CN115806287A - Array carbon nanotube and method for preparing array carbon nanotube and lamellar catalyst - Google Patents
Array carbon nanotube and method for preparing array carbon nanotube and lamellar catalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 106
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims description 39
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 239000012018 catalyst precursor Substances 0.000 claims description 29
- 239000008139 complexing agent Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229940075582 sorbic acid Drugs 0.000 claims description 2
- 235000010199 sorbic acid Nutrition 0.000 claims description 2
- 239000004334 sorbic acid Substances 0.000 claims description 2
- 229960001367 tartaric acid Drugs 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 46
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 5
- 229940069446 magnesium acetate Drugs 0.000 description 5
- 235000011285 magnesium acetate Nutrition 0.000 description 5
- 239000011654 magnesium acetate Substances 0.000 description 5
- 238000003491 array Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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- 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 relates to the technical field of carbon material preparation, and discloses an array carbon nanotube and a method for preparing the array carbon nanotube and a lamellar catalyst. An array carbon nanotube in the form of bundle is grown on a lamellar catalyst, wherein the length of the array carbon nanotube is 10-50 μm, and the specific surface area is 100-180m 2 Per g, saidThe powder resistivity of the array carbon nano tube is 10-25m omega cm. The array carbon nanotube has the characteristics of low specific surface area and short array length, so that the array carbon nanotube with high dispersibility can be prepared, and the application dispersibility of the array carbon nanotube can be improved.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to an array carbon nanotube and a method for preparing the array carbon nanotube and a lamellar catalyst.
Background
The carbon nano tube is a one-dimensional quantum material with a unique nano hollow structure, has excellent conductivity, and can be dispersed in a solvent to form conductive slurry to be applied to a lithium ion battery.
The carbon nanotubes are classified into arrayed carbon nanotubes and agglomerated carbon nanotubes according to the aggregation state. The array carbon nano-tube has better conductivity and dispersibility than the agglomerated carbon nano-tube because of the ordered arrangement and good orientation. However, the length of the array of the carbon nanotubes on the market is long, a certain winding property still exists between the single carbon nanotubes in the tube bundle, and the specific surface area of the long array carbon nanotube is relatively high, so that the dispersion of the long array carbon nanotube has certain difficulty.
Based on this, the inventors thought that it was necessary to provide an array carbon nanotube that was easily dispersed. In industry, a catalyst is usually prepared by catalyzing a carbon source gas with the catalyst, so that the catalyst can significantly affect the physicochemical properties of the array carbon nanotubes, and therefore, it is necessary to develop a catalyst capable of preparing the array carbon nanotubes with good dispersibility.
Disclosure of Invention
In order to prepare the array carbon nano tube with high dispersibility, the application provides the array carbon nano tube and a method for preparing the array carbon nano tube and the lamellar catalyst.
Firstly, the application provides an array carbon nanotube, which adopts the following technical scheme:
the array carbon nanotube is in a bundle shape and grows on at least one surface of the lamellar catalyst, the length of the array carbon nanotube is 10-50 mu m, and the specific surface area is 100-180m 2 (iv) g; the particle size distribution of the lamellar catalyst is5-160μm。
In one embodiment, the powder resistivity of the arrayed carbon nanotubes is 10-25m Ω · cm.
Most of the commercially available carbon nanotubes are arrays with a length of 50 μm or more and a specific surface area of 200m or more 2 And/g or more, the length of the array of the commercially available array carbon nanotubes is longer or the specific surface area is higher, so that the dispersion of the array carbon nanotube powder is poor.
The array carbon nanotube powder prepared by the method not only has better conductivity, but also has the array length of 10-50um and the specific surface area of 100-180m 2 The specific surface area and the array length of the array carbon nano-tubes are obviously lower than those of the array carbon nano-tubes sold in the market, and the dispersibility of the array carbon nano-tubes prepared by the method is obviously improved compared with that of the array carbon nano-tubes in the prior art.
Secondly, the application provides a preparation method of the array carbon nano tube, which adopts the following technical scheme:
and (3) placing the lamellar catalyst into a reactor, introducing protective gas, heating and maintaining the temperature at 650-720 ℃, introducing reducing gas, reacting for 0-60min, introducing carbon source gas, and reacting for 10-90min to obtain the array carbon nanotube powder. In one embodiment, the catalyst is added in an amount of 0.2-2g, and the flow rate of the carbon source gas is 1-3L/min.
In one embodiment, the carbon source gas is any one of methane, ethane, propane, ethylene and propylene.
The carbon source gas is generally a hydrocarbon compound, and as the carbon source gas is continuously cracked at a high temperature of 650 to 720 ℃, C — H bonds are broken, thereby gradually forming carbon and hydrogen. Therefore, the hydrogen generated by the cracking of the carbon source gas can reduce the active metal oxide on the surface of the catalyst to the active metal simple substance without introducing the hydrogen. The active metal simple substance has a good catalytic effect on a carbon source deposited on the surface of the catalyst at 650-720 ℃, and the carbon source gas is subjected to catalytic reaction for 10-90min at 650-720 ℃ so that the carbon source gas is cracked and grown on the surface of the catalyst prepared by the method, and the array carbon nanotube powder with low specific surface area and short array length is obtained.
In one embodiment, the shielding gas is nitrogen or inert gas.
In one embodiment, the reducing gas is hydrogen.
Preferably, before introducing hydrogen, the catalyst is firstly introduced with nitrogen or inert gas to raise the temperature to 680-700 ℃, and after the temperature is stable, hydrogen is introduced; further, after the carbon source gas is introduced, nitrogen or inert gas is introduced, and the array carbon nanotube powder is obtained after natural cooling to 20-30 ℃.
In addition, the application provides a preparation method of the lamellar catalyst, which adopts the following technical scheme:
step S1, dissolving an active component containing an active metal element, a carrier component containing a carrier metal element and a complexing agent in water, and uniformly mixing to obtain a catalyst precursor solution;
and S2, calcining the catalyst precursor solution at 500-900 ℃ for 10min-4h to obtain the lamellar catalyst.
The active component containing active metal elements, the carrier component containing carrier metal elements and the complexing agent are dissolved in water together, the complexing agent is used as an organic ligand and can be simultaneously complexed with the active metal elements and the carrier metal elements to form a metal organic framework compound, the metal organic framework compound expands under the action of calcination and then is cracked and combusted, meanwhile, moisture and non-metal ions in a catalyst precursor solution are evaporated, decomposed and removed, and then the residual metal elements and oxygen in the air are self-assembled to generate the metal oxide catalyst with a lamellar structure. Compared with the catalyst prepared by the impregnation method in the prior art, the lamellar catalyst prepared by the method has a thinner lamellar structure, is higher in activity and is more uniform in active site distribution. The catalyst adopting the lamellar structure is easier to grow the high-dispersity array carbon nano tube with low specific surface area and short array, thereby being beneficial to preparing the conductive slurry with high solid content and further reducing the enterprise cost. The preparation process of the catalyst is simple and easy to implement, the raw material source is wide, the production cost and the production period of the carbon nano tube can be reduced, and the preparation method is suitable for industrial mass production.
In one embodiment, the concentration of the active metal element in the active component is 0.5-3mol/L, the concentration of the carrier metal element in the carrier component is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L.
Further, the molar ratio of the active metal element to the carrier metal element is 1: (0.6-3).
Furthermore, the molar ratio of the complexing agent to the sum of the active metal element and the carrier metal element is 1 (0.5-1.25).
The activity and the appearance of the catalyst can be controlled by adjusting the molar ratio of the active metal element, the carrier metal element and the complexing agent, so that the appearance, the specific surface area, the resistivity and the like of the carbon nano tube prepared by the catalyst are controlled, and finally the array carbon nano tube with high dispersibility is obtained.
Preferably, the complexing agent comprises one or more of citric acid, tartaric acid, sorbic acid, ethylene diamine tetraacetic acid, ethylene glycol, polyethylene glycol and glycerol.
In summary, the present application has the following beneficial effects:
1. the active component, the carrier component and the complexing agent are matched with a specific concentration to form a catalyst precursor solution, and then the catalyst precursor solution is calcined to form the lamellar catalyst. The lamellar catalyst is prepared by adopting a self-assembly method, the uniformity of the distribution of active sites is enhanced, and the bundle array carbon nano tube grows on at least one surface of the lamellar catalyst.
2. By adjusting the molar ratio of the active metal element to the carrier metal element and further adjusting the molar ratio of the sum of the active metal element and the carrier metal element to the complexing agent, the activity and the microscopic morphology of the catalyst can be further regulated and controlled, the catalyst can be used for better catalyzing a carbon source gas, and the array carbon nanotube with low specific surface area and short array length can be obtained.
3. The electric resistivity of the powder of the array carbon nano tube prepared by the method is 10-25m omega cm, the array carbon nano tube has better electric conductivity, the array length is 10-50um, the specific surface area is 100-180m < 2 >/g, the array carbon nano tube has shorter array length and lower specific surface area, and the dispersibility of the array carbon nano tube prepared by the method is obviously improved on the basis of keeping better electric conductivity compared with the dispersibility of the array carbon nano tube in the prior art.
Drawings
FIG. 1 is a scanning electron micrograph (upper panel) of a catalyst prepared in preparation example 1 of the present application and a scanning electron micrograph (lower panel) of a catalyst prepared in comparative preparation example 1.
Fig. 2 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of the carbon nanotubes prepared in example 1 of the present application.
Fig. 3 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of the carbon nanotubes prepared in example 3 of the present application.
Fig. 4 a raman spectrum of the carbon nanotube prepared in example 3 of the present application.
FIG. 5 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of comparative sample 1 prepared in comparative example 1 of the present application.
FIG. 6 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of comparative sample 2 prepared in comparative example 2 of the present application.
Detailed Description
Preparation example 1
A catalyst, the preparation method of which comprises the following steps:
step S1, stirring cobalt nitrate, aluminum nitrate and citric acid in 30mL of water until the cobalt nitrate, the aluminum nitrate and the citric acid are dissolved uniformly to obtain a catalyst precursor solution; wherein, the cobalt nitrate is an active component, and the concentration of the cobalt element is 0.85mol/L; aluminum nitrate is used as a carrier component, and the concentration of aluminum element is 1.6mol/L; citric acid is taken as a complexing agent, and the concentration of the citric acid is 4.9mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 500 ℃ for 2h to obtain the catalyst (the structural morphology is specifically shown in the upper diagram of FIG. 1).
Preparation example 2
A catalyst, the preparation method of which comprises the following steps:
step S1, stirring nickel acetate, ammonium heptamolybdate, magnesium acetate and tartaric acid in 30mL of water until the nickel acetate, the ammonium heptamolybdate, the magnesium acetate and the tartaric acid are dissolved uniformly to obtain a catalyst precursor solution; the nickel acetate and ammonium heptamolybdate are active components, the concentration of nickel element is 3.0mol/L, the concentration of molybdenum element is 0.51mol/L, magnesium acetate is a carrier component, the concentration of magnesium element is 4.98mol/L, tartaric acid is a complexing agent, and the concentration of tartaric acid is 6.79mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 500 ℃ for 4 hours to obtain the catalyst.
Preparation example 3
A catalyst, the preparation method of which comprises the following steps:
step S1, stirring cobalt nitrate, manganese nitrate, aluminum nitrate and citric acid in 30mL of water until the cobalt nitrate and the manganese nitrate are uniformly dissolved to obtain a catalyst precursor solution, wherein the cobalt nitrate and the manganese nitrate are used as active components, the concentration of a cobalt element is 0.73mol/L, the concentration of a manganese element is 0.5mol/L, the aluminum nitrate is used as a carrier component, the concentration of an aluminum element is 2.9mol/L, the citric acid is a complexing agent, and the concentration of the citric acid is 7.0mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 650 ℃ for 30min to obtain the catalyst.
Preparation example 4
A catalyst, the preparation method of which comprises the following steps:
step S1, stirring and uniformly dissolving ferric nitrate, ammonium heptamolybdate, aluminum nitrate, calcium nitrate and ethylene diamine tetraacetic acid in 30mL of water to obtain a catalyst precursor solution, wherein the ferric nitrate and the ammonium heptamolybdate are active components, the concentration of an iron element is 2.45mol/L, the concentration of a molybdenum element is 1.0mol/L, the calcium nitrate and the aluminum nitrate are carrier components, the concentration of a calcium element is 0.5mol/L, the concentration of an aluminum element is 1.57mol/L, the ethylene diamine tetraacetic acid is a complexing agent, and the concentration of the ethylene diamine tetraacetic acid is 4.83mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace to calcine at high temperature of 900 ℃ for 10min to obtain the catalyst.
Preparation example 5
A catalyst, the preparation method of which comprises the following steps:
step S1, stirring and uniformly dissolving ferric nitrate, nickel nitrate, aluminum nitrate, magnesium nitrate and citric acid in 30mL of water to obtain a catalyst precursor solution, wherein the ferric nitrate and the nickel nitrate are active components, the concentration of an iron element is 1.56mol/L, the concentration of a nickel element is 0.5mol/L, the aluminum nitrate and the magnesium nitrate are carrier components, the concentration of an aluminum element is 1mol/L, the concentration of a magnesium element is 4.58mol/L, the citric acid is a complexing agent, and the concentration of the citric acid is 6.11mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace to calcine at a high temperature of 500 ℃ for 1 hour to obtain the catalyst.
Preparation example 6
A catalyst, the preparation method of which comprises the following steps:
step S1, stirring cobalt acetate, manganese nitrate, aluminum nitrate, magnesium acetate and ethylene glycol in 30mL of water until the cobalt acetate, the manganese nitrate and the ethylene glycol are uniformly dissolved to obtain a catalyst precursor solution, wherein the cobalt acetate and the manganese nitrate are used as active components, the concentration of a cobalt element is 0.73mol/L, the concentration of a manganese element is 0.93mol/L, the aluminum nitrate and the magnesium acetate are used as carrier components, the concentration of an aluminum element is 3.32mol/L, the concentration of a magnesium element is 1.66mol/L, the ethylene glycol is a complexing agent, and the concentration of the ethylene glycol is 6.3mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 750 ℃ for 30min to obtain the catalyst.
Preparation of comparative example 1
A comparative sample 1 was prepared, differing from preparation example 1 in that: and (3) carrying out spray drying on the catalyst precursor solution prepared in the step (S1) to obtain catalyst precursor powder. The catalyst precursor powder was then calcined in a muffle furnace at 500 ℃ for 2h to obtain a preparation comparative sample 1 (see the lower diagram of fig. 1 for specific structural morphology).
Preparation of comparative example 2
A comparative sample 2 was prepared, differing from preparation example 3 in that: in the step S1, cobalt nitrate, manganese nitrate and aluminum nitrate are stirred in 30mL of water until the cobalt nitrate, the manganese nitrate and the aluminum nitrate are uniformly dissolved to obtain a catalyst precursor solution, wherein the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.5mol/L, and the concentration of aluminum element is 2.9mol/L.
Preparation of comparative example 3
A comparative sample 3 was prepared, differing from preparation example 3 in that: in the step S1, the concentration of the cobalt element is 0.33mol/L, and the concentration of the manganese element is 0.37mol/L.
Preparation of comparative example 4
A comparative sample 4 was prepared, differing from preparation example 3 in that: step S1, uniformly stirring cobalt nitrate, manganese nitrate and diaspore in 30mL of water to obtain a catalyst precursor suspension, wherein the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.5mol/L, and the concentration of aluminum element is 2.9mol/L.
In each of the above examples and comparative preparation examples, specific components of the active component, the carrier component and the complexing agent, and the molar ratio x of the active metal element to the carrier metal element and the molar ratio y of the complexing agent to the sum of the active metal element and the carrier metal element are specified in table 1.
The molar ratio x of the active metal element to the carrier metal element is calculated as follows:
the method for calculating the molar ratio y of the complexing agent to the sum of the active metal element and the carrier metal element is as follows:
TABLE 1
Example 1
A preparation method of a low specific surface area short array carbon nanotube comprises the following steps of placing 0.2g of a catalyst prepared in preparation example 1 in a vertical fluidized bed reactor, introducing 2L/min of nitrogen protection gas, starting a heating furnace, heating to 700 ℃, introducing 1L/min of hydrogen to reduce for 30min after the temperature is stable, introducing 1L/min of propylene to react for 30min after the reduction is finished, and continuing to cool to room temperature under the protection of 2L/min of nitrogen after the reaction is finished to obtain low specific surface area short array carbon nanotube powder (the specific structure and appearance are shown in figure 2).
Example 2
A preparation method of a short array carbon nanotube with low specific surface area comprises the following steps of placing 2g of a catalyst prepared in preparation example 2 in a vertical fluidized bed reactor, introducing 3L/min of nitrogen protection gas, starting a heating furnace, heating to 700 ℃, directly introducing 2L/min of propylene for reaction for 10min after the temperature is stable, and continuously cooling to room temperature under the protection of 3L/min of nitrogen after the reaction is finished to obtain the short array carbon nanotube powder with low specific surface area.
Example 3
A preparation method of a low specific surface area short array carbon nanotube comprises the following steps of placing 0.5g of a catalyst prepared in preparation example 3 in a vertical fluidized bed reactor, introducing 1L/min of nitrogen protection gas, starting a heating furnace, heating to 680 ℃, introducing 1L/min of hydrogen to reduce for 10min after the temperature is stable, introducing 1L/min of propylene to react for 60min after the reduction is finished, and continuing to cool to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain low specific surface area short array carbon nanotube powder (the specific structural form is shown in figure 3).
Example 4
A preparation method of a low specific surface area short array carbon nanotube comprises the following steps of placing 2g of a catalyst prepared in preparation example 4 in a vertical fluidized bed reactor, introducing argon gas with the flow rate of 2L/min as protective gas, starting a heating furnace, heating to 700 ℃, introducing 1L/min of hydrogen gas to reduce for 60min after the temperature is stable, introducing 3L/min of propylene to react for 90min after the reduction is finished, and continuing cooling to room temperature under the protection of 2L/min of nitrogen gas after the reaction is finished to obtain low specific surface area short array carbon nanotube powder.
Example 5
A preparation method of a short array carbon nanotube with low specific surface area comprises the following steps of placing 1.0g of the catalyst prepared in preparation example 5 in a horizontal fixed bed reactor, introducing 1L/min of nitrogen protection gas, starting a heating furnace, heating to 700 ℃, introducing 1.0L/min of hydrogen to reduce for 30min after the temperature is stable, introducing 1.0L/min of propylene to react for 60min after the reduction is finished, and continuing cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain the short array carbon nanotube powder with low specific surface area.
Example 6
A preparation method of a short array carbon nanotube with low specific surface area comprises the following steps of placing 1.0g of a catalyst prepared in preparation example 6 in a horizontal fixed bed reactor, introducing 1.0L/min of nitrogen protection gas, starting a heating furnace, heating to 680 ℃, introducing 1.0L/min of hydrogen for reduction for 30min after the temperature is stable, introducing 1.0L/min of propylene for reaction for 60min after the reduction is finished, and continuing cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain the short array carbon nanotube powder with low specific surface area.
Comparative example 1 was carried out
A method for preparing a short array carbon nanotube with low specific surface area is different from the method in example 1 in that: the catalyst prepared in example 1 was replaced with comparative sample 1 in equal amounts (see figure 5 for specific structural morphology).
Comparative example 2 was carried out
A method for preparing low specific surface area short array carbon nano tubes is different from the method in example 3 in that: the catalyst prepared in example 3 was replaced with comparative sample 2 in equal amounts (see figure 6 for specific structural morphology).
Comparative example 3 was carried out
A method for preparing a short array carbon nanotube with low specific surface area is different from the method in example 3 in that: the catalyst prepared in example 3 was replaced with comparative sample 3 in equal amounts.
Comparative example 4 was carried out
A method for preparing a short array carbon nanotube with low specific surface area is different from the method in example 3 in that: the catalyst prepared in example 3 was replaced with an equal amount of comparative sample 4.
Specific surface area, multiplying power and powder resistivity data of the short array carbon nanotubes prepared in the examples and the comparative samples are shown in table 2.
The calculation formula of the multiplying power is as follows:
multiplying factor = (carbon nanotube powder weight-catalyst weight)/catalyst weight
TABLE 2
The graphitization degree of the array carbon nanotube powder prepared in example 3 is measured by raman spectroscopy, and the raman spectrogram in fig. 4 proves that the array carbon nanotube powder prepared in example 3 has high graphitization degree and few defects.
The data of examples 1-6 in table 2 show that the rate of the carbon nanotubes array prepared in examples 1-6 is between 14-31, which proves that the method for preparing the short carbon nanotubes array with low specific surface area has better yield. The resistivity of the carbon nanotubes of the arrays prepared in examples 1-6 is between 12.32 and 24.96, which shows that the carbon nanotubes of the arrays prepared in examples 1-6 have better conductivity. The specific surface area of the array carbon nano-tube prepared by the method is 103-179m 2 The specific surface area of the commercial array carbon nano-tube is mostly between 200 m/g 2 The specific surface area of the array carbon nano tube prepared by the method is proved to be obviously lower than that of the array carbon nano tube sold in the market. Arrays prepared in examples 1 and 3, as can be obtained in conjunction with FIGS. 2-3 of the present applicationIn conclusion, the preparation method of the array carbon nanotube in the application not only obtains the carbon nanotube with better conductivity in a mode of higher multiplying power, but also has the characteristics of low specific surface area and short array length, is beneficial to disperse pulping and obtain conductive slurry with high solid content, and is further beneficial to reducing the cost of dispersing pulping of the carbon nanotube.
As can be seen from the data of example 1 and comparative example 1 in table 2, which are compared with fig. 1, 2 and 5, in the preparation process of the catalyst of example 1, the catalyst having a lamellar structure is obtained by calcining the catalyst precursor solution, and the catalyst can be used to prepare the arrayed carbon nanotubes having a distinct array morphology, a low specific surface area and a short array length, in the preparation process of the catalyst of comparative example 1, the catalyst precursor solution is dried into powder and then calcined, so that the catalyst of comparative example 1 cannot be self-assembled to form the catalyst having a lamellar structure as shown in fig. 1 (upper diagram), and the catalyst can be used to prepare a comparative sample 1 having a high specific surface area, a lump and an insignificant array morphology, which shows that the catalyst precursor solution can be directly calcined without drying to prepare the highly dispersed arrayed carbon nanotubes.
By comparing the data of the example 3 and the comparative example 2 in the table 2 with the data of fig. 3 and fig. 6, the complexing agent is added in the catalyst preparation process, so that the catalyst with better morphology and activity can be obtained, the array carbon nanotube with low specific surface area, obvious array morphology and short array length can be prepared, and the array carbon nanotube with high dispersibility can be obtained.
By comparing the data of the example 3 and the comparative example 3 in the table 2, the active metal element, the carrier metal element and the complexing agent are matched at a certain concentration to form the catalyst precursor solution, so that the catalyst precursor solution forms a catalyst with a lamellar structure with better activity after being calcined, and the short array carbon nanotube which can catalyze the carbon source gas to generate the carbon source gas with low specific surface area, high yield and obvious array morphology is obtained.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (11)
1. An arrayed carbon nanotube characterized by:
the array carbon nanotube is in a bundle shape and grows on at least one surface of the lamellar catalyst, the length of the array carbon nanotube is 10-50 mu m, and the specific surface area is 100-180m 2 /g；
The particle size distribution of the lamellar catalyst is 5-160 mu m.
2. The carbon nanotube array of claim 1, wherein: the powder resistivity of the array carbon nano tube is 10-25m omega cm.
3. The method for preparing the carbon nanotube array of claim 1, wherein the lamellar catalyst is placed in a reactor, a shielding gas is introduced, the temperature is raised and maintained at 650-720 ℃, then a reducing gas is introduced, and after reacting for 0-60min, a carbon source gas is introduced for reacting for 10-90min to obtain the carbon nanotube array powder.
4. The method of claim 3, wherein the step of preparing the carbon nanotubes comprises: the input amount of the catalyst is 0.2-2g, and the flow rate of the carbon source gas is 1-3L/min.
5. The method for preparing carbon nanotubes of claim 3 or 4, wherein the carbon source gas is any one of methane, ethane, propane, ethylene and propylene.
6. The method of claim 3, wherein the step of preparing the carbon nanotubes comprises: the protective gas is nitrogen or inert gas.
7. A process for preparing the lamellar catalyst according to claim 1,
step S1, dissolving an active component containing an active metal element, a carrier component containing a carrier metal element and a complexing agent in water, and uniformly mixing to obtain a catalyst precursor solution;
and S2, calcining the catalyst precursor solution at 500-900 ℃ for 10min-4h to obtain the lamellar catalyst.
8. The method for preparing a lamellar catalyst according to claim 7, characterized in that the concentration of the active metal element in the active component is between 0.5 and 3mol/L, the concentration of the carrier metal element in the carrier component is between 0.5 and 5.0mol/L and the concentration of the complexing agent is between 3.0 and 7.0mol/L.
9. The method of claim 8, wherein the molar ratio of active metal element to support metal element is 1: (0.6-3).
10. The method of claim 8, wherein the molar ratio of the complexing agent to the sum of the active metal element and the support metal element is 1 (0.5-1.25).
11. The method for preparing a lamellar catalyst according to any of claims 7-10, characterized in that the active component is one or more combinations of soluble manganese, iron, cobalt, nickel and molybdate salts; the carrier component is one or a combination of soluble magnesium salt, aluminum salt, calcium salt and aluminosilicate; the complexing agent comprises one or more of citric acid, tartaric acid, sorbic acid, ethylene diamine tetraacetic acid, ethylene glycol, polyethylene glycol and glycerol.
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