proceed to fixed bed reactors, at 400 DEG C, pass into 80%Hydrogen and 20% helium (volume fraction), under plasma atmosphere, the weight space velocity of controlling hydrogen is 8g/gUnder the condition of carbon impurity/h, process 2 hours at 0.3MPa (absolute pressure). Then gas velocity is mentioned0.03m/s, the processing time is 0.1 hour, is screened multi-walled carbon nano-tubes and single wall carbon are received by air current classifyingMitron separates, and is then down to room temperature. In products obtained therefrom, SWCN mass fraction is increased to for the first time99.9%. Repeat above-mentioned steps, in products obtained therefrom, SWCN mass fraction is increased to for the second time99.99％。
Claims (5)
1. a method of removing carbon impurity in SWCN, is characterized in that: comprise the steps:
Step 1: the SWCN product of carbon-containing impurities is ground to 1-24h by the method for mechanical lapping;
Step 2: the SWCN product after mechanical lapping is placed in to reactor, passes into hydrogenGas is processed in the environment of high temperature or middle isothermal plasma;
Step 3: by the method processing of SWCN product recycling air current classifying after treatment screening,Then be down to room temperature;
Step 4: repeat above-mentioned steps 1-3 mono-to three time;
The gas of the hydrogen described in step 2 refers to hydrogen, or the mist of hydrogen and helium, or hydrogenWith the mist of argon gas, in the gas of hydrogen, the volume fraction of hydrogen is 50-100%; High-temperature processTime temperature be 700-850 DEG C, absolute pressure is 0.1-0.3Mpa, the processing time is 1-72h, the weight of hydrogenAmount air speed is 0.1-10g/g carbon impurity/h; Temperature when middle isothermal plasma hydrogen treat is 300-550 DEG C,Absolute pressure is 0.1-0.3Mpa, and the processing time is 1-72h, and the weight space velocity of hydrogen is that 0.1-10g/g carbon is assortedMatter/h;
The method processing that utilizes air current classifying screening described in step 3, is specially: make to pass in reactorOne or more gases in hydrogen, helium or argon gas, controlling gas speed is 0.01-0.1m/s, the processing timeFor 0.1-0.5h, carbon impurity is separated with SWCN.
2. a kind of method of removing carbon impurity in SWCN according to claim 1, its spyLevy and be: in the SWCN product of described carbon-containing impurities, the mass fraction of SWCN is50-99.7%, carbon impurity be a kind of in multi-walled carbon nano-tubes, onion carbon nano-particle, amorphous carbon orMultiple, its gross mass mark is 0.3-50%.
3. a kind of method of removing carbon impurity in SWCN according to claim 2, its spyLevy and be: the carbon-coating number of described multi-walled carbon nano-tubes is greater than 5.
4. a kind of method of removing carbon impurity in SWCN according to claim 1, its spyLevy and be: described in step 1, the method for mechanical lapping refers to and uses corundum, boron carbide or zirconia is spherical grindsAbrasive particle, the volume ratio of the SWCN product of spherical grinding particle and carbon-containing impurities is 10:1-1:10.
5. a kind of method of removing carbon impurity in SWCN according to claim 1, its spyLevy and be: the pattern of described reactor is fixed bed, fluid bed or revolving burner.
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| CN105060271A (en) * | 2015-07-30 | 2015-11-18 | 惠州集越纳米材料技术有限责任公司 | Carbon nano-tube purification method |
| CN106185867A (en) * | 2016-08-22 | 2016-12-07 | 赖世权 | The purity of CNT improves method |
| CN106365150A (en) * | 2016-08-31 | 2017-02-01 | 无锡东恒新能源科技有限公司 | Carbon nano tube purification system for recycling acid liquor in different stages |
| CN106365149A (en) * | 2016-08-31 | 2017-02-01 | 无锡东恒新能源科技有限公司 | Carbon nanotube purification system capable of continuously removing impurities |
| CN106365147A (en) * | 2016-08-31 | 2017-02-01 | 无锡东恒新能源科技有限公司 | Carbon nano tube purification system for acid recovery |
| CN106365148A (en) * | 2016-08-31 | 2017-02-01 | 无锡东恒新能源科技有限公司 | Carbon nano-tube purification system |
| CN108101025B (en) * | 2017-11-29 | 2020-08-14 | 航天材料及工艺研究所 | Method for reinforcing tube wall structure of carbon nano tube |
| CN110684392B (en) * | 2019-09-29 | 2022-05-06 | 佛山宜可居新材料有限公司 | Multi-wall carbon nano tube composite conductive material, preparation method and product thereof |
| CN111470489A (en) * | 2019-11-05 | 2020-07-31 | 中山大学 | Conversion method for converting single-wall carbon nanotube into double-wall carbon nanotube |
| CN113956051B (en) * | 2021-11-26 | 2023-03-21 | 厦门钜瓷科技有限公司 | Decarbonization method for preparing aluminum nitride powder by carbothermic method |
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| US7090819B2 (en) * | 2001-02-12 | 2006-08-15 | William Marsh Rice University | Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof |
| US8052075B2 (en) * | 2008-04-03 | 2011-11-08 | Micron Technology, Inc. | Method for purification of semiconducting single wall nanotubes |
| CN101746746A (en) * | 2008-12-19 | 2010-06-23 | 索尼株式会社 | Method for preparing and purifying carbon nano tubes, carbon nano tubes and carbon nano tube elements |
| CN102398901B (en) * | 2010-09-10 | 2013-07-03 | 中国科学院金属研究所 | Method for high-efficiency purification of single-wall carbon nanotubes prepared by chemical vapor deposition |
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