CN101351403A - Method and apparatus for manufacturing colloidal carbon nanoparticles homogeneously dispersed in aqueous solution - Google Patents
Method and apparatus for manufacturing colloidal carbon nanoparticles homogeneously dispersed in aqueous solution Download PDFInfo
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Abstract
A high purity of stable carbon colloid is manufactured under a condition of atmospheric pressure and room temperature. A method of manufacturing colloidal carbon nanoparticles homogeneously dispersed in water or aqueous solution includes preparing an electrolytic cell having a carbon oxidization electrode and an opposite electrode, the electrolytic cell containing an electrolyte and carbon, and performing electrolysis of the carbon by applying electricity between the carbon oxidization electrode and the opposite electrode for 20 to 500 hours in a constant voltage mode or in a constant current mode to sustain a current density of the carbon oxidization electrode in 3 to 20mA/cm2, so that the carbon in the electrolytic cell is oxidized and finely split and a carboxyl group is produced on a surface of the carbon.
Description
Technical field
The present invention relates to be used to make the method and apparatus of colloidal carbon nanoparticles, and more specifically relate to the method and apparatus that is used for being manufactured on aqueous solution homodisperse and the stable colloidal carbon nanoparticles that keeps.
Background technology
The nano particle of gold or titanium dioxide or colloid can have and remarkable different chemistry and the physical propertiess of its block form.Therefore, attempted using carbon granule to make carbon dust turn to nano-scale or manufacturing colloid.
When making carbon black and activated carbon, there are surface and oxygen bonded oxygenated compound.This oxygenated compound comprises phenolic group, quinolyl and carboxyl, and is covalently bonded to carbon granule.These groups are hydrophilic, are used for when by making the hydrophobic carbon particle at the water raising dispersion stabilization when making colloid that suspends.Carboxyl has the highest wetting ability, and the dispersion stabilization of carbon granule is had remarkable contribution.And carbon colloid is by the carboxyl acidifying.
When making carbon granule with the preparation carbon colloid, adjusting process is with further generation carboxyl.Yet because this method has limitation, it is the described carbon granule of chemical oxidation sometimes.By using nitric acid, carbon granule is oxidized basically.Have under the extremely low chemically reactive situation at carbon nanotube, by using the mixture oxidation nanometer pipe of the vitriol oil and concentrated nitric acid, around nanotube, to produce carboxyl.And, in order to produce carboxyl as much as possible by carbon oxide particle, carbon granule need be split into reduced size.The total amount of supposing carbon equates that if particle size is less, the surface-area of carbon then increases so, produces more carboxyls thus.And small-particle is many more, and sedimentary particle is just few more in the aqueous solution, thereby makes carbon colloid become more stable.Especially, if known size less than 50 nanometers, then particle is not subjected to influence of gravity, thereby can not precipitate.
In order making, carbon granule should to be split into the particle of 50 nanometers, and should on carbon surface, to produce a large amount of carboxyls and do not use additive not such as the high purity of carbon colloid of additives such as nitric acid, tensio-active agent.Yet, also the carbon granule of making is not split into the method for smaller szie.And, do not use such as the additive of nitric acid yet and increase the method for carboxyl.Therefore, in order to make high purity of carbon colloid by routine techniques, the technology that need remove additive impurity with the technology and the purification of additive oxidation nitric acid.Simultaneously, if the particle diameter of carbon granule greater than several microns, then can utilize strainer to filter described carbon granule and dissolve once more with neat solvent.In this case,, then be difficult to filter carbon granule, and it is too much to filter carbon granule required cost and time by routine techniques if carbon granule has the particle diameter of several nanometers.Therefore, in order to make highly purified stable carbon colloid, needs division carbon granule does not use the technology such as the oxygenant of nitric acid with making a large amount of carboxyls.
Summary of the invention
Technical problem
Therefore, propose the present invention solving the above-mentioned problems in the prior art, and an object of the present invention is to provide the method that is manufactured on homodisperse and the stable colloidal carbon nanoparticles that keeps in the water or the aqueous solution, wherein do not need to add the technology of additive.
Another object of the present invention provides the equipment that is used for making by aforesaid method colloidal carbon nanoparticles.
Additional advantages of the present invention, purpose and feature are set forth part in explanation subsequently, and to those skilled in the art, part will become apparent maybe and can understand from enforcement of the present invention after the following content of check.
Technical solution
To achieve these goals, provide the method that is manufactured on homodisperse colloidal carbon nanoparticles in the water or the aqueous solution, described method comprises electrochemical oxidation carbon so that the fine division of carbon and produce carboxyl on the surface of described carbon.
Described method comprises that also preparation has the electrolyzer of carbon oxidization electrode and opposite electrode, and this electrolyzer comprises electrolytic solution and carbon, and implements electrolysis by apply electricity between carbon oxidization electrode and opposite electrode.
In electrolysis step, the oxidized and fine division of the carbon in the electrolyzer, and on the surface of carbon, produce carboxyl.
In electrolysis step, electrolytic solution is applied ultrasonic wave.The preferred ultrasonic wave that alternately applies low frequency, intermediate frequency and high frequency.
Preferably, electrolytic solution flows between carbon oxidization electrode and opposite electrode.
Carbon oxidization electrode and opposite electrode are made by any one that is selected from graphitized carbon plate, tinsel and scribble in the tinsel of oxide film.
The carbon that is included in the electrolyzer is the one at least that is selected from carbon black, carbon nanotube, Graphite Powder 99, soccerballene, amorphous carbon and the graphite flake.
Carbon oxidization electrode and opposite electrode are applied volts DS, voltage of alternating current or pulsed voltage.
Electrolysis step kept 20～500 hours, and wherein the current density of carbon oxidization electrode is 3～20mA/cm
2
Described method can further comprise utilizes ultrasonic wave that the colloidal carbon nanoparticles that precipitates at least one day or the manufacturing that is filtered is handled again.
Be in the starting stage of next technology by the carbon nano-particle of aforesaid method manufacturing.
According to a further aspect in the invention, be provided for being manufactured on the equipment of homodisperse colloidal carbon nanoparticles in the water or the aqueous solution, this equipment comprises electrolyzer, the each interval that contains electrolytic solution and carbon and is immersed in carbon oxidization electrode and the opposite electrode in the electrolytic solution and is used for applying electric power subsystem between carbon oxidization electrode and opposite electrode, wherein make the oxidized and fine division of carbon in the electrolyzer, and produce carboxyl on the surface of carbon.
This equipment also comprises the first ultrasonic generating unit that is used for the electrolytic solution of electrolyzer is alternately applied low frequency, intermediate frequency and high-frequency ultrasonic.
This equipment also comprises the electrolyte circulation unit that is used for circular electrolyte between carbon oxidization electrode and opposite electrode.This electrolyte circulation unit comprises flowline and the pump that is connected to this flowline, and wherein said flowline one end is connected to carbon oxidization electrode, and the other end is connected to opposite electrode, makes electrolytic solution discharge and be supplied to subsequently electrolyzer from electrolyzer.Electrolyte circulation unit comprises that also being connected to flowline is used for temporarily storing the auxiliary reservoir of electrolytic solution to be recycled and being used for the electrolytic solution that is stored in auxiliary reservoir is applied the hyperacoustic second ultrasonic generating unit.
The first and second ultrasonic generating units are made up of several unit, and each unit is used to produce the different frequency in 10～1000kHz scope.
The electrolytic solution relief outlet of flowline preferably is connected to the bottom or the bottom of electrolyzer.
Carbon oxidization electrode and opposite electrode have female thread portion, and with outside screw type interelectrode distance governor lever threaded engagement.
The present invention makes highly purified stable colloid carbon solution, and wherein carbon is split into the particle diameter of 1～50 nanometer.For this reason, should make the colloidal carbon nanoparticles that is formed with carboxyl on its surface.
The present invention makes the colloidal carbon nanoparticles with carboxyl by introducing in the simple device such as the carbon granule of carbon black and pure water.Replace carbon granule, can also introduce carbon plate, for example graphite flake.The particle diameter of carbon can be split into 1 nanometer, and if necessary, also can adjust the particle diameter of carbon.The surface of carbon has carboxyl, and the concentration of using sodium hydroxide solution to come the titration carboxyl.Do not use additive because colloidal carbon nanoparticles is scattered in the water equably, and do not caused the positively charged ion of precipitation by metallic ion to pollute, so colloidal carbon nanoparticles stably keeps for a long time.The invention enables constant product quality, product to be easy to a large amount of manufacturings, and reduce manufacturing cost.An object of the present invention is to reduce the investment in production equipment volume, avoid producing waste water and waste gas and do not use hazardous chemical such as nitric acid.
Carbon is carried out electrochemical oxidation so that the fine division of carbon and produce carboxyl on the surface of carbon.For this reason, fill with electrolytic solution and carbon and to have after the electrolyzer of carbon oxidization electrode and opposite electrode, between carbon oxidization electrode and opposite electrode, apply.Carbon granule is divided particle thus and produces carboxyl in its surface by the oxygen institute oxidation that produces by electrochemistry in the electrolytic process.More specifically, the carbon granule surface loses electronics, negatively charged ion hydrogen-oxygen root OH
-Combine generation alcohol radical-OH with electronics.Alcohol radical becomes aldehyde radical-CHO by oxygen, and is oxidized to carboxyl-COOH.The carbon granule surface is coated with carboxyl by above-mentioned mechanism.The part that chemical bond a little less than having is made a concerted effort is continued oxidation by the oxygen that electrochemistry produces, and carbon granule is split into nano particle thus.
Preferably, the electrolytic solution in the electrolyzer is applied ultrasonic wave, and circular electrolyte therein.The oxidation on the division of carbon granule and surface is still further quickened by the circulation of ultrasonic wave and electrolytic solution mainly by electrolysis.The circulation of ultrasonic wave and electrolytic solution makes electrolytic solution disperse equably.
Beneficial effect
According to the present invention, highly purified stable carbon colloid can be made by described simple device and method.The carbon granule that is formed with a plurality of carboxyls on the surface can be split into the nano particle of 1 nanometer, and without mixed nitrate and tensio-active agent.Carbon granule comprises the inorganic and organic constituent as basic impurity.Except the caulking gum of expendable parts such as pump, described equipment does not have expensive apparatus, has significantly reduced manufacturing cost thus.Produce refuse during manufacturing hardly.
Description of drawings
To the description of preferred embodiment, it is more apparent that above-mentioned purpose of the present invention, further feature and advantage will become by with reference to the accompanying drawings, wherein:
Fig. 1 a is explanation is used to make colloidal carbon nanoparticles according to the present invention a synoptic diagram;
Fig. 1 b is the detailed view of the electrode mounting structure shown in the key drawing 1a;
Fig. 2 is TEM (transmission electron microscope) photo by the colloidal carbon nanoparticles of present method manufacturing; With
Fig. 3 is TEM (atomic force microscope (Atomic Force the Microscope)) photo by the colloidal carbon nanoparticles of the inventive method manufacturing.
Optimum way
Now, with the method and apparatus that is used to make colloidal carbon nanoparticles that is described in detail with reference to the attached drawings according to a preferred embodiment of the invention.
At first, referring now to Fig. 1 a and 1b the equipment that is used for being manufactured on water or the homodisperse colloidal carbon nanoparticles of the aqueous solution according to the present invention is described.Fig. 1 a is explanation is used to make the equipment of colloidal carbon nanoparticles according to the present invention a synoptic diagram, and Fig. 1 b is the detailed view of the electrode mounting structure shown in the key drawing 1a.
This equipment comprises the electrolyzer 10 that comprises electrolytic solution 15 and carbon 25, and is immersed in carbon oxidization electrode 11 and opposite electrode 12 in the electrolytic solution 15.Carbon oxidization electrode 11 and opposite electrode 12 are installed on the interelectrode distance governor lever 13 that is supported by framework 14, make the spacing of electrode 11 and 12 to regulate.Preferably, interelectrode distance governor lever 13 is outside screw types, and carbon oxidization electrode 11 and opposite electrode 12 are female type, with interelectrode distance governor lever 13 threaded engagement.
Spacing between carbon oxidization electrode 11 and the opposite electrode 12 is preferably regulated in the scope of 1～100mm.The spacing of electrode depends on the voltage that is applied.Along with spacing shortens, put on the loss of voltage of electrode.Electrolytic solution is a kind of resistance.Interelectrode distance is short more and electrode area is big more, and the voltage that then puts on electrode is just low more, reduces the capacity of energy expenditure and reduction direct supply thus.Therefore, help reducing cost and reduce and give birth to heat.If spacing is too short, then hydrogen and the oxygen that is produced by electrode is difficult to discharge by this spacing.If gas rests between the electrode, then electrolytic solution has just reduced the shared part of gas that stops, and has reduced the area of electrode thus and has therefore reduced electrolytic reaction.Therefore, the existence that reduces for spacing limits.Spacing is adjusted in the scope of 1～100mm, preferred 3～10mm.
Preferably, between electrode, insert spacer 26 to keep the interelectrode distance of various spacings.Spacer 26 is positioned at electrode edge and sentences the installation stability that improves electrode.Spacer 26 is made by isolator.For example, plastic bolt and the plastic nut as isolator can be fixed in electrode.And, preferably can utilize several electrodes with the stacked stacked structure of fixed spacing to boost productivity, as the electrode of representing by the dotted line among Fig. 1 a.
The first ultrasonic generating unit 17 is connected to electrolyzer 10 so that electrolyzer 10 is applied ultrasonic wave.The ultrasonic wave that is produced by the first ultrasonic generating unit 17 comprises low frequency, intermediate frequency and high frequency.As mentioned above, the ultrasonic wave that is applied to electrolytic solution is quickened the division and the surface oxidation of carbon granule, and also helps the homodisperse of electrolytic solution.Preferably electrolytic solution is alternately applied low frequency, intermediate frequency and high frequency.High-frequency ultrasonic has high-penetrability, but has reduced cavitation force.Low-frequency ultrasonic waves has low penetration, but has improved cavitation force.That is,, therefore can divide carbon granule effectively by electrolytic solution is alternately applied high frequency, intermediate frequency and low frequency because hyperacoustic penetrance and cavitation force change with frequency band.And, ultrasonic wave dissolving accumulative carbon granule, thus described uniform particles is dispersed in the electrolytic solution.Preferably, the first ultrasonic generating unit 17 is made up of several unit, and each unit is used to produce the different frequency in 10～1000kHz scope, for example high frequency, intermediate frequency and low frequency.
Equipment of the present invention also comprises the electrolyte circulation means 18 that is used for guiding electrolytic solution 15 between carbon oxidization electrode 11 and opposite electrode 12.Electrolyte circulation means is flowline 18-1, and as pipeline, the one end is connected to carbon oxidization electrode and the other end is connected to opposite electrode, makes electrolytic solution 15 discharge and be supplied to subsequently electrolyzer from electrolyzer 10.Flowline 18-1 disposes the pump 18-2 in order to circular electrolyte.Auxiliary reservoir 19 is connected to flowline 18-1 with temporary transient storage electrolytic solution to be recycled.The second ultrasonic generating unit 20 is connected to auxiliary reservoir 19 so that the electrolytic solution that temporarily is stored in the auxiliary reservoir 19 is applied ultrasonic wave.The second ultrasonic generating unit 20 can be made up of several unit, and each unit is used to produce the different frequency in 10～1000kHz scope, and for example high frequency, intermediate frequency and low frequency are similar to the first ultrasonic generating unit 17.Cycling through to electrode of electrolytic solution carried carbon granule to quicken electrochemical reaction, discharged for example hydrogen of the gas that produces, discharges for example heat that produces between electrode of hydrogen, uniform mixing electrolytic solution and radiation of the gas that produces, prevents that thus local temperature from raising.
In this embodiment, according to instruction, the first ultrasonic generating unit 17 and the second ultrasonic generation frock put 20 makes in low frequency (35kHz), intermediate frequency (72KHz) and high frequency (100kHz) vibrator that is installed in electrolyzer 10 and the auxiliary reservoir 19 each according to inferior sort run.
The electrolytic solution discharge outlet of flowline 18-1 is connected to the bottom or the bottom of electrolyzer 10, to aspirate sedimentary carbon granule.And carbon granule is slight separation by the second ultrasonic generating unit 20 that is connected to auxiliary reservoir 19.Electrolytic solution passes between electrode by electrolyte circulation means 18 thinks that electrolytic solution provides carbon granule, and discharges the gas that is produced by electrode by electrolysis.
Electrolyte supply storage tank 21 is connected to electrolyzer 10 and thinks electrolyzer 10 supply electrolytic solution.If necessary, electrolytic solution 15-1 can offer electrolyzer 10 by control valve 22.Electrolytic solution comprises distilled water, deionized water, tap water, river and underground water.Electrolytic solution can add the pH of additive with control electrolytic solution, and can add in electrolytic solution and the organic substance of water good mixing, for example ethanol and ethylene glycol.In order to make pure carbon colloid economically, deionized water is most preferred.
And product storage tank 23 is connected to the bottom of electrolyzer 10 with stored prod.The colloidal carbon nanoparticles of making is stored in the product storage tank 23 by valve 24.
The method of utilizing according to device fabrication colloidal carbon nanoparticles of the present invention will be described now.
Carbon agent 25 is made up of the one at least that is selected from carbon black, carbon nanotube, Graphite Powder 99, soccerballene, amorphous carbon and the graphite flake.
Electrolytic solution comprises distilled water, deionized water, tap water, river and underground water.Electrolytic solution can add the pH of additive with control electrolytic solution, and can add in electrolytic solution and the organic substance of water good mixing, for example ethanol and ethylene glycol.In order to make pure carbon colloid economically, deionized water is most preferred.
To add electrolytic solution such as the acidic substance of sulfuric acid, acetate and sodium pyrosulfate, and will add electrolytic solution such as the alkaline matter of yellow soda ash, sodium hydroxide and potassium hydroxide with alkalization electrolytic solution with acidifying electrolytic solution.
Under the situation of utilizing deionized water as electrolytic solution, electrolytic solution has the low conductivity of 0.2 μ S/cm in the early stage, thereby causes small amount of current to flow and cause oxidizing reaction slower.Along with reaction is carried out, the specific conductivity of electrolytic solution sharply increases, thereby causes a large amount of electric currents to flow and cause oxidizing reaction to obtain activation.As a result, carbon is covered by carboxyl then by fine division.
Electrolysis is undertaken by three phases.
Fs: power supply 30V, constant voltage mode, low frequency 5 minutes, intermediate frequency 5 minutes, high frequency 3 minutes.
Subordinate phase: power supply 25A, constant current mode, low frequency 2 minutes, intermediate frequency 2 minutes, high frequency 1 minute.
Phase III: power supply 20A, constant current mode, low frequency 1 minute, intermediate frequency 1 minute, high frequency 1/2 minute.
For the state that catch process is carried out, the specific conductivity of monitoring electrolytic solution.If specific conductivity is greater than 1.6 μ S/cm, then colloidal-carbon solution is finished.In addition, can monitor pH and ORP.In the stage of finishing, pH is about 2, and ORP is about 280mV.
During carrying out, electrolytic solution is taken a sample, and use the concentration of sodium hydroxide solution titration carboxyl.The particle diameter of carbon granule is by using the AFM device measuring, therefore with reference to its termination time with definite technology.
According to the specification of material and product, the process implementing of generation carboxyl 20～500 hours.
After this technology was finished, if collect carbon dust from the bottom of electrolyzer and it is added the electrolyzer in initial manufacturing process stage subsequently, thereby then the specific conductivity of electrolytic solution increased and causes a large amount of electric currents to flow and oxidizing reaction obtains activation.As a result, can shorten the process time of the fs of half approximately.
Preferably, electrolytic solution adds acid, alkali or salt material to improve the specific conductivity of electrolytic solution, shortens the process time of fs thus.
And the colloidal carbon nanoparticles of manufacturing preferably precipitates at least one day or by ultrasonic wave filtering carbon granule is carried out pre-treatment being nano particle with particle spliting.
Fig. 2 is TEM (transmission electron microscope) photo by the colloidal carbon nanoparticles of the inventive method manufacturing.In Fig. 2 a, the size of the scale of being represented by red circle is 20nm, and the part of being represented by the indigo plant circle is the size of carbon granule.Fig. 2 b and 2c are partial enlarged drawings, and wherein scale is 5nm.Hence one can see that, and the maximum particle diameter of the carbon nano-particle of generation is 5nm.
Fig. 3 is TEM (atomic force microscope (Atomic Force the Microscope)) photo by the colloidal carbon nanoparticles of the inventive method manufacturing.It verifies particle grain size and roughness by dispersion and scanning particle on substrate.Particle grain size can be verified by line chart.
Industrial applicibility
Can be obvious by above explanation: highly purified stable carbon colloid can be by simple device and method manufacturing.The carbon granule that is formed with a plurality of carboxyls on the surface can be split into the nano particle of 1 nanometer, and nitric acid need not be mixed with tensio-active agent.Carbon granule comprises the inorganic and organic constituent as basic impurity.Except the caulking gum of expendable parts such as pump, equipment does not have expensive apparatus, has reduced manufacturing cost thus significantly.Produce refuse during manufacturing hardly.
Above-mentioned embodiment only is exemplary, should not be construed as limiting the invention.This instruction can easily be applied to the equipment of other type.Illustration of the present invention is illustrative, rather than the scope of restriction claim.Numerous replacement schemes, change and variation are conspicuous for those skilled in the art.
Claims (17)
1. method that is manufactured on homodisperse colloidal carbon nanoparticles in the water or the aqueous solution, described method comprises:
Preparation has the electrolyzer of carbon oxidization electrode and opposite electrode, and described electrolyzer comprises electrolytic solution and carbon; And
Implement the electrolysis of carbon by following steps: applying electricity 20～500 hours with constant voltage mode or constant current mode between described carbon oxidization electrode and described opposite electrode, is 3～20mA/cm with the current density that keeps described carbon oxidization electrode
2, make described carbon in the described electrolyzer oxidized and, and on the surface of described carbon, produce carboxyl by fine division.
2. method according to claim 1 wherein in described electrolysis step, alternately applies the ultrasonic wave of low frequency, intermediate frequency and high frequency to described electrolytic solution.
3. method according to claim 1, wherein in described electrolysis step, described electrolytic solution flows between described carbon oxidization electrode and described opposite electrode.
4. method according to claim 1, wherein said carbon oxidization electrode is made by any one that is selected from graphitized carbon plate, tinsel and scribble in the tinsel of oxide film.
5. method according to claim 1, wherein said opposite electrode is made by graphitized carbon plate, tinsel and any one of scribbling in the tinsel of oxide film.
6. method according to claim 1, the described carbon that wherein is included in the described electrolyzer is the one at least that is selected from carbon black, carbon nanotube, Graphite Powder 99, soccerballene, amorphous carbon and the graphite flake.
7. method according to claim 1 wherein in described electrolysis step, applies volts DS, voltage of alternating current or pulsed voltage to described carbon oxidization electrode and described opposite electrode.
8. according to any described method in the claim 1,3,4,5,6 and 7, also comprise by using ultrasonic wave that the colloidal carbon nanoparticles of the described manufacturing that precipitated at least one day or be filtered is handled again.
9. equipment that is used for being manufactured on water or the homodisperse colloidal carbon nanoparticles of the aqueous solution, described equipment comprises:
The electrolyzer that comprises electrolytic solution and carbon;
Each interval and be immersed in carbon oxidization electrode and opposite electrode in the described electrolytic solution;
Power subsystem is used for applying electricity 20～500 hours with constant voltage mode or constant current mode between described carbon oxidization electrode and described opposite electrode, and the current density of wherein said carbon oxidization electrode is 3～20mA/cm
2With
The first ultrasonic generating unit is used for the described electrolytic solution of described electrolyzer is alternately applied the ultrasonic wave of low frequency, intermediate frequency and high frequency;
Described carbon in the wherein said electrolyzer is oxidized and by fine division, and produces carboxyl on the surface of described carbon.
10. equipment according to claim 9 also comprises the electrolyte circulation unit that is used for circular electrolyte between described carbon oxidization electrode and described opposite electrode.
11. equipment according to claim 10, wherein said electrolyte circulation unit comprises:
Flowline, described flowline one end is connected to described carbon oxidization electrode, and the other end is connected to described opposite electrode, make described electrolytic solution by described electrolyzer discharge and be supplied to subsequently described electrolyzer and
Be connected to the pump of described flowline.
12. equipment according to claim 10, wherein said electrolyte circulation unit comprises:
Be connected to described flowline be used for the temporary transient auxiliary reservoir that stores electrolytic solution to be recycled and
Be used for the electrolytic solution that is stored in described auxiliary reservoir is applied the hyperacoustic second ultrasonic generating unit.
13. according to claim 9 or 12 described equipment, the wherein said first and second ultrasonic generating units are made of several unit, each unit is used to produce the different frequency in 10～1000kHz scope.
14. equipment according to claim 11, the electrolytic solution discharge outlet of wherein said flowline is connected to the bottom or the bottom of described electrolyzer.
15. equipment according to claim 9, wherein said carbon oxidization electrode and described opposite electrode have female thread portion, and with the interelectrode distance governor lever threaded engagement of outside screw type.
16. equipment according to claim 15, the spacing between wherein said carbon oxidization electrode and the described opposite electrode is in the scope of 1～100mm.
17. equipment according to claim 15 wherein inserts spacer between described carbon oxidization electrode and described opposite electrode.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020050135771 | 2005-12-30 | ||
| KR10-2005-0135771 | 2005-12-30 | ||
| KR1020050135771A KR100664664B1 (en) | 2005-12-30 | 2005-12-30 | Method and apparatus for manufacturing colloidal carbon nano homogeneously dispersed in aqueous solution |
| PCT/KR2006/005746 WO2007078082A1 (en) | 2005-12-30 | 2006-12-27 | Method and apparatus for manufacturing colloidal carbon nanoparticles homogeneously dispersed in aqueous solution |
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| CN105602558A (en) * | 2016-03-03 | 2016-05-25 | 东南大学 | Fluorescent carbon dot narrow in full width at half maximum and preparation method and application thereof |
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| JPS58115123A (en) * | 1981-12-29 | 1983-07-08 | Toray Ind Inc | Surface treatment of carbon fiber |
| KR890005015B1 (en) * | 1986-11-20 | 1989-12-06 | 도오아 넨료오 고오교오 가시시끼가이샤 | Surface treatment method of carbon fiber |
| JPH078790A (en) * | 1993-06-24 | 1995-01-13 | Kenichi Fujita | Preparation of colloidal solution of carbon |
| JPH10245213A (en) | 1997-03-05 | 1998-09-14 | Tatsuya Shono | Production of hydrophilic carbonaceous material |
| JP2000086220A (en) | 1998-09-14 | 2000-03-28 | Kenichi Fujita | Ultrafine carbon particle |
| KR20010018921A (en) * | 1999-08-23 | 2001-03-15 | 박현용 | Establishment which relives snakes of impact from the ground in rearing snakes |
| JP2001180921A (en) * | 1999-12-27 | 2001-07-03 | Kenichi Fujita | Oxidized carbon colloid and plant growth agent made of the same |
| FR2805179B1 (en) * | 2000-02-23 | 2002-09-27 | Centre Nat Rech Scient | PROCESS FOR OBTAINING MACROSCOPIC FIBERS AND TAPES FROM COLLOIDAL PARTICLES, IN PARTICULAR CARBON NANOTUBES |
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2005
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| CN107697904A (en) * | 2017-09-12 | 2018-02-16 | 刘云芳 | The process for dispersing and its device of a kind of CNT |
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| CN109537030A (en) * | 2018-11-26 | 2019-03-29 | 江苏科技大学 | A kind of preparation method of carbon nano-particle solution and its application in nickel coating |
| CN109665513A (en) * | 2019-01-31 | 2019-04-23 | 中国科学院山西煤炭化学研究所 | A kind of method and device of electrochemical treatments charcoal particle |
| CN109665513B (en) * | 2019-01-31 | 2020-10-27 | 中国科学院山西煤炭化学研究所 | Method and device for electrochemically treating carbon particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101351403B (en) | 2011-08-24 |
| KR100664664B1 (en) | 2007-01-04 |
| WO2007078082A1 (en) | 2007-07-12 |
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