CN1326613C - Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process - Google Patents
Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process Download PDFInfo
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- CN1326613C CN1326613C CNB200410068043XA CN200410068043A CN1326613C CN 1326613 C CN1326613 C CN 1326613C CN B200410068043X A CNB200410068043X A CN B200410068043XA CN 200410068043 A CN200410068043 A CN 200410068043A CN 1326613 C CN1326613 C CN 1326613C
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Abstract
The present invention discloses a compound metal oxide catalyst for preparing carbon nanometer tubes with a high production rate and a preparing process of the compound metal oxide catalyst. The compound metal oxide catalyst uses magnesium oxide as a carrier. Two or three of cobalt (Co), ferrum and nickel are compounded to form an oxide as a main catalyzing component. Molybdenum is used as a promotion catalyzing component. In the preparing process of the compound metal oxide catalyst, magnesium salt is dissolved into distilled water; main catalyzing component salt and promotion catalyzing component salt are added to be completely dissolved; the molar ratio of the magnesium salt, the main catalyzing component salt and the promotion catalyzing component salt is 0.5 to 2.5/0.1 to 1.0/0.5 to 3.0; foaming agents, such as citric acid, etc., are added to be stirred for 10 to 60 minutes; solution is put into a blast baking oven to be baked and foamed for 3 to 6 hours in 120 to 200 DEG C; after being taken out to be ground into powder, high temperature calcination is made for 10 to 30 minutes in 550 to 850 DEG C. Thus, a catalyst for preparing the carbon nanometer tubes is obtained. The compound metal oxide catalyst for preparing carbon nanometer tubes with a high production rate has the advantages of high catalyzing efficiency, good product graphitization degree, good repeatability of the preparing process, simple procedure and easy operation.
Description
Technical field
The present invention relates to the nano material preparation technical field, relate to O composite metallic oxide catalyst that is used for the produced in high yields CNT and preparation method thereof specifically.
Background technology
CNT is a kind of novel carbon nanomaterial of finding the nineties in 20th century, because machinery, mechanics, electronics, optics, calorifics and the energy-storage property of its excellence, caused sizable concern, have potential extensive use in a plurality of fields such as material, electronics, chemical industry, machinery, the energy: 1, CNT is the best field emmision material of performance up to now, can be used for making flat-panel monitor.2, because CNT has conductor and characteristic of semiconductor, make electronic devices such as diode with it, be expected to bring new leap to the microminiaturization and the high speed of computer industry.3, can be used for making biosensor and biology sensor at life science.4, CNT is present best hydrogen storage material, and this will bring glad tidings to fuel cell car and other energy storage device.5 utilize its huge specific area can make ultracapacitor.But 6, mix the different composite of component property etc. with various metals, nonmetal and macromolecular material.
One of key technology of made of carbon nanotubes is the controlled preparation of nanocatalyst, and the CNT exterior appearance and the internal performance of different nanocatalyst preparations are all different.Because caliber, wall thickness and the winding degree of CNT are all relevant with particle diameter, composition and the decentralization of nanocatalyst, ultra-fine, the high-dispersion nano catalyst that therefore obtains definite composition is the key and the prerequisite of preparation high-performance carbon nanotube.The preparation method of carbon current nanotube mainly contains arc discharge method, laser evaporation method and catalytic pyrolysis carbonaceous gas method, also has some other methods simultaneously, as molten-salt growth method, solar energy method, wet chemistry method.Arc discharge method is mainly used in the preparation SWCN, and reaction temperature is up to more than 3000 ℃.The laser evaporation method is to utilize the high temperature of laser to make the carbon atom volatilization in the graphite be reconstructed, and the experiment condition of requirement is higher; Catalytic pyrolysis carbonaceous gas method is the present modal method for preparing CNT, and its equipment is simple, and operating process is easy, is suitable for large-scale production especially.The problem that the catalyst of present preparation CNT mainly exists is that the productive rate of CNT is not high, and the catalyst residue in the product is higher, needs further purification process, is unfavorable for the direct application of CNT.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of O composite metallic oxide catalyst and above-mentioned Preparation of catalysts method that is used for the produced in high yields CNT at above-mentioned prior art present situation.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the O composite metallic oxide catalyst that this kind is used for the produced in high yields CNT is carrier with magnesia, load has the main catalytic component and promotes catalyst component on the carrier, three's mol ratio is 1.0～2.5: 0.1～0.5: 1.5～3.0, wherein, the main catalytic component is any compound of the two or three's oxide in iron, cobalt, the nickel, promotes that catalyst component is the oxide of molybdenum.
The mol ratio of iron and cobalt is 0.1～1.0: 0.1～1.0 in the binary complex of the oxide of described iron and cobalt, the mol ratio of cobalt and nickel is 0.1～1.0: 0.1～1.0 in the binary complex of the oxide of cobalt and nickel, the mol ratio of iron and nickel is 0.1～1.0: 0.1～1.0 in the binary complex of the oxide of iron and nickel, and the mol ratio of iron, cobalt, nickel is 0.1～1.0: 0.1～1.0 in the ternary complex of the oxide of iron, cobalt, nickel: 0.1～1.0.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the above-mentioned preparation method who is used for the O composite metallic oxide catalyst of produced in high yields CNT may further comprise the steps:
Magnesium salts is dissolved in the distilled water through stirring, adds main catalytic component salt again and promote catalyst component salt, continue stirring it is dissolved fully, three's mol ratio is 1.0～2.5: 0.1～0.5: 1.5～3.0; In the gained mixed solution, add blowing agent, continue to stir 10～120 minutes; The solution that is added with blowing agent is placed 120～200 ℃ of oven dry foaming 3～5 hours, and taking-up is pulverized last, in 550～850 ℃ of high-temperature calcinations 10～30 minutes, promptly obtains to be used to prepare the catalyst of CNT under aerobic environment.
The mol ratio of the addition of described blowing agent and magnesium salts addition is 1～5: 1.
Described blowing agent be ethylene glycol, citric acid, oxalic acid, polyethylene glycol or wherein appoint the two, three or four mixture.
Described magnesium salts be selected from magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate or wherein appoint the two, three or four mixture.
Described main catalytic component salt comprises the binary or the ternary complex of the one pack system salt of iron, cobalt or nickel.
Described molysite comprises ferric nitrate, iron chloride, ferric sulfate, ferric acetate, and cobalt salt comprises cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate, and nickel salt comprises nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate.
The mol ratio of iron and cobalt is 0.1～1.0: 0.1～1.0 in described molysite and the cobalt salt binary complex, the mol ratio of cobalt and nickel is 0.1～1.0: 0.1～1.0 in cobalt salt and the nickel salt binary complex, the mol ratio of iron and nickel is 0.1～1.0: 0.1～1.0 in molysite and the nickel salt binary complex, and the mol ratio of iron, cobalt, nickel is 0.1～1.0: 0.1～1.0 in molysite, cobalt salt, the nickel salt ternary complex: 0.1～1.0.
Described promotion catalyst component salt is the oxide of molybdenum acid ammonia or molybdenum.
The process that this catalyst is used for preparing CNT is generally: catalyst is placed reaction chamber, feed carbon-source gas such as methane, aromatic hydrocarbon, natural gas or its mixture again, flow velocity is that 500～5000sccm, hydrogen flow rate are that 0～2000sccm, nitrogen or inert gas flow velocity are in the atmosphere of 0～500sccm, reacted 20～60 minutes down in 750～1000 ℃, promptly obtain the multi-walled carbon nano-tubes product.In addition, before carbon nano tube growth, also can utilize the air in nitrogen or other inert gas emptying reative cell, after carbon nano tube growth is finished, utilize nitrogen or other inert gas that product is protected.
Compared with prior art, catalyst of the present invention adopts magnesia as carrier, and magnesia can make catalyst metal particles evenly disperse, and reduces its granularity, improves catalyst activity; On this basis, adopt composition metal as the main catalytic component, and control the molar ratio between carrier, main catalytic component and the promotion catalyst component three rightly, therefore make catalytic efficiency obtain significantly improving, after tested, with respect to common catalyst, the weight ratio of product and catalyst is higher than 40 times, the purity of CNT is higher than 95%, and the CNT caliber that is obtained is 20～40nm, and degree of graphitization is good; Method for preparing catalyst of the present invention has repeatable good, and process is simple, the advantage of easy operating.
The analysis contrast of transmission electron microscope (TEM) photo of the multi-walled carbon nano-tubes that Fig. 3 and Fig. 4 are taken as can be seen, when adopting aluminium oxide as carrier, contain more impurity in the multi-walled carbon nano-tubes that makes, and the content of impurity reduces obviously in the multi-walled carbon nano-tubes that makes with catalyst of the present invention.
Description of drawings
Fig. 1 is ESEM (SEM) photo of the multi-walled carbon nano-tubes that makes of the invention process example five;
Fig. 2 is the thermogravimetic analysis (TGA) figure (TGA) of the multi-walled carbon nano-tubes that makes of the invention process example five;
Fig. 3 is transmission electron microscope (TEM) photo of the multi-walled carbon nano-tubes that makes of the invention process example six;
Fig. 4 is transmission electron microscope (TEM) photo of the multi-walled carbon nano-tubes that makes when adopting aluminium oxide as carrier.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment one: a kind of O composite metallic oxide catalyst of produced in high yields CNT, it is carrier with magnesia, load has the binary complex of oxide of iron and cobalt and the oxide of molybdenum on the carrier, three's mol ratio is 2.5: 0.5: 0.5, the mol ratio of iron and cobalt is 0.5: 0.5 in the binary complex of the oxide of iron and cobalt, the mol ratio of cobalt and nickel is 0.1: 1.0 in the binary complex of the oxide of cobalt and nickel, the mol ratio of iron and nickel is 1.0: 0.1 in the binary complex of the oxide of iron and nickel, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 0.1: 0.5: 1.0.
Embodiment two: a kind of O composite metallic oxide catalyst of produced in high yields CNT, it is carrier with magnesia, load has the binary complex of oxide of iron and cobalt and the oxide of molybdenum on the carrier, three's mol ratio is 0.5: 0.5: 3.0, the mol ratio of iron and cobalt is 0.5: 1.0 in the binary complex of the oxide of iron and cobalt, the mol ratio of cobalt and nickel is 1.0: 0.5 in the binary complex of the oxide of cobalt and nickel, the mol ratio of iron and nickel is 0.5: 0.5 in the binary complex of the oxide of iron and nickel, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 1.0: 0.5: 0.1.
Embodiment three: a kind of O composite metallic oxide catalyst of produced in high yields CNT, it is carrier with magnesia, load has the binary complex of oxide of iron and cobalt and the oxide of molybdenum on the carrier, three's mol ratio is 1.0: 0.1: 2.5, the mol ratio of iron and cobalt is 0.5: 0.1 in the binary complex of the oxide of iron and cobalt, the mol ratio of cobalt and nickel is 1.0: 0.1 in the binary complex of the oxide of cobalt and nickel, the mol ratio of iron and nickel is 0.1: 1.0 in the binary complex of the oxide of iron and nickel, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 0.5: 0.1: 0.5.
Embodiment four: a kind of O composite metallic oxide catalyst of produced in high yields CNT, it is carrier with magnesia, load has the binary complex of oxide of iron and cobalt and the oxide of molybdenum on the carrier, three's mol ratio is 2.0: 1.0: 1.5, the mol ratio of iron and cobalt is 1.0: 0.1 in the binary complex of the oxide of iron and cobalt, the mol ratio of cobalt and nickel is 0.5: 0.1 in the binary complex of the oxide of cobalt and nickel, the mol ratio of iron and nickel is 0.5: 1.0 in the binary complex of the oxide of iron and nickel, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 0.5: 1.0: 0.5.
Embodiment five: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Mo: Mg=1 in molar ratio: 4: 50: 50, take by weighing ferric nitrate, cobalt nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, cobalt nitrate and ammonium molybdate more successively, treat four all dissolvings fully, the weighing citric acid that equals the magnesium mole adds above-mentioned solution again, continue to stir after 30 minutes, 160 ℃ of oven dry foaming, the time is 4 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 20 minutes in 650 ℃ of air.
The actual conditions of carbon nano tube growth is as follows: 960 ℃ of reaction temperatures,
The flow-rate ratio of methane and nitrogen was respectively 8: 1, and the reaction time is 40 minutes.The product that adds the acquisition of 1g catalyst is 44.2g.The stereoscan photograph of product such as Fig. 1, thermogravimetic analysis (TGA) as shown in Figure 2.The TGA curve shows that weightlessness mainly is created between 600～700 ℃, is the oxidation warm area of multi-walled carbon nano-tubes, and weightlessness reaches 96.3%, illustrates that product is highly purified multi-walled carbon nano-tubes, and this product can be purified.
Embodiment six: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Ni: Co: Mo: Mg=4 in molar ratio: 7: 110: 150, take by weighing nickelous sulfate, cobaltous sulfate, ammonium molybdate, magnesium sulfate, earlier magnesium sulfate is dissolved in an amount of distilled water, add nickelous sulfate, cobaltous sulfate and ammonium molybdate more successively, treat four all dissolvings fully, 3 times of oxalic acid that equal the magnesium mole of weighing add above-mentioned solution again, continue to stir after 40 minutes, 130 ℃ of oven dry foaming, the time is 5 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 30 minutes in 600 ℃ of air.
The actual conditions of carbon nano tube growth is as follows: 970 ℃ of reaction temperatures, and the flow-rate ratio of methane and nitrogen was respectively 6: 1, and the reaction time is 40 minutes.The product that adds the acquisition of 0.1g catalyst is 6.32g, the transmission electron microscope photo of product such as Fig. 3.
Embodiment seven: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Ni: Mo: Mg=5 in molar ratio: 5: 150: 80, take by weighing iron chloride, nickel chloride, ammonium molybdate, magnesium chloride, earlier magnesium chloride is dissolved in an amount of distilled water, add iron chloride, nickel chloride and ammonium molybdate more successively, treat four all dissolvings fully, 2 times of ethylene glycol that equal the magnesium mole of weighing add above-mentioned solution again, continue to stir after 50 minutes, 150 ℃ of oven dry foaming, the time is 4 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 20 minutes in 750 ℃ of air.
The actual conditions of carbon nano tube growth is as follows: 960 ℃ of reaction temperatures, and the flow-rate ratio of methane and nitrogen was respectively 4: 1, and the reaction time is 60 minutes.The product that adds the acquisition of 0.3g catalyst is 16.8g.
Embodiment eight: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Ni: Mo: Mg=2 in molar ratio: 3: 4: 80: 200, take by weighing ferric acetate, cobalt acetate, nickel acetate, ammonium molybdate, magnesium acetate, earlier magnesium acetate is dissolved in an amount of distilled water, add ferric acetate, nickel acetate, cobalt acetate and ammonium molybdate more successively, treat that it dissolves fully, the weighing polyethylene glycol that equals the magnesium mole adds above-mentioned solution again, continue to stir after 30 minutes, 160 ℃ of oven dry foaming, the time is 4 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 10 minutes in 700 ℃ of air.
Embodiment nine: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Mo: Mg=1 in molar ratio: 10: 330: 55, take by weighing ferric nitrate, cobalt nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, cobalt nitrate and ammonium molybdate more successively, treat four all dissolvings fully, 1.5 times of oxalic acid to the magnesium mole of weighing add above-mentioned solution again, continue to stir after 40 minutes, 180 ℃ of oven dry foaming, the time is 3 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 30 minutes in 700 ℃ of air.
Embodiment ten: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Mo: Mg=10 in molar ratio: 1: 55: 275, take by weighing nickelous sulfate, cobaltous sulfate, ammonium molybdate, magnesium sulfate, earlier magnesium sulfate is dissolved in an amount of distilled water, add nickelous sulfate, cobaltous sulfate and ammonium molybdate more successively, treat four all dissolvings fully, 3 times of oxalic acid to the magnesium mole of weighing add above-mentioned solution again, continue to stir after 60 minutes, 140 ℃ of oven dry foaming, the time is 5 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 20 minutes in 750 ℃ of air.
Embodiment 11: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Ni: Mo: Mg=1 in molar ratio: 10: 330: 275, take by weighing iron chloride, nickel chloride, ammonium molybdate, magnesium chloride, earlier magnesium chloride is dissolved in an amount of distilled water, add iron chloride, nickel chloride and molybdenum oxide more successively, treat four all dissolvings fully, 2 times of citric acids to the magnesium mole of weighing add above-mentioned solution again, continue to stir after 60 minutes, 150 ℃ of oven dry foaming, the time is 3 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 30 minutes in 600 ℃ of air.
Embodiment 12: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Ni: Co: Mo: Mg=1 in molar ratio: 10: 55: 55, take by weighing ferric acetate, cobalt acetate, nickel acetate, ammonium molybdate, magnesium acetate, earlier magnesium acetate is dissolved in an amount of distilled water, add ferric acetate, nickel acetate, cobalt acetate and ammonium molybdate more successively, treat that it dissolves fully, the weighing polyethylene glycol that equals the magnesium mole adds above-mentioned solution again, continue to stir after 30 minutes, 160 ℃ of oven dry foaming, the time is 4 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 10 minutes in 650 ℃ of air.
Embodiment 13: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Ni: Mo: Mg=10 in molar ratio: 1: 330: 150, take by weighing ferric nitrate, cobalt nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, cobalt nitrate and ammonium molybdate more successively, treat four all dissolvings fully, the weighing ethylene glycol that equals the magnesium mole adds above-mentioned solution again, continue to stir after 30 minutes, 140 ℃ of oven dry foaming, the time is 4 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 30 minutes in 550 ℃ of air.
Embodiment 14: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Ni: Co: Mo: Mg=10 in molar ratio: 1: 100: 275, take by weighing nickelous sulfate, cobaltous sulfate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add nickelous sulfate, cobaltous sulfate and ammonium molybdate more successively, treat four all dissolvings fully, the weighing citric acid that equals the magnesium mole adds above-mentioned solution again, continue to stir after 30 minutes, 170 ℃ of oven dry foaming, the time is 3 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 20 minutes in 700 ℃ of air.
Embodiment 15: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Ni: Mo: Mg=10 in molar ratio: 1: 1: 60: 300, take by weighing iron chloride, nickel chloride, ammonium molybdate, magnesium chloride, earlier magnesium chloride is dissolved in an amount of distilled water, add iron chloride, nickel chloride and ammonium molybdate more successively, treat four all dissolvings fully, two times of ethylene glycol that equal the magnesium mole of weighing add above-mentioned solution again, continue to stir after 60 minutes, 150 ℃ of oven dry foaming, the time is 3 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 30 minutes in 600 ℃ of air.
Embodiment 16: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Ni: Mo: Mg=1 in molar ratio: 1: 10: 360: 60, take by weighing ferric nitrate, cobalt nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, cobalt nitrate and ammonium molybdate more successively, treat four all dissolvings fully, the weighing citric acid that equals the magnesium mole adds above-mentioned solution again, continue to stir after 40 minutes, 180 ℃ of oven dry foaming, the time is 3 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 10 minutes in 750 ℃ of air.
Embodiment 17: a kind of preparation method of O composite metallic oxide catalyst of produced in high yields CNT, Fe: Co: Ni: Mo: Mg=1 in molar ratio: 10: 1: 170: 275, take by weighing nickelous sulfate, cobaltous sulfate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add nickelous sulfate, cobaltous sulfate and ammonium molybdate more successively, treat four all dissolvings fully, two times of oxalic acid that equal the magnesium mole of weighing add above-mentioned solution again, continue to stir after 30 minutes, 150 ℃ of oven dry foaming, the time is 4 hours with solution.With the foamed product porphyrize that obtains, calcining promptly obtains can be used to prepare the catalyst of CNT after 20 minutes in 600 ℃ of air.
Claims (10)
1, a kind of O composite metallic oxide catalyst of produced in high yields CNT, it is carrier with magnesia, load has the main catalytic component and promotes catalyst component on the carrier, the mol ratio that it is characterized in that the three is 1.0～2.5: 0.1～0.5: 1.5～3.0, wherein, the main catalytic component is any compound of the two or three's oxide in iron, cobalt, the nickel, promotes that catalyst component is the oxide of molybdenum.
2, the O composite metallic oxide catalyst of produced in high yields CNT as claimed in claim 1, it is characterized in that the mol ratio of iron and cobalt is 0.1～1.0: 0.1～1.0 in the binary complex of oxide of described iron and cobalt, the mol ratio of cobalt and nickel is 0.1～1.0: 0.1～1.0 in the binary complex of the oxide of cobalt and nickel, the mol ratio of iron and nickel is 0.1～1.0: 0.1～1.0 in the binary complex of the oxide of iron and nickel, and the mol ratio of iron, cobalt, nickel is 0.1～1.0: 0.1～1.0 in the ternary complex of the oxide of iron, cobalt, nickel: 0.1～1.0.
3, the preparation method of the O composite metallic oxide catalyst of the described produced in high yields CNT of claim 1 is characterized in that may further comprise the steps:
Magnesium salts is dissolved in the distilled water through stirring, adds main catalytic component salt again and promote catalyst component salt, continue stirring it is dissolved fully, three's mol ratio is 1.0～2.5: 0.1～0.5: 1.5～3.0; In the gained mixed solution, add blowing agent, continue to stir 10～60 minutes; Place convection oven in 120～200 ℃ of oven dry foaming 3～6 hours the solution that is added with blowing agent, taking-up is pulverized last, 550～850 ℃ of high-temperature calcinations, promptly obtains to be used to prepare the catalyst of CNT.
4, the preparation method of the O composite metallic oxide catalyst of produced in high yields CNT as claimed in claim 3 is characterized in that the addition of described blowing agent and the mol ratio of magnesium salts addition are 1～5: 1.
5, as the preparation method of the O composite metallic oxide catalyst of claim 3 or 4 described produced in high yields CNTs, it is characterized in that described blowing agent be ethylene glycol, citric acid, oxalic acid, polyethylene glycol or wherein appoint the two, three or four mixture.
6, as the preparation method of the O composite metallic oxide catalyst of claim 3 or 4 described produced in high yields CNTs, it is characterized in that described magnesium salts be selected from magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate or wherein appoint the two, three or four mixture.
7, as the preparation method of the O composite metallic oxide catalyst of claim 3 or 4 described produced in high yields CNTs, it is characterized in that described main catalytic component salt comprises the binary or the ternary complex of the one pack system salt of iron, cobalt or nickel.
8, the preparation method of the O composite metallic oxide catalyst of produced in high yields CNT as claimed in claim 7, it is characterized in that described molysite comprises ferric nitrate, iron chloride, ferric sulfate, ferric acetate, cobalt salt comprises cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate, and nickel salt comprises nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate.
9, the preparation method of the O composite metallic oxide catalyst of produced in high yields CNT as claimed in claim 7, it is characterized in that the mol ratio of iron and cobalt is 0.1～1.0: 0.1～1.0 in described molysite and the cobalt salt binary complex, the mol ratio of cobalt and nickel is 0.1～1.0: 0.1～1.0 in cobalt salt and the nickel salt binary complex, the mol ratio of iron and nickel is 0.1～1.0: 0.1～1.0 in molysite and the nickel salt binary complex, and the mol ratio of iron, cobalt, nickel is 0.1～1.0: 0.1～1.0 in molysite, cobalt salt, the nickel salt ternary complex: 0.1～1.0.
10, the preparation method of the O composite metallic oxide catalyst of produced in high yields CNT as claimed in claim 3 is characterized in that described promotion catalyst component salt is molybdate.
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| CN114515578B (en) * | 2021-12-31 | 2023-05-23 | 佛山市格瑞芬新能源有限公司 | Catalyst for preparing carbon nano tube and preparation method and application thereof |
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| CN115477300B (en) * | 2022-08-03 | 2024-05-07 | 烯湾科城(广州)新材料有限公司 | Carbon nanotube, fluidized bed preparation process thereof and conductive agent |
| 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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| CN1477057A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Metal oxide catalyst for preparing bundle-formed multiwall nano carbon tube, its preparation method and application |
| CN1476930A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled |
| WO2004073859A1 (en) * | 2003-02-24 | 2004-09-02 | Shell Internationale Research Maatschappij B.V. | Catalyst composition preparation and use |
| CN1530321A (en) * | 2003-03-14 | 2004-09-22 | 中国科学院成都有机化学研究所 | Catalyst for preparing carbon nanometer pipe with small pipe diameter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004073859A1 (en) * | 2003-02-24 | 2004-09-02 | Shell Internationale Research Maatschappij B.V. | Catalyst composition preparation and use |
| CN1530321A (en) * | 2003-03-14 | 2004-09-22 | 中国科学院成都有机化学研究所 | Catalyst for preparing carbon nanometer pipe with small pipe diameter |
| CN1477057A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Metal oxide catalyst for preparing bundle-formed multiwall nano carbon tube, its preparation method and application |
| CN1476930A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled |
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