CN102923692A - Method for purifying carbon nano tube - Google Patents

Method for purifying carbon nano tube Download PDF

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Publication number
CN102923692A
CN102923692A CN2012104769184A CN201210476918A CN102923692A CN 102923692 A CN102923692 A CN 102923692A CN 2012104769184 A CN2012104769184 A CN 2012104769184A CN 201210476918 A CN201210476918 A CN 201210476918A CN 102923692 A CN102923692 A CN 102923692A
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Prior art keywords
carbon nano
tube
purifying
extraction
carbon nanotube
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CN2012104769184A
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贾增芹
刘向红
张薇蓉
李克迪
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Shanghai Bright Dairy and Food Co Ltd
Bright Dairy and Food Co Ltd
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Shanghai Bright Dairy and Food Co Ltd
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Abstract

The invention discloses a method for purifying a carbon nano tube. The method comprises the following steps: impurities in a crude product of the carbon nano tube are extracted by a Soxhlet extraction method; acid with a strong oxidizing property is utilized for extraction and then de-ionized water is utilized for extraction. The method for purifying the carbon nano tube is executed by the acid with the strong oxidizing property at a boiling temperature; the method is simple in processing technology and short in processing time; a suction filtration process, a centrifuging process and other processes are saved and efficiency for purifying the carbon nano tube is greatly improved; damage to the carbon nano tube is small by the purifying method; a purified carbon nano tube is high in heat resistance and good in reactivity and compatibility; and in addition, the acid can be recycled and resources are greatly reduced.

Description

A kind of method of purifying carbon nano-tube
Technical field
The present invention relates to a kind of method of purifying carbon nano-tube.
Background technology
Carbon nanotube as a kind of new carbon since coming out just with the strength and modulus of its superelevation, high length-to-diameter ratio, and the special property that shows in fields such as electromagnetism, Chu Qing, supported catalysts and being with a wide range of applications.Now common carbon nanotube is produced with chemical Vapor deposition process on the market, and the carbon nanotube of production usually contains the impurity such as decolorizing carbon, metal catalyst like this, thereby makes it be subject to certain limitation in application process.
Purification of Carbon Nanotubes mainly is divided into two kinds of physical method and chemical processes.Application number is that the vacuum high-temperature purification process that 03120818.5 Chinese patent adopts is typical physical purification method, and the method places vacuum environment to be heated to 1100-3000 ℃ to remove heat-labile impurity carbon nanotube.The carbon nanotube defective of Physical purifying is few, and carbon nanotube intensity is high, but power consumption is serious.
Application number is that 200710133632.5 Chinese patent discloses a kind of chemical purification carbon nanotube method, and the method adopts respectively the methods such as hydrofluoric acid, acid with strong oxidizing property and high temperature oxidation to process for impurity such as the silicon oxide that contains in the carbon nanotube, transition-metal catalyst and decolorizing carbon.The productive rate of this class chemical treatment method is high, energy consumption is low, can produce carboxyl, hydroxyl isopolarity group in carbon nano tube surface, be particularly useful for being applied to the carbon nanotube of macromolecule resin, but the complex technical process of this class chemical Treatment, carbon nanotube often was subject to larger destruction when the treatment time was long, and the acid of using in the treating processes can not recycle, and caused the wasting of resources.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of purifying carbon nano-tube in order to overcome the defective that complex technical process in the existing purification method of carbon nanometer pipe, treatment time are long, acid can not be recycled.The method of the purifying carbon nano-tube of the present invention acid with strong oxidizing property purifying carbon nano-tube that is in boiling temperature, treatment process is simple, the treatment time is short, and acid can be reclaimed and recycled, greatly saved resource, and purification process of the present invention is little to the damage that carbon nanotube causes, the carbon nanotube good heat resistance behind the purifying and have good reactivity and consistency.
The present invention solves the problems of the technologies described above by the following technical programs:
The invention provides a kind of method of purifying carbon nano-tube, it comprises the steps: to utilize the impurity in the soxhlet extraction extraction carbon nanotube crude product: use first the strong oxidizing property acid extraction, use deionized water extraction again.
Wherein, described soxhlet extraction can be the conventional soxhlet extraction that uses in this area, the better soxhlet extraction for adopting apparatus,Soxhlet's to carry out.For a person skilled in the art, generally the carbon nanotube crude product can be placed the extraction tube of apparatus,Soxhlet's, the extraction flask of heating apparatus,Soxhlet's, make solvent (such as the acid with strong oxidizing property among the present invention or the deionized water) boiling in the extraction flask, enter into prolong by the pipe connecting rising after the solvent gasification, splash in the extraction tube after being condensed, solvent contacts with the carbon nanotube crude product and carries out lixiviate impurity, when the solvent liquid level in the pipe to be extracted reach a certain height, the solvent that is dissolved with impurity flows into extraction flask through siphon pipe, thereby lixiviate goes out a part of impurity, the solvent that passes back in the extraction flask continues gasification, rise, condensation, lixiviate, reflux, so repeat, make impurity constantly be pure solvent institute lixiviate, the impurity enriched that goes out of lixiviate is in extraction flask the most at last.
Wherein, described carbon nanotube crude product can be the carbon nanotube that includes impurity or the carbon nanotube crude product of direct commercially available gained, for example includes Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes of impurity; In general, the carbon nanotube crude product includes the impurity such as metal catalyst, metal oxide and carbon nano-particle.
Wherein, described carbon nanotube crude product can coat with filtering membrane, and what described filtering membrane was better is poly tetrafluoroethylene and/or polypropylene screen; That the aperture of described filtering membrane is better is 0.22 ~ 0.45 μ m.
Wherein, described acid with strong oxidizing property can be the conventional acid with strong oxidizing property of using in this area, better is concentrated nitric acid and/or the vitriol oil, better for massfraction be 60% ~ 70%(preferred 68%) concentrated nitric acid and massfraction be 90% ~ 98%(preferred 98%) the nitration mixture that forms of the vitriol oil, best for massfraction be 60% ~ 70%(preferred 68%) concentrated nitric acid and massfraction be 90% ~ 98%(preferred 98%) the vitriol oil be the nitration mixture of 1:1 ~ 3:1 composition according to mass ratio.
Wherein, what the temperature of described strong oxidizing property acid extraction was better is 120 ~ 160 ℃, and this temperature is the outer temperature of heating extraction flask, so that the acid with strong oxidizing property gasification; What the time of described strong oxidizing property acid extraction was better is 1 ~ 20 hour.
Wherein, described soxhlet extraction can carry out under reduced pressure, and described decompression is so that acid with strong oxidizing property is advisable 120 ~ 160 ℃ of easily gasifications, backflows.
Wherein, the time of described deionized water extraction better to detect deionized water extraction liquid till the neutrality, be generally 1 ~ 5 hour.
Among the present invention, the method for described purifying carbon nano-tube can also further comprise following post-processing step: carbon nanotube is taken out, and oven dry, grinding gets final product.
Wherein, described oven dry better for be evacuated to below the 0.07MPa, temperature is to carry out under 60 ~ 80 ℃ the condition; The time of described oven dry better for to be advisable with twice weight difference in front and back<2%, be generally 2 ~ 10 hours.
Better, the method of purifying carbon nano-tube of the present invention is carried out according to the following step: the carbon nanotube crude product is placed in the extraction tube of apparatus,Soxhlet's with the filtering membrane wrapping, be that 68% concentrated nitric acid and massfraction be 98% the vitriol oil according to mass ratio are the extraction flask that nitration mixture that 3:1 forms is put into apparatus,Soxhlet's with massfraction, be heated to 140 ℃ of extractions, then change to do and use deionized water extraction, until till deionized water extraction liquid is neutrality, with carbon nanotube take out, oven dry, grind and get final product.
On the basis that meets this area general knowledge, above-mentioned each optimum condition, but arbitrary combination namely get the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is:
(1) the present invention adopts the strong oxidizing property acid concentration higher, and cleansing temp is higher, and the carbon nanotube yield is higher;
(2) working method of the present invention is simple, has saved suction filtration, the process such as centrifugal and has greatly improved the efficient of purifying carbon nano-tube, the carbon nanotube good heat resistance behind the purifying and have good reactivity and consistency;
(3) purification process of the present invention is little to the damage that carbon nanotube causes;
(4) the present invention's acid with strong oxidizing property of extracting employing can be recycled repeatedly, greatly economizes on resources, and has the application prospect of heavy industrialization.
Description of drawings
Fig. 1 a is the stereoscan photograph of the carbon nanotube before the purifying.
Fig. 1 b is the stereoscan photograph of the carbon nanotube behind embodiment 1 purifying.
Fig. 1 c is the stereoscan photograph of the carbon nanotube behind embodiment 2 purifying.
Fig. 2 be before and after the embodiment 1,2 purifying carbon nanotube at the thermogravimetric curve figure of nitrogen atmosphere, before a is purifying among the figure, after b is embodiment 1 purifying, after c is embodiment 2 purifying.
Fig. 3 a is that the XPS spectrum figure of the carbon nanotube before the purifying is at the high resolution peak of C1S.
Fig. 3 b is that the XPS spectrum figure of the carbon nanotube behind embodiment 1 purifying is at the high resolution peak of C1S.
Fig. 3 c is that the XPS spectrum figure of the carbon nanotube behind embodiment 2 purifying is at the high resolution peak of C1S.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to ordinary method and condition, or is selected according to catalogue.
The carbon nanotube crude product that following embodiment uses is the multi-walled carbon nano-tubes crude product, be purchased from Nanometer Port Co., Ltd., Shenzhen, purity〉95%, diameter 10 ~ 20nm, length 0.5 ~ 500 μ m, the carbon nanotube crude product includes the impurity such as metal catalyst, metal oxide and carbon nano-particle.
Embodiment 1
Take by weighing and put into the 250ml apparatus,Soxhlet's after 20g carbon nanotube crude product is wrapped up with poly tetrafluoroethylene, in 500ml single port flask, put into the concentrated nitric acid of 250ml massfraction 68%, in the stink cupboard said apparatus is put up rear logical water of condensation, condensate temperature is controlled at 0 ~ 4 ℃.Be heated to 140 ℃ (the outer temperature of extraction flask) and extract 5h.Nitric acid has decomposed and is reddish-brown in the heat-processed, so this process should be noted lucifuge and air draft.Change to 110 ℃ of (temperature outside the extraction flask) extraction 2h in the deionized water flask after extracting end, after detection deionized water extraction liquid becomes neutrality, carbon nanotube is taken out, dry, grinding is the carbon nanotube behind the purifying.The carbon nanotube yield is 94% behind the purifying.
Fig. 1 a, 1b are the stereoscan photograph of the carbon nanotube before and after embodiment 1 purifying, and wherein a is carbon nanotube crude product photo, can see the adhesion that bulk is arranged between the carbon nanotube; B is the carbon nanotube photo behind the purifying, can see that boundary is clear between the carbon nanotube, does not have adhesion.
Fig. 2 is the thermogravimetric curve figure (in nitrogen atmosphere) of carbon nanotube before and after embodiment 1 purifying, and wherein a curve is the thermogravimetric curve of carbon nanotube crude product, can see that the carbon nanotube crude product to thermally-stabilised, does not have weightlessness substantially; The b curve is the thermogravimetric curve of the carbon nanotube behind embodiment 1 purifying, because acid treatment makes carbon nano tube surface produce the defectives such as hydroxyl, carbonyl, thereby the carbon nanotube thermostability is reduced, carbon nanotube 6.2% of the total mass of having degraded in the time of 800 ℃, this carbon nanotube degradation rate than most of chemical Treatment is little, and (similarly treatment process carbon nanotube degrading quality is greater than 10%:Yan-Xin Liu(Chin.J.Chem., 2006, Vol.24, No.4)), illustrate that method of the present invention is little to the destructiveness of carbon nanotube.
Fig. 3 a, 3b are that the XPS spectrum figure of carbon nanotube before and after embodiment 1 purifying is at the high resolution peak of C1S, as we can see from the figure, carbon nanotube the phenomenon that broadens occur in conjunction with the energy eminence behind the purifying, also to moving in conjunction with the energy eminence, this has illustrated that all carbon nano tube surface combines the high element of electronegativity to the peak position of C1S.Find through the swarming analysis, carbon nano tube surface contains 12% hydroxyl and 7% carboxyl (with the molar ratio computing of carbon) after the purification process.A large amount of polar groups had appearred in carbon nano tube surface after this showed purifying, had increased reactivity and the consistency of carbon nanotube.
Embodiment 2
Take by weighing and put into the 250ml apparatus,Soxhlet's after 20g carbon nanotube crude product is wrapped up with poly tetrafluoroethylene, in 500ml single port flask, put into the 250ml massfraction and be 68% concentrated nitric acid and massfraction and be the nitration mixture that 98% the vitriol oil forms according to mass ratio 1:1, in the stink cupboard said apparatus is put up rear logical water of condensation, condensate temperature is controlled at 0-4 ℃.Although the vitriol oil is diluted by nitric acid but boiling point is still higher, need to add vacuum extractor at apparatus,Soxhlet's.The system air pressure of being evacuated to is 10kpa, is heated to 150 ℃ (the outer temperature of extraction flask) and extracts 5h.Change to 110 ℃ of (temperature outside the extraction flask) extraction 2h in the deionized water flask after extracting end, after detection deionized water extraction liquid becomes neutrality, carbon nanotube is taken out, dry, grinding is the carbon nanotube behind the purifying.The carbon nanotube yield is 91% behind the purifying.
Fig. 1 c is the carbon nanotube stereoscan photograph behind embodiment 2 purifying, can see that boundary is clear between the carbon nanotube, does not have adhesion.
C curve among Fig. 2 is the thermogravimetric curve (in nitrogen atmosphere) of carbon nanotube behind embodiment 2 purifying.As can be seen from the figure the thermal destruction rate of carbon nanotube illustrates that a little more than embodiment 1 the method is large than embodiment 1 to the degree of oxidation of carbon nanotube.
Fig. 3 c be the XPS spectrum figure of carbon nanotube behind embodiment 2 purifying at the high resolution peak of C1S, find through the swarming analysis, carbon nano tube surface contains 11.3% hydroxyl and 8.5% carboxyl (with the molar ratio computing of carbon) after the purification process.

Claims (11)

1. the method for a purifying carbon nano-tube is characterized in that, it comprises the steps: to utilize the impurity in the soxhlet extraction extraction carbon nanotube crude product: use first the strong oxidizing property acid extraction, use deionized water extraction again.
2. the method for purifying carbon nano-tube as claimed in claim 1 is characterized in that, described carbon nanotube crude product includes metal catalyst, metal oxide and carbon nano-particle impurity.
3. the method for purifying carbon nano-tube as claimed in claim 1 is characterized in that, described carbon nanotube crude product coats with filtering membrane.
4. the method for purifying carbon nano-tube as claimed in claim 3 is characterized in that, described filtering membrane is poly tetrafluoroethylene and/or polypropylene screen.
5. the method for purifying carbon nano-tube as claimed in claim 1 is characterized in that, described acid with strong oxidizing property is concentrated nitric acid and/or the vitriol oil.
6. the method for purifying carbon nano-tube as claimed in claim 5 is characterized in that, described acid with strong oxidizing property is that massfraction is that 60% ~ 70% concentrated nitric acid and massfraction are that 90% ~ 98% the vitriol oil is the nitration mixture that 1:1 ~ 3:1 forms according to mass ratio.
7. the method for purifying carbon nano-tube as claimed in claim 1 is characterized in that, the temperature of described strong oxidizing property acid extraction is 120 ~ 160 ℃, and the time of described strong oxidizing property acid extraction is 1 ~ 20 hour.
8. the method for purifying carbon nano-tube as claimed in claim 1 is characterized in that, the time of described deionized water extraction is for to detect deionized water extraction liquid till the neutrality.
9. such as the method for the described purifying carbon nano-tube of any one in the claim 1 ~ 8, it is characterized in that, the method for described purifying carbon nano-tube also comprises following post-processing step: carbon nanotube is taken out, and oven dry, grinding gets final product.
10. the method for purifying carbon nano-tube as claimed in claim 9 is characterized in that, described oven dry be evacuated to below the 0.07MPa, temperature is to carry out under 60 ~ 80 ℃ the condition, the time of described oven dry is for to be as the criterion with twice weight difference in front and back<2%.
11. the method for purifying carbon nano-tube as claimed in claim 1, it is characterized in that, it comprises the steps: the carbon nanotube crude product is placed in the extraction tube of apparatus,Soxhlet's with the filtering membrane wrapping, be that 68% concentrated nitric acid and massfraction be 98% the vitriol oil according to mass ratio are the extraction flask that nitration mixture that 3:1 forms is put into apparatus,Soxhlet's with massfraction, be heated to 140 ℃ of extractions, then change to do and use deionized water extraction, until till deionized water extraction liquid is neutrality, carbon nanotube is taken out, dries, and grinding gets final product.
CN2012104769184A 2012-11-21 2012-11-21 Method for purifying carbon nano tube Pending CN102923692A (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN105334249A (en) * 2015-09-29 2016-02-17 洛阳暖盈电子技术有限公司 Carbon nanotube modified electrode for determining enoxacin
CN106185869A (en) * 2016-08-31 2016-12-07 无锡东恒新能源科技有限公司 The Carbon nanotube purification system of the multistage reuse of heat energy
CN106185870A (en) * 2016-08-31 2016-12-07 无锡东恒新能源科技有限公司 The Carbon nanotube purification system of reuse heat energy
CN107473205A (en) * 2017-10-19 2017-12-15 焦作集越纳米材料技术有限公司 A kind of purification process of CNT
CN109110763A (en) * 2018-08-31 2019-01-01 华南农业大学 A kind of Sic nanotube and its preparation method and application
CN109350996A (en) * 2018-12-15 2019-02-19 浙江省食品药品检验研究院 A kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application
CN109594329A (en) * 2019-01-25 2019-04-09 嘉兴学院 A kind of conduction ramee and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105334249A (en) * 2015-09-29 2016-02-17 洛阳暖盈电子技术有限公司 Carbon nanotube modified electrode for determining enoxacin
CN106185869A (en) * 2016-08-31 2016-12-07 无锡东恒新能源科技有限公司 The Carbon nanotube purification system of the multistage reuse of heat energy
CN106185870A (en) * 2016-08-31 2016-12-07 无锡东恒新能源科技有限公司 The Carbon nanotube purification system of reuse heat energy
CN107473205A (en) * 2017-10-19 2017-12-15 焦作集越纳米材料技术有限公司 A kind of purification process of CNT
CN109110763A (en) * 2018-08-31 2019-01-01 华南农业大学 A kind of Sic nanotube and its preparation method and application
CN109350996A (en) * 2018-12-15 2019-02-19 浙江省食品药品检验研究院 A kind of graphite multi-walled carbon nano-tube solid-phase extraction column and its application
CN109594329A (en) * 2019-01-25 2019-04-09 嘉兴学院 A kind of conduction ramee and preparation method thereof

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Application publication date: 20130213