CN114524466A - Synthesis method of high-activity catalyst - Google Patents
Synthesis method of high-activity catalyst Download PDFInfo
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- CN114524466A CN114524466A CN202210171373.XA CN202210171373A CN114524466A CN 114524466 A CN114524466 A CN 114524466A CN 202210171373 A CN202210171373 A CN 202210171373A CN 114524466 A CN114524466 A CN 114524466A
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- carbon nanotubes
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 230000000694 effects Effects 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 117
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 117
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 79
- 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 abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 44
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 36
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 238000005336 cracking Methods 0.000 claims abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010668 complexation reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- BKXSOPQSPJELMF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BKXSOPQSPJELMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 229960001484 edetic acid Drugs 0.000 abstract description 41
- 230000002194 synthesizing effect Effects 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical group [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/30—
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a catalyst synthesized by a carbon nanotube complexing method for olefin gas cracking growth. The invention uses a two-step complexing method of Citric Acid (CA) and Ethylene Diamine Tetraacetic Acid (EDTA) ammonia solution, and prepares the high-activity metal oxide catalyst for synthesizing the carbon nano tube by carbonizing, roasting, crushing and sieving. The high-activity catalyst prepared by the invention has the advantages of simple process, good stability, proper structure and good catalytic activity, the high-performance carbon nano tube is successfully obtained through experiments, the yield of the carbon nano tube obtained by the catalyst with the unit weight of the metal element of the catalyst is 169-246g/g, and the high-activity catalyst has good economic benefit.
Description
Technical Field
The invention relates to a synthesis method of a high-activity catalyst, belonging to the technical field of catalysts.
Background
In recent years, carbon nanotubes have been widely used as excellent conductive agents in the industries of new energy automobile lithium batteries and the like. This is because it has the advantages of excellent thermal and electrical conductivity and good mechanical strength. In addition, the one-dimensional structure of the carbon nano tube can enhance the bonding of the active material and improve the performance of the pole piece. Therefore, the battery has a great application prospect when being used for new energy batteries. The current methods for synthesizing carbon nanotubes mainly include arc discharge, thermal decomposition, chemical vapor deposition, and the like. Compared with other preparation methods, the chemical vapor deposition method shows better superiority, and large-scale industrial application is realized. This is due to the advantages of the carbon nanotubes of the method, such as low growth temperature, easy control and optimization of reaction conditions.
The preparation of the carbon nano tube by the chemical vapor deposition method needs to be completed under the action of a catalyst, the catalyst mainly used in the method at present is an iron-based catalyst and other transition metal catalysts, but the existing reported catalyst has the technical defects of low yield of the synthesized carbon nano tube, high metal residue in the prepared carbon nano tube, high preparation cost caused by the subsequent processes of acid cleaning and purification and the like.
Disclosure of Invention
[ problem ] to
The existing reported catalyst has the technical defects of low yield of synthesized carbon nanotubes, high metal residue in the prepared carbon nanotubes, subsequent processes of acid cleaning, purification and the like, and high preparation cost.
In addition, the length of the synthesized carbon nano tube is short, and is mostly 5-30 micrometers; while carbon nanotubes of hundreds of microns or even millimeter-scale length have been reported only rarely and are difficult to synthesize.
[ solution ]
The first purpose of the present invention is to provide a method for preparing a carbon nanotube catalyst with high activity, which adopts a citric acid-ethylene diamine tetraacetic acid complexation method, wherein the method comprises the following steps:
(1) mixing metal precursor salt, pure water and citric acid to prepare a mixed solution, adding ammonium heptamolybdate, and stirring to dissolve to obtain a citrate mixed solution; stirring and concentrating the citrate mixed solution in water bath, and cooling to obtain a solution A; wherein the molar ratio of the citric acid to the metal precursor salt is (1-1.5): 1;
(2) dissolving EDTA in ammonia water to obtain EDTA ammonia solution; mixing the solution A with an EDTA ammonia solution to obtain a mixed solution B; then, placing the mixed solution B in an open porcelain original vessel, and carbonizing the mixed solution B for 30min at 500 ℃ in a muffle furnace; then, roasting the mixture in a muffle furnace at 450 ℃ for 240min, and sieving and crushing the mixture by a screen to form a powdery catalyst; wherein the molar ratio of EDTA to the metal precursor salt is (0.35-0.75): 1.
As an embodiment of the present invention, the metal precursor salt in step (1) is Mg2+Salt, Al3+Salt, Fe3 +Salt, Co2+A mixture of salts.
As an embodiment of the invention, the mass fraction of ammonia water is 25 wt%; the mass ratio of the ammonia water to the EDTA is (4-7) to 1.
As an embodiment of the present invention, the step (1) is specifically: mixing 102.6g of magnesium nitrate hexahydrate, 30g of aluminum nitrate nonahydrate, 8.9g of ferric nitrate nonahydrate, 5.2g of cobalt nitrate hexahydrate, 585g of pure water and 100g of citric acid, and stirring and dissolving in a water bath with constant temperature of 92 ℃ to obtain a mixed solution; then 0.71g of ammonium heptamolybdate is added into the solution, stirred and dissolved, stirred continuously, heated and concentrated until the volume of the solution is 500mL, and cooled to the normal temperature to obtain a solution A.
As an embodiment of the present invention, the step (2) is specifically: dissolving 83.6g of EDTA in 493.1g of 25 wt% ammonia water to obtain EDTA ammonia solution; and mixing the solution A with an EDTA ammonia solution to obtain a mixed solution B.
The second object of the present invention is to provide a carbon nanotube catalyst having high activity prepared by the foregoing method.
The third objective of the present invention is to provide an application of the carbon nanotube catalyst with high activity in the preparation of carbon nanotubes by cracking olefin gases.
A fourth object of the present invention is to provide a method for increasing the yield of carbon nanotubes prepared by cracking olefin-based gas, which uses the above carbon nanotube catalyst having high activity, the method comprising the steps of:
placing the carbon nano tube catalyst with high activity in a tube furnace, and heating to 300 ℃ under the protection of inert gas; after the temperature reaches 300 ℃, continuously introducing 1000sccm hydrogen, and heating to 700 ℃ at a speed of 10 ℃/min; and after the temperature reaches 700 ℃, continuously introducing mixed gas of 300sccm ethylene, 300sccm nitrogen and 100sccm hydrogen, reacting for 60min at constant temperature, and cooling to obtain the carbon nano tube.
The fifth object of the present invention is to provide a carbon nanotube in which the metallic element residue is not higher than 0.6%, and the structure thereof is an ultra-long bundle structure.
Has the beneficial effects that:
(1) the invention uses a two-step complexing method of Citric Acid (CA) and Ethylene Diamine Tetraacetic Acid (EDTA) ammonia solution to synthesize a high-activity metal oxide catalyst for synthesizing the carbon nano tube. The yield of the carbon nano tube obtained by the high-efficiency catalyst of the unit weight of the metal element of the catalyst is not lower than 169g/g and can reach 246g/g at most, namely, the metal residue in the carbon nano tube is about 0.4 percent, the purification treatment of the carbon nano tube can be reduced or even avoided, and the production cost of the carbon nano tube is reduced.
(2) The catalyst prepared by the CA-EDTA ammonia solution two-step complexation method has a loose sheet-shaped stacking mode, so that the grown carbon nanotubes are in an ultra-long bundle shape, and the utilization efficiency of the catalyst is greatly improved; the more uniform distribution of the active centers enables the full utilization of the active centers and the carbon nano tubes with higher yield.
(3) The method for preparing the catalyst based on the CA-EDTA ammonia solution two-step complexing method has simple process, greatly reduces the production cost and improves the production profit of enterprises.
(4) The carbon nano tube prepared by the invention has the characteristic structure of an ultra-long beam shape, the length of the carbon nano tube can reach more than 50 microns, the length-diameter ratio is large, the electric conduction and the heat conduction are good, and the carbon nano tube can be used as a carbon fiber, a lithium battery cathode material and a conductive agent.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst prepared in example 2 of the present invention, with a scale of 1 μm.
FIG. 2 is a scanning electron micrograph of a catalyst prepared in example 2 of the present invention, with a 5 μm scale.
FIG. 3 is a scanning electron microscope image of a carbon nanotube synthesized using the catalyst prepared in example 2 of the present invention, with a 2 μm scale.
FIG. 4 is a scanning electron micrograph of a carbon nanotube synthesized using the catalyst prepared in example 2 of the present invention, with a scale of 10 μm.
FIG. 5 is a scanning electron micrograph of a carbon nanotube synthesized using the catalyst prepared in example 2 according to the present invention, with a scale of 20 μm.
FIG. 6 is a scanning electron micrograph of a carbon nanotube synthesized using the catalyst prepared in example 2 according to the present invention, with a scale of 50 μm.
Detailed Description
The mass fraction of the aqueous ammonia in each example and comparative example was 25 wt%, and the aqueous ammonia solution was reagent grade.
Yield of carbon nanotubes-weight of carbon nanotubes/weight of catalyst metal element;
catalyst metal element weight ═ catalyst weight ═ iron cobalt element/all elements ═ 0.13 catalyst weight.
Example 1
A preparation method of a synthetic carbon nanotube catalyst comprises the following steps:
(1) 102.6g of magnesium nitrate hexahydrate, 30g of aluminum nitrate nonahydrate, 8.9g of ferric nitrate nonahydrate, 5.2g of cobalt nitrate hexahydrate, 585g of pure water and 100g of citric acid are sequentially added into a 1L beaker, the mixture is placed into a constant-temperature water bath kettle at the temperature of 92 ℃, a tetrafluoro blade is mechanically stirred at 400rpm to dissolve the raw materials, then 0.71g of ammonium heptamolybdate is added, the mixture is stirred and dissolved, and the mixture is continuously stirred, heated and concentrated until the liquid level of the solution is 500 mL. Taking out the beaker and cooling to normal temperature to obtain a solution A.
(2) 60.8g of EDTA and 359g of ammonia water were sequentially added to a 1L beaker, and dissolved at room temperature with stirring to form an EDTA ammonia solution.
(3) And pouring the solution A into an EDTA ammonia solution, continuously stirring for 30min, and then weighing 30g of the solution and filling the solution into an open porcelain cell. And (3) after the temperature of the muffle furnace is raised to 500 ℃ and the temperature is constant, putting the porcelain element containing the solution into the muffle furnace for carbonization for 30min to form a loose and porous catalyst precursor, setting the temperature of the muffle furnace to 450 ℃ after the carbonization is finished, and roasting at the constant temperature for 240 min. The product was sieved through a 80 mesh sieve and crushed to form a powdery catalyst.
The method for preparing carbon nanotubes using the catalyst prepared in example 1 was as follows:
weighing 0.3g of the prepared powdery catalyst, placing the powdery catalyst in a middle area of a tubular furnace with the diameter of 60mm, raising the temperature to 300 ℃ at the temperature raising rate of 10 ℃/min under the protection of 1000sccm nitrogen, starting to continuously introduce 1000sccm hydrogen, continuing to raise the temperature to 700 ℃ at the temperature raising rate of 10 ℃/min, starting to introduce mixed gas of 300sccm ethylene, 300sccm nitrogen and 100sccm hydrogen after the temperature reaches 700 ℃, and reacting for 60 minutes at constant temperature. Cooling and taking out the product, namely the carbon nano tube.
The results show that the catalyst of example 1 can successfully produce carbon nanotubes, the weight of which is 6.6g and the bulk density of which is 0.006 g/ml. The yield of carbon nanotubes obtained from the catalyst of example 1 per weight of the catalytic metal element was 169 g/g. The residue of the metal element of iron and cobalt in the carbon nano tube is about 0.6 percent.
Example 2
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 1, except that the amounts of EDTA and ammonia were adjusted, specifically:
(1) 102.6g of magnesium nitrate hexahydrate, 30g of aluminum nitrate nonahydrate, 8.9g of ferric nitrate nonahydrate, 5.2g of cobalt nitrate hexahydrate, 585g of pure water and 100g of citric acid are sequentially added into a 1L beaker, the mixture is placed into a constant-temperature water bath kettle at the temperature of 92 ℃, a tetrafluoro blade is mechanically stirred at 400rpm to dissolve the raw materials, then 0.71g of ammonium heptamolybdate is added, the mixture is stirred and dissolved, and the mixture is continuously stirred, heated and concentrated until the liquid level of the solution is 500 mL. Taking out the beaker and cooling to normal temperature to obtain a solution A.
(2) 83.6g of EDTA and 493.1g of ammonia water were sequentially added to a 1L beaker, and dissolved at room temperature with stirring to form an EDTA ammonia solution.
(3) And pouring the solution A into an EDTA ammonia solution, continuously stirring for 30min, and then weighing 30g of the solution and filling the solution into an open porcelain cell. And (3) after the muffle furnace is heated to 500 ℃ and the constant temperature is kept, putting the porcelain element containing the solution into the muffle furnace for carbonization to form a loose and porous catalyst precursor, setting the temperature of the muffle furnace to 450 ℃ after the carbonization is completed for 30min at 500 ℃, and roasting at the constant temperature for 240 min. The product was sieved through a 80 mesh sieve and crushed to form a powdery catalyst.
The method for preparing carbon nanotubes using the catalyst prepared in example 2 was the same as in example 1.
Scanning electron micrographs of the powdered catalyst of example 2 and the product carbon nanotubes prepared therefrom are shown in fig. 1-2 and fig. 3-4, respectively. As shown in fig. 1-2, the catalyst of the present invention exhibits a loose plate packing pattern, a relatively uniform distribution of active sites, which structure has the effect of: the sheet structure enables the grown carbon nano tubes to be in a super-long bundle shape; the more uniform distribution of the active centers leads the activity of the catalyst to be improved, the carbon nano tube with higher yield is obtained, and the utilization efficiency of the catalyst is greatly improved. The carbon nano tube prepared by the method has good electric conduction, heat conduction and mechanical properties, and can be used as a lithium battery cathode material and a conductive agent.
The results show that the catalyst of example 2 can successfully prepare the carbon nanotube product, and the weight of the carbon nanotube product obtained in example 2 is 9.6g, and the bulk density is 0.006 g/ml. The yield of carbon nanotubes obtained from the catalyst of example 2 per weight of the catalyst metal element was 246 g/g. The residue of the metal element of iron and cobalt in the carbon nano tube is about 0.4 percent.
Example 3
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 1, except that the amount of EDTA and ammonia was adjusted, specifically:
(1) 102.6g of magnesium nitrate hexahydrate, 30g of aluminum nitrate nonahydrate, 8.9g of ferric nitrate nonahydrate, 5.2g of cobalt nitrate hexahydrate, 585g of pure water and 100g of citric acid are sequentially added into a 1L beaker, the mixture is placed into a constant-temperature water bath kettle at the temperature of 92 ℃, a tetrafluoro blade is mechanically stirred at 400rpm to dissolve the raw materials, then 0.71g of ammonium heptamolybdate is added, the mixture is stirred and dissolved, and the mixture is continuously stirred, heated and concentrated until the liquid level of the solution is 500 mL. Taking out the beaker and cooling to normal temperature to obtain a solution A.
(2) 98.78g of EDTA and 582.8g of ammonia water were sequentially added to a 1L beaker, and dissolved by stirring at room temperature to form an EDTA ammonia solution.
(3) And pouring the solution A into an EDTA ammonia solution, continuously stirring for 30min, and then weighing 30g of the solution and filling the solution into an open porcelain cell. And (3) after the temperature of the muffle furnace is raised to 500 ℃ and the temperature is constant, putting the porcelain element containing the solution into the muffle furnace for carbonization for 30min to form a loose and porous catalyst precursor, setting the temperature of the muffle furnace to 450 ℃ after the carbonization is finished, and roasting at the constant temperature for 240 min. The product is sieved by a 80-mesh sieve and crushed to form the powdery catalyst.
The method for preparing carbon nanotubes using the catalyst prepared in example 3 was the same as in example 1.
The results show that the catalyst of example 3 can successfully prepare the carbon nanotube product, and the weight of the carbon nanotube product obtained in example 3 is 7.8g, and the bulk density is 0.006 g/ml. The yield of carbon nanotubes obtained from the catalyst of example 3 per weight of the catalyst metal element was 200 g/g. The residue of the metal element of iron and cobalt in the carbon nano tube is about 0.5 percent.
From examples 1-3, it can be analyzed that the yield of the carbon nanotubes prepared in example 2 is the highest, and is as high as 246g/g, which indicates that the content of EDTA and ammonia in example 2 is the best, and too high or too low may cause the structure of the catalyst to change, thereby affecting the activity of the catalyst in synthesizing the carbon nanotubes.
Comparative example 1
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that only the amount of EDTA used is adjusted such that the molar ratio of EDTA to metal precursor salt is less than 0.35: 1. For example, the molar ratio of EDTA to metal precursor salt is 0.3: 1.
The carbon nanotubes were prepared using the catalyst of comparative example 1 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 1 was 3.3 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 1 per weight of the metal element of the catalyst was 85 g/g.
Comparative example 2
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that only the amount of EDTA used is adjusted so that the molar ratio of EDTA to the metal precursor salt is higher than 0.75: 1. For example, the molar ratio of EDTA to metal precursor salt is 0.8: 1.
The carbon nanotubes were prepared using the catalyst of comparative example 2 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 2 was 5.1 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 2 per the weight of the metal element of the catalyst was 131 g/g.
As can be seen from comparative analysis of examples 1-3 and comparative examples 1-2, the optimal range of the molar ratio of EDTA to the metal precursor salt is 0.35-0.75: 1, 6.6-9.6 g of product carbon nanotubes can be successfully prepared within the range, and the yield of the carbon nanotubes obtained by the high-efficiency catalyst per unit weight of the metal element of the catalyst is not lower than 169 g/g; outside this range, the aforementioned effects cannot be achieved.
Comparative example 3
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that only the amount of ammonia water is adjusted such that the mass ratio of ammonia water to EDTA is less than 4:1, for example, 3: 1.
The carbon nanotubes were prepared using the catalyst of comparative example 3 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 3 was 5.4 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 3 per weight of catalyst metal element was only 138 g/g.
Comparative example 4
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that only the amount of ammonia water is adjusted so that the mass ratio of ammonia water to EDTA is higher than 7:1, for example, 8: 1.
The carbon nanotubes were prepared using the catalyst of comparative example 4 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 4 was 6.0 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 4 per weight of the catalyst metal element was 153.8 g/g.
As can be seen from comparative analysis of examples 1-3 and comparative examples 3-4, the optimal mass ratio of ammonia water to EDTA is 4-7: 1, 6.6 g-9.6 g of carbon nanotubes can be successfully prepared, and the yield of the carbon nanotubes obtained by the catalyst with the unit weight of the metal element of the catalyst is not lower than 169 g/g; outside this range, the aforementioned effects cannot be achieved.
Comparative example 5
A method for preparing a catalyst for synthesizing carbon nanotubes, with reference to example 2, except that only the amount of citric acid used is adjusted such that the molar ratio of citric acid to the metal precursor salt is less than 1:1, for example, such that the molar ratio of citric acid to the metal precursor salt is 0.7: 1.
The carbon nanotubes were prepared using the catalyst of comparative example 5 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 5 was 2.6 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 5 per weight of catalyst metal element was only 66.7 g/g.
Comparative example 6
A method for preparing a catalyst for synthesizing carbon nanotubes, with reference to example 2, except that only the amount of citric acid used is adjusted such that the molar ratio of citric acid to the metal precursor salt is higher than 1.5:1, for example, such that the molar ratio of citric acid to the metal precursor salt is 2: 1.
The carbon nanotubes were prepared using the catalyst of comparative example 6 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes of comparative example 6 was 4.6 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 6 per the weight of the metal element of the catalyst was only 118 g/g.
Comparative example 7 citric acid alone complexation method
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that the addition of EDTA was omitted and the amount of citric acid was adjusted to an optimal amount of 149.9g (determined according to the highest yield of carbon nanotubes obtained by the catalyst per weight of the metal element of the catalyst).
The carbon nanotubes were prepared using the catalyst of comparative example 7 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 7 was 1.8 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 7 per weight of catalyst metal element was only 46 g/g.
Analysis of example 2 and comparative example 7 revealed that the catalytic activity (yield of carbon nanotubes obtained per weight of the metal element of the catalyst) of the prepared catalyst was significantly reduced by omitting the EDTA complexing agent, indicating that the addition of EDTA had an unexpected effect on the improvement of the activity of the catalyst of the present invention.
Comparative example 8 EDTA complexation alone
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that the addition of citric acid was omitted and the amount of EDTA was adjusted to an optimal amount of 98.78 g.
The carbon nanotubes were prepared using the catalyst of comparative example 8 in the same manner as in example 2, and the results showed that the weight of the product carbon nanotubes obtained in comparative example 8 was 0.90 g. The yield of carbon nanotubes obtained from the catalyst of comparative example 8 per weight of catalyst metal element was only 23 g/g.
Analysis of example 2 and comparative example 8 revealed that the catalyst prepared after omitting citric acid had a significantly reduced catalytic activity (yield of carbon nanotubes obtained per weight of catalyst metal element), indicating that the addition of citric acid had an unexpected effect on the improvement of the catalytic activity of the present invention.
Comparative example 9
A method for preparing a catalyst for synthesizing carbon nanotubes, referring to example 2, except that complexing is performed using an ammonium EDTA solution and then adding citric acid, specifically:
(1) 102.6g of magnesium nitrate hexahydrate, 30g of aluminum nitrate nonahydrate, 8.9g of ferric nitrate nonahydrate, 5.2g of cobalt nitrate hexahydrate and 585g of pure water are sequentially weighed into a 1L beaker, 83.6g of EDTA and 493.1g of ammonia water are added, stirred and dissolved, 0.71g of ammonium heptamolybdate is added, and the mixture is stirred at normal temperature for 30min to be fully dissolved to obtain a solution B.
(2) Weighing 100g of citric acid to prepare an aqueous solution;
(3) and (2) pouring the solution B obtained in the step (1) into a citric acid aqueous solution, putting the solution B into a constant-temperature water bath kettle at the temperature of 92 ℃, mechanically stirring by using a tetrafluoro blade at 400rpm, and heating and concentrating until the volume of the solution is equal to that of the mixed solution obtained in the step (3) in the example 1. After taking out the beaker and cooling to normal temperature, 30g of the solution is weighed and put into an open porcelain cell. And (3) after the temperature of the muffle furnace is raised to 500 ℃ and the temperature is constant, putting the porcelain element containing the solution into the muffle furnace for carbonization for 30min to form a loose and porous catalyst precursor, setting the temperature of the muffle furnace to 450 ℃ after the carbonization is finished, and roasting at the constant temperature for 240 min. The product was sieved through a 80 mesh sieve and crushed to form a powdery catalyst.
The carbon nanotubes were prepared using the catalyst of comparative example 9 in the same manner as in example 2, and it was found that the weight of the carbon nanotubes obtained in comparative example 9 was only 0.3g, and almost no carbon nanotube product was produced.
Claims (9)
1. A preparation method of a carbon nano tube catalyst with high activity is characterized in that a citric acid-ethylene diamine tetraacetic acid two-step complexation method is adopted, and the method comprises the following steps:
(1) mixing metal precursor salt, pure water and citric acid to prepare a mixed solution, adding ammonium heptamolybdate, and stirring to dissolve to obtain a citrate mixed solution; stirring and concentrating the citrate mixed solution in a water bath, and cooling to obtain a solution A; wherein the molar ratio of the citric acid to the metal precursor salt is (1-1.5): 1;
(2) dissolving EDTA in ammonia water to obtain EDTA ammonia solution; mixing the solution A with an EDTA ammonia solution to obtain a mixed solution B; then, placing the mixed solution B in an open porcelain original vessel, and carbonizing the mixed solution B for 30min at 500 ℃ in a muffle furnace; then, roasting the mixture in a muffle furnace at 450 ℃ for 240min, and sieving and crushing the mixture by a screen to form a powdery catalyst; wherein the molar ratio of EDTA to the metal precursor salt is (0.35-0.75): 1.
2. The method of claim 1, wherein the metal precursor salt in step (1) is Mg2+Salt, Al3+Salt, Fe3+Salt, Co2+A mixture of salts.
3. The method of claim 1, wherein the mass fraction of ammonia is 25 wt%; the mass ratio of the ammonia water to the EDTA is (4-7) to 1.
4. The method according to claim 2, wherein step (1) is specifically: mixing 102.6g of magnesium nitrate hexahydrate, 30g of aluminum nitrate nonahydrate, 8.9g of ferric nitrate nonahydrate, 5.2g of cobalt nitrate hexahydrate, 585g of pure water and 100g of citric acid, and stirring and dissolving in a water bath with constant temperature of 92 ℃ to obtain a mixed solution; then 0.71g of ammonium heptamolybdate is added into the solution, stirred and dissolved, stirred continuously, heated and concentrated until the volume of the solution is 500mL, and cooled to the normal temperature to obtain a solution A.
5. The method according to claim 4, wherein the step (2) is specifically: dissolving 83.6g of EDTA in 493.1g of 25 wt% ammonia water to obtain EDTA ammonia solution; and mixing the solution A with an EDTA ammonia solution to obtain a mixed solution B.
6. A carbon nanotube catalyst having high activity produced by the method of any one of claims 1 to 5.
7. The use of the carbon nanotube catalyst with high activity according to claim 6 in the preparation of carbon nanotubes by olefin gas cracking.
8. A method for increasing the yield of carbon nanotubes prepared by cracking olefin gases, which comprises the step of applying the carbon nanotube catalyst with high activity of claim 6:
placing the carbon nanotube catalyst with high activity of claim 6 in a tube furnace, and heating to 300 ℃ under the protection of inert gas; after the temperature reaches 300 ℃, continuously introducing 1000sccm hydrogen, and heating to 700 ℃ at a speed of 10 ℃/min; and after the temperature reaches 700 ℃, continuously introducing mixed gas of 300sccm ethylene, 300sccm nitrogen and 100sccm hydrogen, reacting at constant temperature for 60min, and cooling to obtain the carbon nano tube.
9. The carbon nanotube according to claim 8, wherein the carbon nanotube has a structure of an ultra-long bundle structure, and the metal element residue in the carbon nanotube is not more than 0.6%.
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| CN115672327A (en) * | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | High specific surface area superfine nano catalyst and preparation method and application thereof |
| CN115414937B (en) * | 2022-08-17 | 2024-04-16 | 华东理工大学 | Catalyst for preparing carbon nano tube by microwave catalytic pyrolysis of waste plastics and preparation method and application thereof |
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