CN116395675A - Pickling and purifying method for carbon nano tube - Google Patents
Pickling and purifying method for carbon nano tube Download PDFInfo
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- CN116395675A CN116395675A CN202310334351.5A CN202310334351A CN116395675A CN 116395675 A CN116395675 A CN 116395675A CN 202310334351 A CN202310334351 A CN 202310334351A CN 116395675 A CN116395675 A CN 116395675A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 114
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005554 pickling Methods 0.000 title claims description 17
- 239000002253 acid Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 238000000746 purification Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 238000005406 washing Methods 0.000 claims abstract description 26
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 15
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- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 9
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 9
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 6
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- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
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- -1 polyoxyethylene propylene glycol Polymers 0.000 claims description 4
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 3
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- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
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- 229910052742 iron Inorganic materials 0.000 description 12
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- C01B2202/34—Length
-
- 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
- C01B2202/36—Diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an acid washing purification method of a carbon nano tube, belonging to the technical field of carbon nano tube purification. Mixing carbon nano tubes to be purified, an acid-resistant water-soluble dispersing agent and water, and carrying out modification treatment to obtain modified carbon nano tube feed liquid; mixing the modified carbon nanotube feed liquid with acid liquid, and purifying to obtain purified carbon nanotube feed liquid; and (3) carrying out solid-liquid separation on the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying to obtain the purified carbon nanotube. According to the invention, the acid-resistant water-soluble dispersing agent is introduced in the acid washing purification process, so that the soaking effect of the acid liquor on the carbon nano tube can be improved, the acid liquor is fully contacted with impurity particles, meanwhile, the transition metal impurities in the carbon nano tube are complexed, the solubility of transition metal ions in the acid liquor is increased, the acid washing times are reduced, the treatment period is shortened, the acid liquor use amount and the water use amount are reduced, and the production cost is obviously reduced.
Description
Technical Field
The invention relates to the technical field of carbon nanotube purification, in particular to an acid washing purification method of carbon nanotubes.
Background
Carbon nanotubes are one type of tubular one-dimensional nanomaterial that is typically produced by catalytic pyrolysis deposition of carbon-containing compounds, particularly hydrocarbons, using a transition metal catalyst. During catalytic pyrolysis deposition, the transition metal catalyst may remain in the carbon nanotube meal. In some applications where purity is high, such as in the field of power cells, it is desirable that the content of transition metal impurities remaining in the carbon nanotubes be low, and therefore further purification of the carbon nanotube meal is required.
Currently, the main purification methods include two main types, namely a chemical purification method and a physical purification method. The chemical purification method, such as the acid washing method, has the special advantages in the aspect of removing the transition metal impurities, such as simple reaction process, is generally limited to the change of surface interfaces, is not easy to form integral structure defects, and can control the residual transition metal impurities in the carbon nano tube coarse powder within 500 ppm. However, the carbon nanotubes are treated by adopting the traditional acid washing method, so that more acid liquor, longer treatment time (more than 15 hours) and heating (80-90 ℃) are usually required to achieve better treatment effect, and the production cost is higher. And a large amount of deionized water is needed to wash out impurity ions after the treatment of a large amount of acid liquor, and the carbon nano tube powder is washed to be neutral, so that a large amount of acid washing liquor is generated, and further the production cost and the environmental protection cost are greatly increased.
Disclosure of Invention
The invention aims to provide a pickling purification method for carbon nanotubes, which has good pickling purification effect and low cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a pickling and purifying method of a carbon nano tube, which comprises the following steps:
(1) Mixing the carbon nano tube to be purified, an acid-resistant water-soluble dispersing agent and water, and carrying out modification treatment to obtain a modified carbon nano tube feed liquid;
(2) Mixing the modified carbon nanotube feed liquid with acid liquid, and purifying to obtain purified carbon nanotube feed liquid;
(3) And (3) carrying out solid-liquid separation on the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying to obtain the purified carbon nanotube.
Preferably, the length of the carbon nano tube to be purified in the step (1) is 10-200 μm, and the outer diameter is 1-100 nm; the agglomerate size of the carbon nano tube to be purified is 1-2000 mu m.
Preferably, the acid-resistant water-soluble dispersing agent in the step (1) comprises one or more of polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethylidene diphosphonic acid, a cellulose compound and a compound containing polyoxyethylene ether functional groups.
Preferably, the cellulose compound in the step (1) comprises hydroxyethyl cellulose and/or hydroxypropyl methylcellulose.
Preferably, the polyoxyethylene ether functional group-containing compound includes C 8-10 One or more of glyceride polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dodecylphenol polyoxyethylene ether and polyoxypropylene polyoxyethylene propylene glycol ether.
Preferably, the mass ratio of the acid-resistant water-soluble dispersing agent to water in the step (1) is (5-35): 100.
preferably, the mass ratio of the carbon nanotubes to be purified in the step (1) to the total mass ratio of the acid-resistant water-soluble dispersant and water is (10 to 50): 100.
preferably, the temperature of the modification treatment in the step (1) is 50-60 ℃ and the time is 30-90 min; the modification treatment is carried out under stirring conditions.
Preferably, the acid liquid in the step (2) is hydrochloric acid, and the concentration of the hydrochloric acid is 36-38 wt%; the mass ratio of the hydrochloric acid to the modified carbon nanotube feed liquid is 1: (4-30).
Preferably, the purification treatment in the step (2) is carried out at a temperature of 50-60 ℃ for 2-4 hours; the purification treatment is carried out under stirring.
The invention provides a pickling and purifying method of a carbon nano tube, which comprises the following steps: mixing the carbon nano tube to be purified, an acid-resistant water-soluble dispersing agent and water, and carrying out modification treatment to obtain a modified carbon nano tube feed liquid; mixing the modified carbon nanotube feed liquid with acid liquid, and purifying to obtain purified carbon nanotube feed liquid; and (3) carrying out solid-liquid separation on the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying to obtain the purified carbon nanotube. According to the invention, the acid-resistant water-soluble dispersing agent is introduced in the acid washing purification process, so that the soaking effect of the acid liquor on the carbon nano tube can be improved, the acid liquor is fully contacted with impurity particles, meanwhile, the transition metal impurities in the carbon nano tube are complexed, the solubility of transition metal ions in the acid liquor is increased, the acid washing times are reduced, the treatment period is shortened, the acid liquor use amount and the water use amount are reduced, and the production cost is obviously reduced. The results of the examples show that the time for pickling and purifying the carbon nano tube to be purified can be shortened to be less than 8 hours by adopting the method provided by the invention, the main iron impurities can be reduced from 500ppm to be less than 210ppm by carrying out one-time pickling and purifying (namely carrying out one-time modifying treatment and one-time purifying treatment), and the cobalt impurities can be reduced from 105ppm to be less than 41ppm by carrying out one-time pickling and purifying, so that the water consumption is reduced.
Drawings
Fig. 1 is a flow chart of acid washing purification of carbon nanotubes according to the present invention.
Detailed Description
The invention provides a pickling and purifying method of a carbon nano tube, which comprises the following steps:
(1) Mixing the carbon nano tube to be purified, an acid-resistant water-soluble dispersing agent and water, and carrying out modification treatment to obtain a modified carbon nano tube feed liquid;
(2) Mixing the modified carbon nanotube feed liquid with acid liquid, and purifying to obtain purified carbon nanotube feed liquid;
(3) And (3) carrying out solid-liquid separation on the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying to obtain the purified carbon nanotube.
Fig. 1 is a flow chart of the pickling and purifying process of the carbon nanotubes according to the present invention, and the following describes the pickling and purifying process of the carbon nanotubes according to the present invention in detail with reference to fig. 1.
The invention mixes the carbon nano tube to be purified, the acid-resistant water-soluble dispersing agent and water, and carries out modification treatment to obtain modified carbon nano tube feed liquid. In the present invention, the carbon nanotubes to be purified are preferably carbon nanotube coarse powder (i.e., unrefined carbon nanotube coarse powder) prepared by catalytic pyrolysis deposition of carbon-containing compounds using a transition metal catalyst, and the transition metal catalyst remains in the carbon nanotubes to be purified. In the present invention, the main impurities of the carbon nanotubes to be purified comprise iron and cobalt, the content of iron is preferably 3000-3500 ppm, and the content of cobalt is preferably 700850ppm. In the present invention, the length of the carbon nanotube to be purified is preferably 10 to 200. Mu.m, more preferably 10 to 50. Mu.m, still more preferably 10 to 30. Mu.m; the outer diameter is preferably 1 to 100nm, more preferably 5 to 40nm, still more preferably 5 to 30nm; the agglomerate size of the carbon nanotubes to be purified is preferably 1 to 2000. Mu.m, more preferably 1 to 1000. Mu.m, still more preferably 1 to 100. Mu.m, still more preferably 10 to 100. Mu.m; in the invention, the carbon nano tube coarse powder prepared by utilizing the transition metal catalyst to catalytically crack and deposit the carbon-containing compound usually exists in a form of aggregates, and the size of the aggregates of the carbon nano tube to be purified is specifically the size of the aggregates formed by the carbon nano tube coarse powder. In the present invention, the water is preferably deionized water. In the present invention, the acid-resistant water-soluble dispersant preferably includes one or more of polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethylidene diphosphonic acid (HEDP), a cellulose-based compound, and a compound containing a polyoxyethylene ether functional group; the cellulose-based compound preferably comprises hydroxyethyl cellulose (HEC) and/or hydroxypropyl methylcellulose (HPMC), and the polyoxyethylene ether functional group-containing compound preferably comprises C 8-10 One or more of glyceride polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dodecylphenol polyoxyethylene ether and polyoxypropylene polyoxyethylene propylene glycol ether. The acid-resistant water-soluble dispersing agent of the type is preferably adopted, so that the wettability of the acid liquor to the carbon nano tube can be increased, meanwhile, transition metal impurities in the carbon nano tube are complexed, the solubility of transition metal ions in the acid liquor is increased, and further the acid-washing purification effect is improved; and the acid-resistant water-soluble dispersing agent of the type can be removed by subsequent water washing, and no new impurities are introduced.
In the present invention, the mixing mode of the carbon nanotube to be purified, the acid-resistant water-soluble dispersant and water preferably comprises: dissolving an acid-resistant water-soluble dispersing agent in water to obtain an acid-resistant water-soluble dispersing agent water solution; mixing the acid-resistant water-soluble dispersant aqueous solution with the carbon nanotubes to be purified. In the invention, the mass ratio of the acid-resistant water-soluble dispersant to water is preferably (5-35): 100, more preferably (10 to 30): 100, more preferably (20 to 30): 100; the mass ratio of the carbon nano tube to be purified to the total mass ratio of the acid-resistant water-soluble dispersant aqueous solution is preferably (10-50): 100, more preferably (15 to 40): 100. the acid-resistant water-soluble dispersing agent is preferably mixed with water, and the acid-resistant water-soluble dispersing agent is fully dissolved in the water under the conditions of heating and stirring; the rotation speed of the stirring is preferably 100-120 r/min, more preferably 110-120 r/min; the heating temperature is preferably 50 to 60 ℃, more preferably 55 to 60 ℃; the stirring and heating time is based on the complete dissolution of the acid-resistant water-soluble dispersant in water.
In the present invention, the temperature of the modification treatment is preferably 50 to 60 ℃, more preferably 55 to 60 ℃; the time is preferably 30 to 90 minutes, more preferably 30 to 60 minutes; the modification treatment is preferably performed under stirring conditions, and the stirring speed is preferably 60 to 120r/min, more preferably 80 to 120r/min. In the modification treatment process, the surface of the carbon nano tube to be purified is fully soaked by the acid-resistant water-soluble dispersing agent aqueous solution.
In the invention, after the modification treatment, the obtained modified carbon nanotube feed liquid is directly mixed with acid liquor without any post-treatment, and the purification treatment is carried out to obtain the purified carbon nanotube feed liquid. In the invention, the acid liquid is preferably hydrochloric acid, the concentration of the hydrochloric acid is preferably 36-38 wt%, and the mass ratio of the hydrochloric acid to the modified carbon nanotube feed liquid is preferably 1: (4 to 30), more preferably 1: (4.5 to 20), more preferably 1: (5-10). In the present invention, the temperature of the purification treatment is preferably 50 to 60 ℃, more preferably 55 to 60 ℃; the time is preferably 2 to 4 hours, more preferably 2 to 3 hours; the purification treatment is preferably carried out under stirring conditions, and the stirring speed is preferably 60 to 120r/min, more preferably 80 to 120r/min.
In the invention, the process of modifying and purifying the carbon nano tube to be purified is preferably carried out in a Teflon reaction kettle with a heating water jacket and a stirring device, wherein the stirring device comprises a stirring paddle and a stirring shaft, and the surfaces of the stirring paddle and the stirring shaft are coated with Teflon.
After the purified carbon nanotube feed liquid is obtained, the purified carbon nanotube feed liquid is subjected to solid-liquid separation, and the obtained solid material is washed to be neutral and then dried, so that the purified carbon nanotube is obtained. The solid-liquid separation method is not particularly limited, and may be performed by any method known to those skilled in the art, such as filtration. In the invention, the washing liquid used for washing is preferably deionized water; the drying is preferably carried out in a continuous mesh belt furnace with a graphite lining.
The method provided by the invention is used for carrying out acid cleaning purification on the carbon nano tube, the main iron impurities can be reduced from 500ppm to less than 210ppm through one-time acid cleaning purification (namely, one-time modification treatment and one-time purification treatment), and the cobalt impurities can be reduced from 105ppm to less than 41ppm through one-time acid cleaning purification, so that the purification effect is good. In order to improve the acid washing purification effect so as to be suitable for certain application fields with higher purity requirements, the invention preferably repeatedly carries out the modification treatment and the purification treatment for 2-6 times, specifically, the solid material obtained after each solid-liquid separation is taken as a raw material, the modification treatment and the purification treatment are carried out again, after the last solid-liquid separation, the obtained solid material is washed to be neutral, and then is dried, so that the purified carbon nano tube is obtained.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In the embodiment, the carbon nano tube to be purified is carbon nano tube coarse powder which is not purified, wherein the iron content of main impurities of the carbon nano tube to be purified is 3000ppm, and the cobalt content is 708ppm; the length of the carbon nano tube to be purified is 10-30 mu m, the outer diameter is 5-30 nm, and the agglomerate size is 1-100 mu m.
The mass ratio of polyvinylpyrrolidone to deionized water is 5:100, placing the two materials into a Teflon reaction kettle with a heating water jacket and a stirring device (the stirring device comprises a stirring paddle and a stirring shaft, the surfaces of the stirring paddle and the stirring shaft are coated with Teflon), and stirring at 55 ℃ and 120r/min to completely dissolve polyvinylpyrrolidone and obtain polyvinylpyrrolidone aqueous solution;
the mass ratio of the polyvinylpyrrolidone aqueous solution to the carbon nano tube to be purified is 100:15, adding the carbon nano tube to be purified into a reaction kettle, and carrying out primary modification treatment for 60min at 55 ℃ and 120r/min to obtain modified carbon nano tube feed liquid;
the mass ratio of the modified carbon nano tube feed liquid to the hydrochloric acid is 4:1, adding hydrochloric acid with the concentration of 38wt% into a reaction kettle, and carrying out primary purification treatment for 3 hours at the temperature of 60 ℃ and under the condition of 120r/min to obtain purified carbon nano tube feed liquid;
and filtering the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying in a continuous mesh belt furnace with a graphite lining to obtain the purified carbon nanotube, wherein the content of iron impurities is 210ppm and the content of cobalt is 41ppm.
Example 2
In the embodiment, the carbon nano tube to be purified is carbon nano tube coarse powder which is not purified, the main impurity iron content of the carbon nano tube to be purified is 3500ppm, and the cobalt content of the carbon nano tube to be purified is 821ppm; the length of the carbon nano tube to be purified is 10-30 mu m, the outer diameter is 5-30 nm, and the agglomerate size is 1-100 mu m.
The mass ratio of the hydroxyethyl cellulose (HEC) to the deionized water is 10:100, placing the two materials into a Teflon reaction kettle with a heating water jacket and a stirring device (the stirring device comprises a stirring paddle and a stirring shaft, the surfaces of the stirring paddle and the stirring shaft are coated with Teflon), and stirring at 60 ℃ under the condition of 120r/min to completely dissolve the hydroxyethyl cellulose to obtain a hydroxyethyl cellulose aqueous solution;
the mass ratio of the hydroxyethyl cellulose aqueous solution to the carbon nano tube to be purified is 100:10, adding the carbon nano tube to be purified into a reaction kettle, and carrying out primary modification treatment for 60min at 60 ℃ and 120r/min to obtain modified carbon nano tube feed liquid;
the mass ratio of the modified carbon nano tube feed liquid to the hydrochloric acid is 5:1, adding hydrochloric acid with the concentration of 38wt% into a reaction kettle, and carrying out primary purification treatment for 4 hours at the temperature of 60 ℃ and under the condition of 120r/min to obtain purified carbon nano tube feed liquid;
and filtering the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying in a continuous mesh belt furnace with a graphite lining to obtain the purified carbon nanotube, wherein the content of iron impurities is 105ppm and the content of cobalt is 18ppm.
Example 3
In the embodiment, the carbon nano tube to be purified is carbon nano tube coarse powder which is not purified, wherein the iron content of main impurities of the carbon nano tube to be purified is 3300ppm, and the cobalt content is 800ppm; the length of the carbon nano tube to be purified is 10-60 mu m, the outer diameter is 5-30 nm, and the agglomerate size is 10-1000 mu m.
The mass ratio of the hydroxyethylidene diphosphonic acid (HEDP) to the deionized water is 30:100, placing the two materials into a Teflon reaction kettle with a heating water jacket and a stirring device (the stirring device comprises a stirring paddle and a stirring shaft, the surfaces of the stirring paddle and the stirring shaft are coated with Teflon), and stirring at 55 ℃ and 120r/min to completely dissolve the hydroxyethylidene diphosphonic acid to obtain an aqueous solution of the hydroxyethylidene diphosphonic acid;
the mass ratio of the hydroxyethylidene diphosphonic acid aqueous solution to the carbon nano tube to be purified is 100:10, adding the carbon nano tube to be purified into a reaction kettle, and carrying out primary modification treatment for 60min at 55 ℃ and 120r/min to obtain modified carbon nano tube feed liquid;
the mass ratio of the modified carbon nano tube feed liquid to the hydrochloric acid is 5:1, adding hydrochloric acid with the concentration of 38wt% into a reaction kettle, and carrying out primary purification treatment for 4 hours at the temperature of 60 ℃ and under the condition of 120r/min to obtain purified carbon nano tube feed liquid;
and filtering the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying in a continuous mesh belt furnace with a graphite lining to obtain the purified carbon nanotube, wherein the content of iron impurities is 50ppm, and the content of cobalt is 4.8ppm.
Comparative example 1
The carbon nano tube to be purified in the comparative example is carbon nano tube coarse powder which is not purified, wherein the iron content of main impurities of the carbon nano tube to be purified is 3000ppm, and the cobalt content is 720ppm; the length of the carbon nano tube to be purified is 10-60 mu m, the outer diameter is 5-30 nm, and the agglomerate size is 10-1000 mu m.
The mass ratio of deionized water to the carbon nano tube to be purified is 100:10, placing the two materials in a Teflon reaction kettle with a heating water jacket and a stirring device (the stirring device comprises a stirring paddle and a stirring shaft, and the surfaces of the stirring paddle and the stirring shaft are coated with Teflon) to obtain carbon nano tube aqueous dispersion;
the mass ratio of the carbon nano tube aqueous dispersion liquid to the hydrochloric acid is 5:1, adding hydrochloric acid with the concentration of 38wt% into a reaction kettle, and carrying out primary purification treatment for 8 hours at the temperature of 80 ℃ and under the condition of 120r/min to obtain purified carbon nano tube feed liquid;
and filtering the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying in a continuous mesh belt furnace with a graphite lining to obtain the purified carbon nanotube, wherein the content of iron impurities is 500ppm and the content of cobalt impurities is 105ppm.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for pickling and purifying carbon nanotubes, comprising the following steps:
(1) Mixing the carbon nano tube to be purified, an acid-resistant water-soluble dispersing agent and water, and carrying out modification treatment to obtain a modified carbon nano tube feed liquid;
(2) Mixing the modified carbon nanotube feed liquid with acid liquid, and purifying to obtain purified carbon nanotube feed liquid;
(3) And (3) carrying out solid-liquid separation on the purified carbon nanotube feed liquid, washing the obtained solid material to be neutral, and drying to obtain the purified carbon nanotube.
2. The acid cleaning purification method according to claim 1, wherein the carbon nanotubes to be purified in the step (1) have a length of 10 to 200 μm and an outer diameter of 1 to 100nm; the agglomerate size of the carbon nano tube to be purified is 1-2000 mu m.
3. The acid washing purification method according to claim 1, wherein the acid-resistant water-soluble dispersant in the step (1) comprises one or more of polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethylidene diphosphonic acid, a cellulose-based compound, and a compound containing a polyoxyethylene ether functional group.
4. A pickling purification process according to claim 3, characterised in that the cellulose-based compound comprises hydroxyethyl cellulose and/or hydroxypropyl methylcellulose.
5. The acid washing purification method according to claim 3, wherein the polyoxyethylene ether functional group-containing compound comprises C 8-10 One or more of glyceride polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dodecylphenol polyoxyethylene ether and polyoxypropylene polyoxyethylene propylene glycol ether.
6. The acid cleaning purification method according to any one of claims 3 to 5, wherein the mass ratio of the acid-resistant water-soluble dispersant to water in the step (1) is (5 to 35): 100.
7. the acid cleaning purification method according to claim 6, wherein the mass ratio of the carbon nanotubes to be purified in the step (1) to the total mass ratio of the acid-resistant water-soluble dispersant and water is (10 to 50): 100.
8. the pickling purification method according to claim 1, wherein the temperature of the modification treatment in the step (1) is 50 to 60 ℃ for 30 to 90 minutes; the modification treatment is carried out under stirring conditions.
9. The pickling purification method according to claim 1, wherein the acid liquid in the step (2) is hydrochloric acid, and the concentration of the hydrochloric acid is 36-38 wt%; the mass ratio of the hydrochloric acid to the modified carbon nanotube feed liquid is 1: (4-30).
10. The pickling purification method according to claim 1, wherein the purification treatment in the step (2) is performed at a temperature of 50 to 60 ℃ for a time of 2 to 4 hours; the purification treatment is carried out under stirring.
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| CN202310334351.5A CN116395675A (en) | 2023-03-30 | 2023-03-30 | Pickling and purifying method for carbon nano tube |
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