CN109626359A - A kind of method of purifying carbon nano-tube and by its carbon nanotube after purification - Google Patents
A kind of method of purifying carbon nano-tube and by its carbon nanotube after purification Download PDFInfo
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- CN109626359A CN109626359A CN201910079342.XA CN201910079342A CN109626359A CN 109626359 A CN109626359 A CN 109626359A CN 201910079342 A CN201910079342 A CN 201910079342A CN 109626359 A CN109626359 A CN 109626359A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
Abstract
The present invention relates to a kind of methods of purifying carbon nano-tube comprising: carbon nanotube is successively handled using the aqueous solution of industrial nitric acid and technical hydrochloric acid under 90~150 DEG C for the treatment of temperature, obtains carbon nanotube after purification.The present invention greatly reduces the heating temperature in existing purification process, meets the requirement that energy consumption in industrialized production is lower, more energy efficient, operation is safer by setting 90~150 DEG C for treatment temperature；Industrial mass production is also achieved simultaneously, processing capacity is at least up to several hundred kilograms, and yield is 85% or more；This method is to more targeted as the carbon nanotube of major impurity using nickel magnesium, and more effective to the removal of nickel magnesium addition, purification efficiency is higher.
Description
Technical field
The present invention relates to a kind of methods of purifying carbon nano-tube, relate more specifically to one kind and receive by using low-temperature treatment carbon
Mitron remains in the method for metal impurities in carbon nanotube to remove.
Background technique
Carbon nanotube has excellent conductive, thermally conductive and mechanical performance, can be used as high-performance additives applied to electrode material
In the products such as material, coating, composite material.The preparation process of carbon nanotube mainly has graphite acr method, chemical vapor deposition at present
Method, laser evaporization method, electrolysis method etc., industry in commonly use chemical vapour deposition technique to produce carbon nanotube.Due to chemical vapor deposition
Area method uses transition-metal catalyst when preparing carbon nanotube, causes miscellaneous containing a large amount of metal in prepared carbon nanotube
The impurity such as matter, such as iron, nickel, cobalt, aluminium, tenor is higher to may cause self-discharge of battery, internal micro-short circuit, and there are certain
Security risk.Therefore, it is necessary to provide a kind of efficient and convenient purifying process to overcome the above problem.
Since the property of carbon nanotube obtained by different preparation methods and introduced impurity are different from, it increase accordingly
The difficulty of Purification of Carbon Nanotubes research.For the purification process of the carbon nanotube proposed at present there are many kind, these methods are big
Cause can be divided into physical method, chemical method and synthesis.Physical method is mainly according to carbon nanotube and impurity physical property (such as grain
Degree, shape, specific gravity, electrical property etc.) difference and separated；Chemical method mainly according to carbon nanotube with it is other carbon containing miscellaneous
The chemical stability of matter is different, using oxidant to the oxidation rate of the impurity such as carbon nanotube and carbon nanoparticle, amorphous carbon
It is different and gradually separate；Comprehensive rule is that the two is used in combination with according to physical method and chemical method respective advantage and disadvantage
A kind of method.
Currently used is to combine acid processing with gaseous oxidation, and wherein Hou etc. is synthesized for drift catalyst CVD method
MWNTs propose a kind of purification process of efficient multistep: impregnated in 90 DEG C of bromine water after ultrasonic vibration and dirt count
Then residue is calcined 45min at 520 DEG C, gained black product is put at room temperature in the hydrochloric acid of 5mol/L by 3h
Except Fe particle, and gained sample is washed with deionized.12h is toasted at 150 DEG C in an oven again, and last gained MWNTs's is pure
Degree > 94%, yield is up to 50%.Yield obtained by the purification process mainly determined by oxidization time and temperature (document P X Hou,
SBai, QHYangetal.Carbon, 2002,40:81~85).
A kind of purification method of carbon nanometer pipe is disclosed in CN106794991A comprising: in vacuum or atmosphere of inert gases
In, react the kish in carbon nanotube with chlorine-containing compound, to make the kish chlorine
The step of change；And under the second temperature for being higher than first temperature, the step of evaporating and remove the kish of chlorination；Its
In, the first temperature is selected from 700~1000 DEG C, and second temperature is selected from 800~1500 DEG C；The purification process eliminates carbon nanotube
The denaturation of physical injury and shape.
Although the above method realizes effective purifying to carbon nanotube, and can to impurity removal rate with higher,
However, it there is problems: (1) heating temperature is excessively high, operate at this temperature there is very big risk, energy consumption and at
This is also high, is not suitable for industrialized mass production；(2) although the purification efficiency to carbon nanotube is high, energy is handled
Power is limited, cannot achieve hundred kilograms or more for the treatment of scale, while yield is relatively low, is only capable of reaching 80~85% or so；(3) to carbon
The purifying object of nanotube is lack of pertinence, especially for using nickel magnesium as the carbon nanotube of major impurity.
Therefore, a kind of pair of Purification of Carbon Nanotubes object how is provided more targetedly and to be widely used in industrialization big
The purification method of carbon nanometer pipe of batch production has become current urgent problem to be solved.
Summary of the invention
In view of problems of the prior art, one of the objects of the present invention is to provide a kind of sides of purifying carbon nano-tube
Method, the purification process are a kind of methods of purifying carbon nano-tube suitable for industrial mass production.
Due to that when temperature is risen to 700 DEG C or more or even 1500 DEG C, will have in industrial mass production
Biggish risk operates inconvenient；But also cost and energy consumption greatly improve；Meanwhile having at present up to
99% or more purifying rate, impurity content control only rest on laboratory level, the carbon of processing in 10ppm the following method majority
Nanotube quality only reaches within tens grams, is unable to satisfy industrialized mass production completely, meanwhile, such method there is also
The lower problem of yield, therefore, even if having many purification process for being able to achieve high-purity rate, low impurity content at present, still without
Method realizes the industrial carbon nanotube for producing purifying in enormous quantities.
And the present invention is then proposed in view of the above technical problems, purification process provided by the invention is widely portable to
Large batch of industrialized production, processing capacity is at least up to several hundred jin or more, and improves yield, can reach 85% or more；
Due to significantly reducing the treatment temperature in existing purification process, is controlled at 90~150 DEG C, can farthest be reduced
Operation difficulty, makes to operate safer, and low energy consumption, more energy efficient；Simultaneously can also make the purification efficiency of carbon nanotube be maintained at 97% with
On, impurity content is low, meets the purification requirements of carbon nanotube after purification.
For this purpose, present invention employs following technical solutions:
A kind of method of purifying carbon nano-tube comprising:
Under 90~150 DEG C for the treatment of temperature, first time purifying is first carried out using the aqueous solution of industrial nitric acid, then will purifying
Carbon nanotube afterwards carries out second using the aqueous solution of technical hydrochloric acid and purifies, to obtain carbon nanotube after purification.
The treatment temperature used in the present invention, can be high by cooperation strong acid treatment under the treatment temperature for 90~150 DEG C
Effect removal mixes the transition metal impurity in carbon nanotube, so that the purification efficiency of carbon nanotube can reach 97% or more, with
The purification efficiency under laboratory level remains basically stable in the prior art；And since heating temperature is lower, so that easy to operate, safety
Property it is high, be more suitable for industrialized mass production, and totally small to the damage of carbon nanotube, carbon nanotube after purification is received
Rate is up to 85% or more.
In the present invention, the treatment temperature is 90~150 DEG C, such as can be 90 DEG C, 92 DEG C, 95 DEG C, 100 DEG C, 105
DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C or 150 DEG C.
In the range of preferred process temperature of the present invention is 90~120 DEG C, further preferred 90~100 DEG C.When in should be into
When at the preferred temperature of one step, those skilled in the art can be realized under normal pressure, it is easier to operate, be more advantageous to energy conservation and drop
Low cost.
In the present invention, when treatment temperature be higher than 150 DEG C, when other treatment conditions are identical, carbon nanotube can't be made
Purification efficiency further increase, will increase the damage to carbon nanotube instead；I.e. the present invention be balance purification efficiency and
It avoids in the case where being damaged to carbon nanotube, the selection to the optimization that treatment temperature is made, is exactly that treatment temperature control exists
In the range of 90~150 DEG C.
In the present invention, the carbon nanotube is selected from using nickel magnesium as the carbon nanotube of major impurity, using cobalt aluminium as major impurity
Carbon nanotube or using iron nickel aluminium as in the carbon nanotube of major impurity any one or at least two mixture, wherein allusion quotation
Type but unrestricted mixture are as follows: using nickel magnesium as the carbon nanotube of major impurity and using cobalt aluminium as the carbon nanometer of major impurity
Pipe；Using cobalt aluminium as the carbon nanotube of major impurity and using iron nickel aluminium as the carbon nanotube of major impurity；Using nickel magnesium as major impurity
Carbon nanotube and using iron nickel aluminium as the carbon nanotube of major impurity.
The present invention is preferably using nickel magnesium as the carbon nanotube of major impurity.Using purification process of the invention, it is to nickel magnesium
Nickel and magnesium addition removal in carbon nanotube made from the catalyst of major metal is more targeted, and nickel impurity content can be by handling
Preceding 2~30,000 ppm are down to 500ppm or lower, and content of magnesium can be down to 200ppm hereinafter, making by 0.8 before handling~10,000 ppm
Carbon amounts is improved to 97.2% or more.
Preferably, the concentration of industrial nitric acid employed in the present invention is 60%~65%.
Preferably, the concentration of the technical hydrochloric acid is 30%~35%.
The aqueous solution of industrial nitric acid in the present invention, the preferably final concentration of nitric acid are controlled 10%~65%；The present invention is logical
It crosses using the concentrated nitric acid after dilution, also reduces cost and energy consumption to a certain extent, while operation can also be made safer, and
And do not have an adverse effect to purification efficiency.
The present invention uses the nitric acid solution of the concentration under 90~150 DEG C for the treatment of temperature, can targetedly remove
Most of nickel and magnesium addition, especially nickel impurity in carbon nanotube.
The aqueous solution of technical hydrochloric acid in the present invention, the preferably final concentration of hydrochloric acid are controlled 10%~35%；By using
HCl treatment can further remove nickel and magnesium addition in carbon nanotube, meanwhile, for remaining other impurity, such as iron,
Aluminium, zinc etc. can control within critical field, carbon amounts made to reach 97% or more.
In the purification process of the invention, the either aqueous solution of the aqueous solution of industrial nitric acid or technical hydrochloric acid, in addition to
It needs to control outside its concentration, the time of reaction is also an important factor for influencing final carbon nano pipe purity and quality.
Preferably, use industrial nitric acid aqueous solution carry out first time purifying time for 5~20h, such as 5h, 6h, 8h,
10h, 12h, 15h, 18h, 19h or 20h, preferably 12~18h；It, can be to carbon nanotube knot when being higher than the range between when treated
It is configured to certain destruction, and is helpless to improve the impurity-eliminating effect of carbon nanotube；And when treated between be lower than the range when,
It is inadequate to the removal dynamics of the impurity in carbon nanotube, especially nickel, therefore, it will only control within the above range the processing time
When, it can just take into account that carbon nano tube structure is complete and the removal effect of impurity.
Preferably, the aqueous solution of technical hydrochloric acid is used to carry out time of second purifying as 5~20h, for example, 5h, 6h, 8h,
10h, 12h, 15h, 18h, 19h or 20h, preferably 12~18h.In the processing time range, can effectively it realize to iron, aluminium, zinc
The removal of equal impurity.
In the present invention, in the aqueous solution using industrial nitric acid before 90~150 DEG C of Temperature Treatment further include: by carbon nanometer
Pipe dissolves in the aqueous solution of industrial nitric acid, is sufficiently stirred, and 1~6h, preferably 2~5h are reacted under room temperature.
By first dissolving in carbon nanotube in the aqueous solution of industrial nitric acid, through being sufficiently stirred, 1~6h is reacted under room temperature, is made
The impurity obtained in carbon nanotube is fully dissolved in nitric acid solution, to further increase the removal efficiency to impurity.
Preferably, in the aqueous solution using industrial nitric acid after 90~150 DEG C of Temperature Treatment, and in the water of technical hydrochloric acid
Before solution processing, further includes: by the aqueous solution of industrial nitric acid, treated that solution is washed to neutrality and filters.The processing can wash
Unreacted nitric acid ingredient is removed, to make system be more conducive to subsequent HCl treatment, but also carbon nano pipe purity after purification
It is higher.
When being washed, it is preferred to use warm water, further preferred 20 DEG C or more of warm water, such as can be 20 DEG C, 22
DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 60 DEG C or 80 DEG C etc., temperature is higher, is more conducive to the removal of impurity.
Likewise, in the aqueous solution using technical hydrochloric acid after 90~150 DEG C of Temperature Treatment, further includes: after processing
Solution be washed to neutrality and filter；The washing is also, it is preferred that using warm water, and preferably 20 DEG C or more of the warm water.
In the present invention, mass ratio and carbon by advanced optimizing carbon nanotube crude samples and industrial nitric acid and water are received
The mass ratio of mitron crude samples and technical hydrochloric acid and water can make purification efficiency be further improved.Wherein, the first time
When purifying, carbon nanotube is 1:(5~10 with the mass ratio of industrial nitric acid and water): (10-12), such as can be 1:5:10,1:
6:11,1:7:12,1:9:10, preferably 1:(6~9): 11.
Preferably, when second of purifying, carbon nanotube is 1:(7~12 with the mass ratio of technical hydrochloric acid and water): (10-
12) 1:8:10,1:9:11,1:10:12,1:12:10, preferably 1:(8~11 be can be, such as): 11.
As a preferred solution of the present invention, the purifying carbon nano-tube method the following steps are included:
(1) carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, under 90~150 DEG C for the treatment of temperature
Carry out first time purifying；The mass ratio of the carbon nanotube and industrial nitric acid and water is 1:(5~10): (10-12)；The purifying
Time is 5~20h；
(2) after carbon nanotube for the first time after purification being washed to neutral and filtering, existed using the aqueous solution of technical hydrochloric acid
It carries out purifying for second under 90~150 DEG C for the treatment of temperature；The mass ratio of the carbon nanotube and technical hydrochloric acid and water is 1:(7
~12): (10-12)；The purification time is 5~20h；
(3) it after carbon nanotube for the second time after purification being washed to neutral and filtering, dries, obtains at 80~200 DEG C
Obtain carbon nanotube after purification.
The second object of the present invention is the provision of the carbon nanometer after purification prepared by method described in the first purpose
Pipe.
In the carbon nanotube after purification, carbon amounts is 97% or more, wherein the amount of nickel impurity is for 500ppm or more
Low, the amount of magnesium addition is 200ppm or lower.
Compared with prior art, the present invention is at least had the advantages that
(1) present invention significantly reduces the processing in existing purification process by controlling treatment temperature at 90~150 DEG C
Temperature can farthest reduce operation difficulty, make to operate safer, and low energy consumption, more energy efficient, the purification efficiency of carbon nanotube
It can reach 97% or more, impurity content is low；
(2) purification process provided by the invention is widely portable to large batch of industrialized production, and processing capacity is at least
Reach several hundred jin or more, yield can reach 85% or more；
(3) purification method of carbon nanometer pipe of the present invention is more targeted, using nickel magnesium as the carbon of major impurity
When nanotube is as purifying object, enabling to the amount of nickel impurity is 500ppm or lower, and the amount of magnesium addition is
200ppm or lower, while other impurity can be made, such as iron, aluminium, zinc etc., same control is in reduced levels.
Detailed description of the invention
Fig. 1 is the SEM figure of the carbon nanotube of the embodiment of the present invention 1 after purification.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Initial impurity content in the sample used in following embodiment and the sample is respectively as follows:
Sample one is as using nickel magnesium as multi-walled carbon nanotube made from the catalyst of major metal, sample two is to be with cobalt aluminium
Multi-walled carbon nanotube made from the catalyst of major metal, sample three are using iron nickel aluminium to be more made from the catalyst of major metal
The initial impurity content of wall carbon nano tube, each sample is as shown in table 1.
Table 1
| Fe/ppm | Ni/ppm | Al/ppm | Mg/ppm | Co/ppm | Carbon amounts | |
| Sample one | 134.47 | 15289 | 25.31 | 5058 | 14.36 | 85.32% |
| Sample two | 156.5 | 18.31 | 2284 | 2.88 | 5765 | 97.35% |
| Sample three | 4580 | 1589 | 1273 | 6.32 | 5.62 | 97.44% |
Embodiment 1
A method of purifying multi-walled carbon nanotube as made from nickel magnesium alloy catalyst comprising following steps:
(1) carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, carried out under 100 DEG C for the treatment of temperature
It purifies for the first time；The mass ratio of the carbon nanotube and industrial nitric acid and water is 1:7:11；The purification time is 15h；
(2) after carbon nanotube for the first time after purification being washed to neutral and filtering, existed using the aqueous solution of technical hydrochloric acid
It carries out purifying for second under 100 DEG C for the treatment of temperature；The mass ratio of the carbon nanotube and technical hydrochloric acid and water is 1:9:11；Institute
Stating purification time is 15h；
(3) after carbon nanotube for the second time after purification being washed to neutral and filtering, 10h is dried at 150 DEG C, is obtained
Carbon nanotube after purification.
Carbon nanotube after purification as shown in Figure 1, as can be seen from this figure by the damage very little of carbon nanotube after purification,
The basic characteristic for keeping script.
Embodiment 2
A method of purifying multi-walled carbon nanotube as made from cobalt aluminium alloy catalyst comprising following steps:
(1) carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, is carried out under 95 DEG C for the treatment of temperature
Primary purifying；The mass ratio of the carbon nanotube and industrial nitric acid and water is 1:8:10；The purification time is 12h；
(2) after carbon nanotube for the first time after purification being washed to neutral and filtering, existed using the aqueous solution of technical hydrochloric acid
It carries out purifying for second under 100 DEG C for the treatment of temperature；The mass ratio of the carbon nanotube and technical hydrochloric acid and water is 1:10:11；
The purification time is 12h；
(3) after carbon nanotube for the second time after purification being washed to neutral and filtering, 10h is dried at 150 DEG C, is obtained
Carbon nanotube after purification.
Carbon nanotube through the above method after purification maintains the characteristic of its script substantially, damages very little.
Embodiment 3
A method of purifying multi-walled carbon nanotube as made from calite catalyst comprising following steps:
(1) carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, carried out under 150 DEG C for the treatment of temperature
It purifies for the first time；The mass ratio of the carbon nanotube and industrial nitric acid and water is 1:10:12；The purification time is 20h；
(2) after carbon nanotube for the first time after purification being washed to neutral and filtering, existed using the aqueous solution of technical hydrochloric acid
It carries out purifying for second under 90 DEG C for the treatment of temperature；The mass ratio of the carbon nanotube and technical hydrochloric acid and water is 1:12:12；Institute
Stating purification time is 10h；
(3) after carbon nanotube for the second time after purification being washed to neutral and filtering, 10h is dried at 100 DEG C, is obtained
Carbon nanotube after purification.
Carbon nanotube through the above method after purification maintains the characteristic of its script substantially, damages very little.
Embodiment 4
A method of purifying multi-walled carbon nanotube carbon nanotube as made from nickel magnesium alloy catalyst comprising following step
It is rapid:
(1) carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, is carried out under 92 DEG C for the treatment of temperature
Primary purifying；The mass ratio of the carbon nanotube and industrial nitric acid and water is 1:5:10；The purification time is 16h；
(2) after carbon nanotube for the first time after purification being washed to neutral and filtering, existed using the aqueous solution of technical hydrochloric acid
It carries out purifying for second under 145 DEG C for the treatment of temperature；The mass ratio of the carbon nanotube and technical hydrochloric acid and water is 1:10:11；
The purification time is 12h；
(3) after carbon nanotube for the second time after purification being washed to neutral and filtering, 10h is dried at 120 DEG C, is obtained
Carbon nanotube after purification.
Carbon nanotube through the above method after purification maintains the characteristic of its script substantially, damages very little.
Comparative example 1
Compared with Example 1, the processing sequence of industrial nitric acid and technical hydrochloric acid is adjusted to first to carry out the water of technical hydrochloric acid
The purifying of solution, then the purifying of the aqueous solution of industrial nitric acid is carried out, it is other same as Example 1.
Comparative example 2
Compared with Example 1, the processing of industrial nitric acid and technical hydrochloric acid is adjusted to the aqueous solution only with industrial nitric acid
Purifying, omit the processing of technical hydrochloric acid, it is other same as Example 1.
Comparative example 3
Compared with Example 1, the processing of industrial nitric acid and technical hydrochloric acid is adjusted to the aqueous solution only with technical hydrochloric acid
Purifying, omit the processing of industrial nitric acid, it is other same as Example 1.
Comparative example 4
Compared with Example 1, except the treatment temperature of industrial nitric acid and aqueous hydrochloric acid solution is adjusted to 80 DEG C, it is other with it is real
It is identical to apply example 1.
Following table 2 is purified carbon nanotube impurity situation and carbon amounts feelings in Examples 1 to 4 and comparative example 1~4
Condition.
Table 2
| Fe/ppm | Ni/ppm | Al/ppm | Mg/ppm | Co/ppm | Carbon amounts/% | |
| Embodiment 1 | 10.64 | 329.74 | 4.91 | 126.40 | 4.43 | 98.37 |
| Embodiment 2 | 32.27 | 378.51 | 146.87 | 2.64 | 684.04 | 98.82 |
| Embodiment 3 | 454.87 | 302.68 | 107.62 | 5.57 | 4.88 | 98.23 |
| Embodiment 4 | 68.65 | 483.46 | 13.54 | 183.25 | 7.92 | 97.43 |
| Comparative example 1 | 77.32 | 858.43 | 18.43 | 395.26 | 13.54 | 96.87 |
| Comparative example 2 | 81.32 | 876.49 | 17.34 | 584.39 | 10.28 | 96.53 |
| Comparative example 3 | 75.32 | 1073.32 | 18.98 | 672.47 | 15.83 | 95.78 |
| Comparative example 4 | 105.32 | 1533.52 | 23.21 | 854.42 | 16.54 | 95.16 |
It can be seen that in the present invention by the result of table 2 by reducing treatment temperature, purification efficiency (carbon amounts) can be made to reach
97% or more, while also there is up to 85% or more yield；Also, it is directed in the present invention and is received by the carbon of major impurity of nickel magnesium
Mitron, using cobalt aluminium as the carbon nanotube of major impurity and using iron nickel aluminium as the carbon nanotube of major impurity, be able to achieve and effectively remove
Miscellaneous, especially for using nickel magnesium as the carbon nanotube of major impurity, the amount of nickel is 500ppm or more in the product of purifying
Low, the amount of magnesium is 200ppm or lower, therefore more targeted to such carbon nanotube.
The Applicant declares that the present invention is explained by the above embodiments detailed construction feature of the invention, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention must rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And increase, selection of concrete mode of accessory etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of method of purifying carbon nano-tube characterized by comprising
Under 90~150 DEG C for the treatment of temperature, first time purifying is first carried out using the aqueous solution of industrial nitric acid, then will after purification
Carbon nanotube carries out second using the aqueous solution of technical hydrochloric acid and purifies, to obtain carbon nanotube after purification.
2. the method as described in claim 1, which is characterized in that the carbon nanotube is selected from and receives by the carbon of major impurity of nickel magnesium
Mitron, using cobalt aluminium as the carbon nanotube of major impurity or using iron nickel aluminium as any one in the carbon nanotube of major impurity or extremely
Few two kinds of mixture, preferably using nickel magnesium as the carbon nanotube of major impurity；
Preferably, when the metal remained in the carbon nanotube after purification is nickel, the amount of nickel is for 500ppm or more
It is low；When the metal remained in the carbon nanotube after purification is magnesium, the amount of magnesium is 200ppm or lower.
3. method according to claim 1 or 2, which is characterized in that the treatment temperature is excellent in the range of 90~120 DEG C
Select 90~100 DEG C.
4. the method as described in one of claim 1-3, which is characterized in that the concentration of the industrial nitric acid is 60%~65%；
Preferably, the concentration of the technical hydrochloric acid is 30%~35%；
Preferably, the time of the first time purifying is 5~20h, preferably 12~18h；
Preferably, the time of second of purifying is 5~20h, preferably 12~18h.
5. the method as described in one of claim 1-4, which is characterized in that in the aqueous solution using industrial nitric acid in 90~150
DEG C Temperature Treatment before further include: carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, under room temperature react 1~
6h, preferably 2~5h；
Preferably, in the aqueous solution using industrial nitric acid after 90~150 DEG C of Temperature Treatment, and in the aqueous solution of technical hydrochloric acid
Before processing, further includes: by the aqueous solution of industrial nitric acid, treated that solution is washed to neutrality and filters；
Preferably, described wash uses warm water, and preferably 20 DEG C or more of the warm water.
6. the method as described in one of claim 1-5, which is characterized in that in the aqueous solution using technical hydrochloric acid in 90~150
DEG C Temperature Treatment after, further includes: will treated that solution is washed to neutrality and filters；
Preferably, described wash uses warm water, and preferably 20 DEG C or more of the warm water.
7. the method as described in one of claim 1-6, which is characterized in that when the first time purifies, carbon nanotube and industry
The mass ratio of nitric acid and water is 1:(5~10): (10-12), preferably 1:(6~9): 11；
Preferably, when second of purifying, carbon nanotube is 1:(7~12 with the mass ratio of technical hydrochloric acid and water): (10-12), it is excellent
Select 1:(8~10): 11.
8. the method as described in one of claim 1-7, which is characterized in that the described method comprises the following steps:
(1) carbon nanotube is dissolved in the aqueous solution of industrial nitric acid, is sufficiently stirred, carried out under 90~150 DEG C for the treatment of temperature
It purifies for the first time；The mass ratio of the carbon nanotube and industrial nitric acid and water is 1:(5~10): (10-12)；The purification time
For 5~20h；
(2) carbon nanotube for the first time after purification is washed to it is neutral and after filtering, using the aqueous solution of technical hydrochloric acid 90~
It carries out purifying for second under 150 DEG C for the treatment of temperature；The mass ratio of the carbon nanotube and technical hydrochloric acid and water be 1:(7~
12):(10-12)；The purification time is 5~20h；
(3) it after carbon nanotube for the second time after purification being washed to neutral and filtering, dries, obtains pure at 80~200 DEG C
Carbon nanotube after change.
9. passing through the carbon nanotube after purification of method preparation described in one of claim 1-8.
10. carbon nanotube after purification as claimed in claim 9, which is characterized in that nickel in the carbon nanotube after purification
Amount be 500ppm or lower；
Preferably, the amount of magnesium is 200ppm or lower in the carbon nanotube after purification.
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| CN201910079342.XA CN109626359A (en) | 2019-01-28 | 2019-01-28 | A kind of method of purifying carbon nano-tube and by its carbon nanotube after purification |
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| CN113860289B (en) * | 2021-10-21 | 2023-07-07 | 江苏天奈科技股份有限公司 | Method for purifying carbon nano tube |
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