CN116281964A - Efficient carbon nano tube purification method and purification equipment - Google Patents
Efficient carbon nano tube purification method and purification equipment Download PDFInfo
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- CN116281964A CN116281964A CN202310574330.0A CN202310574330A CN116281964A CN 116281964 A CN116281964 A CN 116281964A CN 202310574330 A CN202310574330 A CN 202310574330A CN 116281964 A CN116281964 A CN 116281964A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 101
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 101
- 238000000746 purification Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 239000007790 solid phase Substances 0.000 claims abstract description 19
- 239000006096 absorbing agent Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 80
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000005243 fluidization Methods 0.000 claims description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 5
- 239000012433 hydrogen halide Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009471 action Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- C01B32/159—Carbon nanotubes single-walled
-
- 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
- C01B2202/06—Multi-walled nanotubes
-
- 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 invention discloses a high-efficiency carbon nano tube purification method and purification equipment, wherein the purification equipment comprises a reaction cavity, a heater, an air inlet, an air outlet, a solid phase feed inlet and a solid phase discharge outlet, wherein the air outlet is communicated with a gas absorber, a spiral guide plate is also arranged in the reaction cavity, a plurality of fluidized beds are arranged on the lower sides of the spiral guide plate, lifting pipelines are communicated on the lower sides of the fluidized beds, and fluidizing gas is continuously introduced into the lifting pipelines; the solid carbon nano tube introduced into the purification equipment can be effectively fluidized, the carbon nano tube in a fluidized state can be reacted, and the reaction efficiency and the purification efficiency are improved; the purification method provided by the invention utilizes the mixed gas to convert impurities such as carbon impurities, catalysts, metal oxides and the like into gaseous compounds at one time in purification equipment at high temperature to remove the gaseous compounds, and the high-purity carbon nano tube is obtained, and the method has the advantages of no acid washing, water treatment, simple process, energy conservation and consumption reduction.
Description
Technical Field
The invention relates to the technical field of carbon nanotube purification, in particular to a high-efficiency carbon nanotube purification method and purification equipment.
Background
The carbon nanotube is a hollow tubular carbon material, and the tube wall is composed of a single layer to hundreds of layers of carbon walls, and has excellent mechanical property, electric conductivity, heat resistance and stable chemical property. At present, the yield of the carbon nano tube is greatly increased, and the application field is rapidly expanded.
Carbon nanotubes are widely used in the new energy field, and are known as the optimal conductive agent for improving the high rate and long cycle performance of lithium ion batteries, but the field has more severe requirements on the purity of the carbon nanotubes, and excessive metal impurities tend to remain in the preparation process of the carbon nanotubes. At present, whether PVD, an arc discharge method, a laser ablation method or a polymerization reaction synthesis method is used, the purity requirements of new energy fields such as lithium ion batteries are difficult to ensure, and safety problems such as reduced thermal stability, reduced chemical stability, short circuit of the batteries and the like exist in the use process of the lithium ion batteries.
In order to remove the carbon impurities, catalyst and other residues in the carbon nanotube primary product, the carbon nanotube primary product needs to be purified. In the current purification method, the impurity carbon is oxidized first by adopting an oxidation method and then removed in a carbon dioxide form, and residual metals such as a catalyst and metal oxides are removed after being soaked in strong acid (hydrochloric acid, sulfuric acid and the like). The prior art has the following disadvantages: complex process and equipment, high cost and low removal efficiency.
Disclosure of Invention
The first object of the present invention is to provide a method for purifying carbon nanotubes with high efficiency, which aims at the problem of low efficiency of the existing batch purification of carbon nanotubes.
In order to achieve the first object, the present invention provides the following technical solutions: a method for purifying high-efficiency carbon nanotubes, comprising the following steps:
s1: feeding the carbon nano tube containing impurities into purification equipment, introducing oxygen, reacting for 10-120 min at 1000-1200 ℃, and discharging gas after the reaction is finished;
s2: reducing the temperature to 500-1000 ℃, introducing acid gases such as hydrogen halide and the like, continuing the reaction for 5-60 min, and discharging the gases after the reaction is finished;
s3: after the gas in the purifying equipment is exhausted, introducing inert gas to cool to below 80 ℃, and stopping gas inlet;
and S4, extracting the purified carbon nano tube solid.
Through the technical scheme, S1 preferentially oxidizes the carbon impurities through oxygen and discharges the carbon impurities through gas; s2, removing impurities such as iron/cobalt/nickel/molybdenum and oxides thereof from the metal catalyst in a gas form through acid gases such as hydrogen halide.
Preferably, the carbon nanotubes in S1 react in a fluidized state, and the mass ratio of oxygen to carbon nanotubes is 1: 50-1:1000.
Preferably, the carbon nano-tubes in the S2 are carried out in a fluidized state, and the mass ratio of the acid gas to the carbon nano-tubes is 1:20-1:2000.
Preferably, the hydrogen halide gas in S2 includes one or more of hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide; and one or more of gaseous fluorine, chlorine, bromine and iodine.
Taking hydrogen chloride gas as an example, the reaction equation is as follows:
Ni+HCl= NiCl（G）+1/2H 2 ；
or Ni 2 O+2HCl= 2NiCl（G）+H 2 （G）。
Preferably, the carbon nanotubes include iron-based, nickel-based, cobalt-based, single-walled, multi-walled, and the like.
The second object of the present invention is to provide a high-efficiency carbon nanotube purifying apparatus, which aims at the problems of complex existing apparatus and low purifying efficiency.
In order to achieve the second object, the present invention provides the following technical solutions:
a high-efficiency carbon nano tube device:
the purification equipment comprises a reaction cavity, a heater, an air inlet, an air outlet, a solid phase feeding hole and a solid phase discharging hole, wherein the air outlet is communicated with a gas absorber.
Preferably, a spiral guide plate is further arranged in the reaction cavity, and a plurality of fluidized beds are arranged on the lower side of the spiral guide plate.
Preferably, the lower side of the fluidized bed is communicated with a lifting pipeline, the lifting pipeline is continuously introduced with fluidizing gas, and the flow rate of the fluidizing gas is 0.1-3 m/s.
Preferably, the inclination angle of the spiral guide piece is 10-15 °.
Preferably, a baffle is also arranged between the adjacent fluidized beds.
Preferably, the fluidizing gas in S1 is an inert gas.
Through the technical scheme, the solid carbon nano tube is fed through the solid feed inlet at the upper side of the reaction cavity, and continuously moves downwards under the guiding action of the spiral guide piece; under the action of a plurality of fluidized beds at the bottom of the spiral guide plate, the solid carbon nano tube is always in a fluidized state, which is beneficial to improving the purification efficiency; under the inclination angle of 10-15 degrees, the gas moves upwards and is discharged through the gas outlet, the solid carbon nano tube slowly moves downwards, and the purified carbon nano tube is discharged through the solid phase discharge hole.
The beneficial effects are that:
the purification method provided by the invention utilizes the mixed gas to convert impurities such as carbon impurities, catalysts, metal oxides and the like into gaseous compounds at one time in purification equipment at high temperature to remove the gaseous compounds, and the high-purity carbon nano tube is obtained, and the method has the advantages of no acid washing, water treatment, simple process, energy conservation and consumption reduction.
The purification equipment provided by the invention can effectively fluidize the solid carbon nanotubes introduced into the purification equipment, react the carbon nanotubes in a fluidized state, prevent the solid carbon nanotubes from adhering to the inner wall of the reaction cavity or the spiral guide plate, and improve the reaction efficiency and the purification efficiency.
The invention can achieve the purpose of multistage fluidization in the actual reaction process by arranging a plurality of fluidized beds on the spiral guide sheet and enabling a certain inclination angle between the adjacent fluidized beds, namely, solid matters continuously move downwards and are always in a fluidization state under the action of the plurality of fluidized beds, thereby preventing solid carbon nano tubes from adhering to the spiral guide sheet and improving the reaction efficiency and the purification efficiency.
Based on the purification equipment, the purification process can rapidly fluidize the carbon nano tube, has high starting speed and simple process flow, and greatly shortens the subsequent reaction time.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a high-efficiency carbon nanotube purifying apparatus according to the present invention;
FIG. 2 is a partial schematic view of a plurality of fluidized beds of the present invention on a helical blade guide;
FIG. 3 is a TEM image of a carbon nanotube of the present invention prior to purification;
FIG. 4 is a TEM image of a purified carbon nanotube according to the invention.
In the figure: 1. a reaction chamber; 2. a heater; 3. an air inlet; 4. an air outlet; 5. a solid phase feed inlet; 6. a solid phase discharge port; 7. a spiral guide piece; 8. a fluidized bed; 9. lifting the pipeline; 91. and a baffle.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. 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.
The following describes embodiments of the present invention in detail:
example 1
As shown in FIG. 1, the high-efficiency carbon nanotube purifying device comprises a reaction cavity 1, a heater 2, an air inlet 3, an air outlet 4, a solid-phase feed inlet 5 and a solid-phase discharge outlet 6, wherein the air outlet 4 is communicated with a gas absorber.
As shown in fig. 2, a spiral guide plate 7 is further disposed in the reaction chamber 1, a plurality of fluidized beds 8 are disposed at the lower sides of the spiral guide plate 7, lifting pipes 9 are communicated at the lower sides of the fluidized beds 8, and a baffle 91 is further disposed between adjacent fluidized beds. The lifting pipe 9 is continuously fed with fluidizing gas.
In this example, the flow rate of the fluidizing gas was 1m/s; the inclination angle of the spiral guide piece 7 is 10 °.
The purification method based on the carbon nanotube purification equipment comprises the following steps:
the carbon nano tube containing impurities is sent into a reaction cavity 1 through a solid phase feed port 5, and the mass ratio of oxygen to the carbon nano tube is 1:50, oxygen is introduced from the gas inlet 3 and heated to 1000 ℃ by the heater 2, the oxygen continuously moves downwards under the guiding action of the spiral guiding sheet 7, and the gas purified by the solid carbon nano tube is discharged to the gas absorber from the gas outlet 4 under the high-temperature oxidation reaction. The solid matter continues to move downwards, and as a certain inclination angle is arranged between the adjacent fluidized beds 8, under the action of gravity, the fluidized solid carbon nano tubes turn over a plurality of baffles in sequence, so that the purpose of multistage fluidization is achieved, the solid carbon nano tubes can be prevented from adhering to the spiral guide plates 7, and the reaction efficiency and the purification efficiency are improved. The spiral guide piece prolongs the reaction path on the basis of the equipment with the same volume, and the baffle plate enables the solid matters in the fluidization state to slowly and continuously move downwards, so that the reaction is more sufficient, and the reaction rate is higher.
After the reaction for 20min, the temperature is reduced to 500 ℃, acid gases such as hydrogen chloride, chlorine, hydrogen bromide, iodine and the like are introduced, the reaction is continued for 10min, the purified gases rise and are discharged to a gas absorber through a gas outlet 4, and the solid substances are continuously moved downwards.
And (3) evacuating gas in the purifying equipment, introducing nitrogen, cooling to 70 ℃, stopping air inlet, and extracting purified carbon nanotube solids from the solid-phase discharge port 6.
In this embodiment, the carbon nanotubes are iron-based.
In this embodiment, the gas absorber is composed of a cavity and a gas diffuser, and the cavity contains an absorption liquid in which alkaline substances such as sodium hydroxide, sodium bicarbonate, sodium carbonate and the like are dissolved.
In this embodiment, the gas diffuser is provided as a shower-like porous gas jet, immersed in the absorption liquid for 30cm.
Example 2
The difference from example 1 is that:
in this example, the flow rate of the fluidizing gas was 1.5m/s; the inclination angle of the spiral guide piece 7 is 12 °.
The purification method based on the carbon nanotube purification equipment comprises the following steps:
the carbon nano tube containing impurities is sent into a reaction cavity 1 through a solid phase feed port 5, and the mass ratio of oxygen to the carbon nano tube is 1:100, introducing oxygen from an air inlet 3, heating to 1000 ℃ by a heater 2, continuously moving downwards under the guiding action of a spiral guide sheet 7, and discharging the purified gas of the solid carbon nano tube to a gas absorber from an air outlet 4 under the high-temperature oxidation reaction; the solid matter moves down continuously and under the action of the fluidized beds 8, the solid carbon nano tubes are always in a fluidized state, so that the solid carbon nano tubes can be prevented from adhering to the spiral guide sheet 7, and the reaction efficiency and the purification efficiency are improved.
After the reaction is carried out for 40min, the temperature is reduced to 600 ℃, acid gases such as hydrogen chloride, chlorine, hydrogen bromide, iodine and the like are introduced, the reaction is continued for 20min, the purified gases rise and are discharged to a gas absorber through a gas outlet 4, and the solid substances are continuously moved downwards.
And (3) evacuating gas in the purifying equipment, introducing nitrogen, cooling to 60 ℃, stopping air inlet, and extracting purified carbon nanotube solids from the solid-phase discharge port 6.
In this embodiment, the carbon nanotubes are nickel-based.
In this embodiment, the gas absorber is composed of a cavity and a gas diffuser, and the cavity contains an absorption liquid in which alkaline substances such as potassium hydroxide, potassium carbonate, potassium bicarbonate and the like are dissolved.
In this embodiment, the gas diffuser is provided as a shower-like porous gas jet, immersed 20cm into the absorption liquid.
Example 3
The difference from example 1 is that:
in this example, the flow rate of the fluidizing gas was 2m/s; the inclination angle of the spiral guide piece 7 is 13 °.
The purification method based on the carbon nanotube purification equipment comprises the following steps:
the carbon nano tube containing impurities is sent into a reaction cavity 1 through a solid phase feed port 5, and the mass ratio of oxygen to the carbon nano tube is 1:200, introducing oxygen from an air inlet 3, heating to 1200 ℃ by a heater 2, continuously moving downwards under the guiding action of a spiral guiding sheet 7, and discharging the purified gas of the solid carbon nano tube to a gas absorber from an air outlet 4 under the high-temperature oxidation reaction; the solid matter moves down continuously and under the action of the fluidized beds 8, the solid carbon nano tubes are always in a fluidized state, so that the solid carbon nano tubes can be prevented from adhering to the spiral guide sheet 7, and the reaction efficiency and the purification efficiency are improved.
After the reaction for 60min, the temperature is reduced to 700 ℃, acid gases such as hydrogen chloride, chlorine, hydrogen bromide, iodine and the like are introduced, the reaction is continued for 30min, the purified gases rise and are discharged to a gas absorber through a gas outlet 4, and the solid substances are continuously moved downwards.
And (3) evacuating gas in the purifying equipment, introducing nitrogen, cooling to 50 ℃, stopping air inlet, and extracting purified carbon nanotube solids from the solid-phase discharge port 6.
In this embodiment, the carbon nanotubes are of the single-wall type.
In this embodiment, the gas absorber is composed of a cavity and a gas diffuser, and the cavity contains an absorption liquid in which alkaline substances such as magnesium oxide, calcium hydroxide, magnesium hydroxide and the like are dissolved.
In this example, the gas diffuser was configured as a shower-like porous gas jet, immersed 40cm into the absorption liquid.
Example 4
The difference from example 1 is that:
in this example, the flow rate of the fluidizing gas was 3m/s; the inclination angle of the spiral guide piece 7 is 15 °.
The purification method based on the carbon nanotube purification equipment comprises the following steps:
the carbon nano tube containing impurities is sent into a reaction cavity 1 through a solid phase feed port 5, and the mass ratio of oxygen to the carbon nano tube is 1:500, oxygen is introduced from the air inlet 3 and heated to 1200 ℃ by the heater 2, the oxygen continuously moves downwards under the guiding action of the spiral guide sheet 7, and the purified gas of the solid carbon nano tube is discharged to the gas absorber from the air outlet 4 under the high-temperature oxidation reaction; the solid matter moves down continuously and under the action of the fluidized beds 8, the solid carbon nano tubes are always in a fluidized state, so that the solid carbon nano tubes can be prevented from adhering to the spiral guide sheet 7, and the reaction efficiency and the purification efficiency are improved.
After the reaction is carried out for 100min, the temperature is reduced to 700 ℃, acid gases such as hydrogen chloride, chlorine, hydrogen bromide, iodine and the like are introduced, the reaction is continued for 60min, the purified gases rise and are discharged to a gas absorber from a gas outlet 4, and the solid substances are continuously moved downwards.
And (3) evacuating gas in the purifying equipment, introducing nitrogen, cooling to 50 ℃, stopping air inlet, and extracting purified carbon nanotube solids from the solid-phase discharge port 6.
In this embodiment, the carbon nanotubes are of the multi-wall type.
In this embodiment, the gas absorber is composed of a cavity and a gas diffuser, and the cavity contains an absorption liquid in which alkaline substances such as magnesium oxide, calcium hydroxide, magnesium hydroxide and the like are dissolved.
In this example, the gas diffuser was configured as a shower-like porous gas jet, immersed 40cm into the absorption liquid.
Comparative example 1
The difference from example 1 is that:
the fluidized bed was not provided on the lower side of the spiral guide sheet in this example, and the other steps were the same as in example 1.
Test example 1 image test
The purified carbon nanotubes of example 1 were subjected to electron microscopy, the images before purification are shown in FIG. 2, and the images after purification are shown in FIG. 3.
As can be seen from fig. 2 and 3, the carbon nanotubes before purification coexist with amorphous carbon and metal oxide catalyst, and the pure carbon nanotubes obtained after the treatment of the present invention have no obvious impurities, which proves that the purification effect of the solid carbon nanotubes by the scheme of embodiment 1 of the present invention is good.
Test example 2 ash data sheet of purified carbon nanotubes
The carbon nanotubes purified in examples 1 to 4 and comparative example 1 were each calcined in a muffle furnace at 950℃for 2 hours to obtain test ashes, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the purity of the high purity carbon nanotubes obtained by the purification apparatus and the purification method of the present invention was greater than 99%, and the purification effect was remarkable. Among them, comparative example 1 and comparative example 1, in the same condition of other steps, comparative example 1 was lower in purity than example 1 because no fluidized bed was provided, and it was confirmed that the present invention can further improve purification efficiency by providing several fluidized beds.
Test example 3 high purity carbon nanotube metal impurity content data sheet
The purified carbon nanotubes were immersed in 10% hydrochloric acid for 20 minutes, and the supernatant was filtered and added with sodium hydroxide to ph=7, and ICP test was performed, and the impurity contents after the test are shown in table 2.
TABLE 2
As is clear from Table 2, the contents of metal impurities in the high purity carbon nanotubes prepared in examples 1 to 4 were all lower than 1ppm, and it was confirmed that the carbon nanotubes purified by the purification apparatus and the purification method of the present invention were substantially free of metal catalyst residues and had a good purification effect. The purification efficiency was slightly inferior by using the purification apparatus of comparative example 1 not comprising a fluidized bed.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The high-efficiency carbon nano tube purification method is characterized by comprising the following steps of:
s1: feeding the carbon nano tube containing impurities into purification equipment, introducing oxygen, reacting for 10-120 min at 1000-1200 ℃, and discharging gas after the reaction is finished;
s2: reducing the temperature to 500-1000 ℃, introducing hydrogen halide, continuing to react for 5-60 min, and discharging gas after the reaction is finished;
s3: after the gas in the purifying equipment is exhausted, introducing inert gas to cool to below 80 ℃, and stopping gas inlet;
s4, extracting the purified carbon nano tube solid;
the purification equipment comprises a reaction cavity (1), wherein a spiral guide sheet (7) is further arranged in the reaction cavity (1), and a plurality of fluidized beds (8) are arranged on the lower side of the spiral guide sheet (7); the plurality of fluidized beds (8) are arranged at an inclination angle of 10-15 degrees.
2. The method for purifying high-efficiency carbon nanotubes according to claim 1, wherein: the carbon nano tube in S1 reacts in a fluidization state, and the mass ratio of oxygen to the carbon nano tube is 1: 50-1:1000.
3. The method for purifying high-efficiency carbon nanotubes according to claim 1, wherein: the carbon nano tube in the S2 is carried out in a fluidization state, and the mass ratio of the acid gas to the carbon nano tube is 1:20-1:2000.
4. The method for purifying high-efficiency carbon nanotubes according to claim 1, wherein: the hydrogen halide gas in S2 comprises one or more of hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide; and one or more of gaseous fluorine, chlorine, bromine and iodine.
5. The method for purifying high-efficiency carbon nanotubes according to claim 1, wherein: the carbon nano tube is one of iron series, nickel series, cobalt series, single wall, multi-wall and other types.
6. A high efficiency carbon nanotube purification apparatus in which the purification method of any one of claims 1 to 5 is carried out, characterized in that:
the purification equipment further comprises a heater (2), an air inlet (3), an air outlet (4), a solid-phase feeding hole (5) and a solid-phase discharging hole (6), wherein the air outlet (4) is communicated with a gas absorber.
7. The efficient carbon nanotube purifying apparatus of claim 6, wherein: the lower side of the fluidized bed (8) is communicated with a lifting pipeline (9), the lifting pipeline (9) is continuously introduced with fluidizing gas, and the flow rate of the fluidizing gas is 0.1-3 m/s.
8. The efficient carbon nanotube purifying apparatus of claim 7, wherein: the inclination angle of the spiral guide piece is 10-15 degrees.
9. The efficient carbon nanotube purification apparatus of claim 8, wherein: a baffle plate (91) is also arranged between the adjacent fluidized beds.
10. The efficient carbon nanotube purification apparatus of claim 8, wherein: the fluidizing gas is an inert gas as described in S1.
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