CN1308071C - Lanthanum doped catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof - Google Patents
Lanthanum doped catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof Download PDFInfo
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- CN1308071C CN1308071C CNB2004100935941A CN200410093594A CN1308071C CN 1308071 C CN1308071 C CN 1308071C CN B2004100935941 A CNB2004100935941 A CN B2004100935941A CN 200410093594 A CN200410093594 A CN 200410093594A CN 1308071 C CN1308071 C CN 1308071C
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Abstract
The present invention discloses a lanthanum doped catalyst for preparing carbon nano tubes with uniform diameters and a preparing method of the lanthanum doped catalyst. The lanthanum doped monometallic catalyst uses magnesium oxide as a carrier, uses an oxide compounded by two or three of cobalt (Co), ferrum and nickel as the component of a composite metal oxide, uses an oxide of lanthanum as a doped component, and uses an oxide of molybdenum as a promotion catalyzing component. In the preparing method of the lanthanum doped catalyst, magnesium salt is dissolved into distilled water; composite metal oxide component salt, lanthanum doped component salt and promotion catalyzing component salt are added to be completely dissolved; the molar ratio of the magnesium salt, the composite metal oxide component salt, the lanthanum doped component salt and the promotion catalyzing component salt is 0.5 to 3.0/0.1 to 1.0/0.01 to 1.0/0.5 to 3.0; the solution is placed in 120 to 200 DEG C to be baked for 3 to 5 hours, and then is calcinated in high temperature of 550 to 850 DEG C for 10 to 30 minutes; after taken out to be porphyrized into powder, a catalyst for preparing the carbon nano tubes is obtained. The lanthanum doped catalyst for preparing carbon nano tubes with uniform diameters has the advantages of high catalyzing efficiency, uniform product tube diameter and good graphitization degree; the preparing process of the lanthanum doped catalyst has the advantages of good repeatability, simple procedure and easy operation.
Description
Technical field
The present invention relates to prepare the catalyst of CNT, especially relate to a kind of lanthanum doped catalyst and preparation method who prepares carbon nano tube with uniform diameter.
Background technology
CNT is a kind of novel carbon structure of finding the nineties in 20th century, have excellent machinery, mechanics, electronics, optics, calorifics and energy-storage property, thereby caused sizable concern, had potential extensive use in a plurality of fields such as electronics, chemistry, micromechanics, the energy.Utilize machinery, mechanical property and the electric property of its excellence, it is added in various metals, the nonmetal or macromolecular material, various performances that can reinforcing material, and improve its electric conductivity; Utilize the emission Electronic Performance of its excellence, can obtain the EED of low driving voltage; Utilize its nano-scale and electric conductivity, can carry out the Micro Electro Mechanical System design; Utilize its unique cavity structure as reactor, can study of the behavior of multiple material at nano-scale; The same high-specific surface area that utilizes its cavity structure to produce can be used as the electrode material of Ni-MH battery, lithium ion battery or fuel cell.
The preparation method of carbon current nanotube mainly contains arc discharge method, laser evaporation method and catalytic chemical gaseous phase deposition (CCVD) method, also has some other methods simultaneously, as molten-salt growth method, solar energy method, wet chemistry method etc.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.But it is the Preparation of catalysts technology that the CCVD legal system is equipped with the key of CNT, the CNT of different Preparation of Catalyst has different patterns and performance, the homogeneity question that problem is a CNT of Cun Zaiing wherein is because the performance of CNT and its caliber have very confidential relation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of lanthanum doped composite metal oxide catalyst and preparation method who is used to prepare carbon nano tube with uniform diameter at above-mentioned prior art present situation, obtains uniform-caliber nanometre in the high yield that guarantees CNT.
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of lanthanum doped catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has composite metal oxide component, lanthanum doping component and promotes catalyst component on the carrier, four mol ratio is 0.5～3.0: 0.1～1.0: 0.01～1.0: 0.5～3.0, wherein, the composite metal oxide component is any compound of the two or three's oxide in iron, cobalt, the nickel, the lanthanum doping component is the oxide of lanthanum, 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.
This kind is used to prepare the preparation method of the lanthanum doped catalyst of carbon nano tube with uniform diameter, may further comprise the steps:
Magnesium salts is dissolved in the distilled water through stirring, adds composite metal oxide component salt, lanthanum doping component salt again and promote catalyst component salt, continue stirring it is dissolved fully, four mol ratio is 0.5～3.0: 0.1～1.0: 0.01～1.0: 0.5～3.0; Above-mentioned solution is placed 120～200 ℃ of oven dry 3～5 hours, again under aerobic environment in 550～850 ℃ of high-temperature calcinations 10～30 minutes, take out porphyrize, promptly obtain to be used to prepare the catalyst of CNT.
Described magnesium salts be selected from magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate or wherein appoint the two, three or four mixture.
Described composite metal oxide 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 lanthanum doping component salt comprises lanthanum nitrate, lanthanum carbonate, lanthanum acetate.
Described promotion catalyst component is the oxide of ammonium molybdate 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 has higher catalytic efficiency, and product (containing catalyst) is higher than 35 times with catalyst weight than generally, and the purity of CNT generally is higher than 90%, the CNT caliber that is obtained is evenly distributed, between 10～20nm.Method for preparing catalyst of the present invention has repeatable good, and process is simple, the advantage of easy operating.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of the multi-walled carbon nano-tubes that makes of the catalyst with the embodiment of the invention one.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment one
A kind of lanthanum doped catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has the binary complex of the oxide of nickel and cobalt on the carrier, the oxide of lanthanum and the oxide of molybdenum, four mol ratio is 105: 10: 5: 120, the mol ratio of nickel and cobalt is 6: 4 in the binary complex of the oxide of nickel and cobalt, the mol ratio of nickel and iron is 0.1: 1.0 in the binary complex of the oxide of nickel and iron, the mol ratio of iron and cobalt is 1.0: 0.1 in the binary complex of the oxide of iron and cobalt, 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 lanthanum doped catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has the binary complex of the oxide of nickel and cobalt on the carrier, the oxide of lanthanum and the oxide of molybdenum, four mol ratio is 10: 1: 0.25: 12.5, the mol ratio of nickel and cobalt is 5: 5 in the binary complex of the oxide of nickel and cobalt, the mol ratio of nickel and iron is 1.0: 0.5 in the binary complex of the oxide of nickel and iron, the mol ratio of iron and cobalt is 1.0: 0.8 in the binary complex of the oxide of iron and cobalt, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 0.4: 0.6: 1.0.
Embodiment three
A kind of lanthanum doped catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has the binary complex of the oxide of nickel and cobalt on the carrier, the oxide of lanthanum and the oxide of molybdenum, four mol ratio is 15: 1: 0.1: 8, the mol ratio of nickel and cobalt is 4: 1 in the binary complex of the oxide of nickel and cobalt, the mol ratio of nickel and iron is 0.5: 0.5 in the binary complex of the oxide of nickel and iron, the mol ratio of iron and cobalt is 0.1: 1.0 in the binary complex of the oxide of iron and cobalt, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 0.1: 1.0: 0.1.
Embodiment four
A kind of lanthanum doped catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has the binary complex of the oxide of nickel and cobalt on the carrier, the oxide of lanthanum and the oxide of molybdenum, four mol ratio is 20: 1: 1: 10, the mol ratio of nickel and cobalt is 9: 1 in the binary complex of the oxide of nickel and cobalt, the mol ratio of nickel and iron is 7: 3 in the binary complex of the oxide of nickel and iron, the mol ratio of iron and cobalt is 5: 5 in the binary complex of the oxide of iron and cobalt, iron, cobalt, iron in the ternary complex of the oxide of nickel, cobalt, the mol ratio of nickel is 1.0: 1.0: 1.0.
Embodiment five
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Fe: Co: La: Mo: Mg=1 in molar ratio: 10: 1: 330: 155, take by weighing ferric nitrate, cobalt nitrate, lanthanum nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, cobalt nitrate, lanthanum nitrate and ammonium molybdate more successively, treat four all dissolvings fully, 180 ℃ of oven dry, the time is 3 hours with solution.The product that obtains is calcined porphyrize after 30 minutes in 700 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment six
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Fe: Co: La: Mo: Mg=10 in molar ratio: 1: 10: 55: 175, take by weighing ferric sulfate, cobaltous sulfate, lanthanum acetate, ammonium molybdate, magnesium sulfate, earlier magnesium sulfate is dissolved in an amount of distilled water, add ferric sulfate, cobaltous sulfate, lanthanum acetate and ammonium molybdate more successively, treat four all dissolvings fully, 140 ℃ of oven dry, the time is 5 hours with solution.The product that obtains is calcined porphyrize after 20 minutes in 750 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment seven
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Fe: Ni: La: Mo: Mg=1 in molar ratio: 10: 7: 230: 275, take by weighing iron chloride, nickel chloride, lanthanum carbonate, ammonium molybdate, magnesium chloride, earlier magnesium chloride is dissolved in an amount of distilled water, add iron chloride, nickel chloride, lanthanum carbonate and ammonium molybdate more successively, treat four all dissolvings fully, 150 ℃ of oven dry, the time is 3 hours with solution.The product that obtains is calcined porphyrize after 30 minutes in 600 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment eight
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Ni: Co: La: Mo: Mg=1 in molar ratio: 10: 4: 55: 55, take by weighing nickel acetate, cobalt acetate, lanthanum carbonate, ammonium molybdate, magnesium acetate, earlier magnesium acetate is dissolved in an amount of distilled water, add nickel acetate, cobalt acetate, lanthanum carbonate and ammonium molybdate more successively, treat that it dissolves fully, 160 ℃ of oven dry, the time is 4 hours with solution.The product that obtains is calcined porphyrize after 10 minutes in 650 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment nine
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Fe: Ni: La: Mo: Mg=10 in molar ratio: 1: 8: 250: 150, take by weighing ferric nitrate, nickel nitrate, lanthanum carbonate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, nickel nitrate, lanthanum carbonate and ammonium molybdate more successively, treat four all dissolvings fully, 140 ℃ of oven dry, the time is 4 hours with solution.The product that obtains is calcined porphyrize after 30 minutes in 550 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment ten
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Ni: Co: La: Mo: Mg=10 in molar ratio: 1: 1: 100: 275, take by weighing nickelous sulfate, cobaltous sulfate, lanthanum nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add nickelous sulfate, cobaltous sulfate, lanthanum nitrate and ammonium molybdate more successively, treat four all dissolvings fully, 170 ℃ of oven dry, the time is 3 hours with solution.The product that obtains is calcined porphyrize after 20 minutes in 700 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment 11
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Fe: Co: Ni: La: Mo: Mg=4 in molar ratio: 5: 1: 8: 160: 200, take by weighing iron chloride, cobalt chloride, nickel chloride, lanthanum acetate, ammonium molybdate, magnesium chloride, earlier magnesium chloride is dissolved in an amount of distilled water, add iron chloride, cobalt chloride, nickel chloride, lanthanum carbonate and ammonium molybdate more successively, treat that it dissolves fully, 150 ℃ of oven dry, the time is 3 hours with solution.The product that obtains is calcined porphyrize after 30 minutes in 600 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment 12
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Ni: Fe: Co: La: Mo: Mg=1 in molar ratio: 1: 10: 1: 360: 60, take by weighing nickel nitrate, ferric nitrate, cobalt nitrate, lanthanum nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add nickel nitrate, ferric nitrate, cobalt nitrate, lanthanum nitrate and ammonium molybdate more successively, treat that it dissolves fully, 180 ℃ of oven dry, the time is 3 hours with solution.The product that obtains is calcined porphyrize after 10 minutes in 750 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment 13
A kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter, Fe: Co: Ni: La: Mo: Mg=1 in molar ratio: 10: 1: 12: 170: 275, take by weighing ferric sulfate, cobaltous sulfate, nickelous sulfate, lanthanum acetate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric sulfate, cobaltous sulfate, nickelous sulfate, lanthanum acetate and ammonium molybdate more successively, treat four all dissolvings fully, 150 ℃ of oven dry, the time is 4 hours with solution.The product that obtains is calcined porphyrize after 20 minutes in 600 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Claims (8)
1, a kind of lanthanum doped catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has composite metal oxide component, lanthanum doping component and promotes catalyst component on the carrier, it is characterized in that four mol ratio is 0.5～3.0: 0.1～1.0: 0.01～1.0: 0.5～3.0, wherein, the composite metal oxide component is any compound of the two or three's oxide in iron, cobalt, the nickel, and the lanthanum doping component is the oxide of lanthanum, promotes that catalyst component is the oxide of molybdenum.
2, a kind of lanthanum doped catalyst for preparing carbon nano tube with uniform diameter according to 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 lanthanum doped catalyst of the described preparation carbon nano tube with uniform diameter of claim 1 is characterized in that may further comprise the steps:
Magnesium salts is dissolved in the distilled water through stirring, adds composite metal oxide component salt, lanthanum doping component salt again and promote catalyst component salt, continue stirring it is dissolved fully, four mol ratio is 0.5～3.0: 0.1～1.0: 0.01～1.0: 0.5～3.0; Above-mentioned solution is placed 120～200 ℃ of oven dry 3～5 hours, under aerobic environment,, take out porphyrize, promptly obtain to be used to prepare the catalyst of CNT in 550～850 ℃ of high-temperature calcinations 10～30 minutes.
4, a kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter according to claim 3, 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.
5, a kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter according to claim 3 is characterized in that described composite metal oxide component salt comprises the binary or the ternary complex of molysite, cobalt salt or nickel salt.
6, a kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter according to claim 5, it is characterized in that described molysite comprises ferric nitrate, iron chloride, ferric sulfate or ferric acetate, cobalt salt comprises cobalt nitrate, cobalt chloride, cobaltous sulfate or cobalt acetate, and nickel salt comprises nickel nitrate, nickel chloride, nickelous sulfate or nickel acetate.
7, a kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter according to claim 3 is characterized in that described lanthanum doping component salt comprises lanthanum nitrate, lanthanum carbonate or lanthanum acetate, and described promotion catalyst component salt is molybdate.
8, a kind of preparation method who prepares the lanthanum doped catalyst of carbon nano tube with uniform diameter according to claim 6, 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.
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| CN106044838B (en) * | 2016-07-28 | 2017-05-24 | 乐山沃耐稀电子材料有限公司 | Production technology of low-sulfur lanthanum hydroxide |
| CN108793390A (en) * | 2018-05-25 | 2018-11-13 | 广东博宇集团有限公司 | A kind of catalyst filling and its preparation method and application for purifying aquarium water quality |
| CN113620277A (en) * | 2021-06-10 | 2021-11-09 | 北京化工大学 | Method for preparing carbon nano tube and hydrogen by high-valued utilization of waste medical masks |
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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 |
| 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 |
| WO2004096704A2 (en) * | 2002-07-31 | 2004-11-11 | Carbon Nanotechnologies, Inc. | Method for making single-wall carbon nanotubes using supported catalysts |
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| WO2004096704A2 (en) * | 2002-07-31 | 2004-11-11 | Carbon Nanotechnologies, Inc. | Method for making single-wall carbon nanotubes using supported catalysts |
| 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 |
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