CN1302846C - Lanthanum doped monometallic catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof - Google Patents
Lanthanum doped monometallic catalyst for preparing carbon nano tube with uniform diameter and preparing process thereof Download PDFInfo
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- CN1302846C CN1302846C CNB2004100935937A CN200410093593A CN1302846C CN 1302846 C CN1302846 C CN 1302846C CN B2004100935937 A CNB2004100935937 A CN B2004100935937A CN 200410093593 A CN200410093593 A CN 200410093593A CN 1302846 C CN1302846 C CN 1302846C
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Abstract
The present invention discloses a lanthanum doped monometallic catalyst for preparing carbon nanometer tubes with uniform diameters and a preparing process of the lanthanum doped monometallic catalyst. The lanthanum doped monometallic catalyst uses magnesium oxide as a carrier. Oxides of cobalt (co), ferrum or nickel are used as metal oxide components. A lanthanum oxide is used as a doped component. A molybdenic oxide is used as a promotion catalyzing component. Magnesium salt is dissolved in distilled water, and 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 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. Solution is baked for 3 to 5 hours in 120 to 200 DEG C to be calcined in 550 to 850 DEG C of high temperature for 10 to 30 minutes. After being taken out to be porphyrized into powder, a catalyst for preparing carbon nanometer tubes is obtained. The lanthanum doped monometallic catalyst for preparing carbon nanometer 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 monometallic 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 the lanthanum doping single-metal reforming catalyst and the preparation method that prepare 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 can be 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 design Micro Electro Mechanical System; 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, and the CNT of different Preparation of Catalyst has different patterns and performance, wherein the homogeneity question that important problem is the CNT caliber of Cun Zaiing.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of lanthanum doping single metal oxides catalyst and above-mentioned Preparation of catalysts method that is used to prepare carbon nano tube with uniform diameter at above-mentioned prior art present situation, obtains uniform-caliber nanometre when guaranteeing the CNT high yield.
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of lanthanum doping single-metal reforming catalyst that is used to prepare carbon nano tube with uniform diameter, it is carrier with magnesia, load has single metal oxides 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 single metal oxides component is the oxide of iron, cobalt, nickel, doping component is the oxide of lanthanum, promotes that catalyst component is the oxide of molybdenum.
This kind is used to prepare the preparation method of the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter, may further comprise the steps:
Magnesium salts is dissolved in the distilled water through stirring, adds single metal oxides 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 in 120～200 ℃ of oven dry 3～5 hours, in 550～850 ℃ of high-temperature calcinations 10～30 minutes, is taken out porphyrize under aerobic environment, 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 single metal oxides component salt comprises 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.
Described lanthanum doping component salt comprises lanthanum nitrate, lanthanum carbonate, lanthanum acetate.
Described promotion catalyst component salt 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 30 times with catalyst weight than generally, the purity of CNT generally is higher than 90%, the CNT caliber that is obtained is 10～20nm, is evenly distributed, 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.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of the multi-walled carbon nano-tubes that makes of the catalyst with example one of the present invention.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment one
A kind of lanthanum doping single metal oxides catalyst for preparing carbon nano tube with uniform diameter, it is a carrier with magnesia, and load has nickel metal oxide component, lanthanum doping component and promotes catalyst component on the carrier, and four mol ratio is 50: 10: 1: 50.
Embodiment two
A kind of lanthanum doping single metal oxides catalyst for preparing carbon nano tube with uniform diameter, it is a carrier with magnesia, and load has nickel metal oxide component, lanthanum doping component and promotes catalyst component on the carrier, and four mol ratio is 25: 10: 1: 25.
Embodiment three
A kind of preparation method who prepares the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter, Co: La: Mo: Mg=5 in molar ratio: 5: 75: 125, take by weighing cobalt chloride, lanthanum carbonate, ammonium molybdate, magnesium chloride, earlier magnesium chloride is dissolved in an amount of distilled water, add cobalt chloride, 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 20 minutes in 700 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment four
A kind of preparation method who prepares the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter, Fe: La: Mo: Mg=1 in molar ratio: 1: 25: 15, take by weighing ferric acetate, lanthanum acetate, ammonium molybdate, magnesium acetate, earlier magnesium acetate is dissolved in an amount of distilled water, add ferric acetate, lanthanum acetate 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 700 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment five
A kind of preparation method who prepares the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter, Fe: La: Mo: Mg=9 in molar ratio: 1: 100: 200, take by weighing ferric nitrate, lanthanum nitrate, ammonium molybdate, magnesium nitrate, earlier magnesium nitrate is dissolved in an amount of distilled water, add ferric nitrate, lanthanum nitrate and ammonium molybdate more successively, treat that it dissolves fully, 140 ℃ of oven dry, the time is 4 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 six
A kind of preparation method who prepares the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter, Ni: La: Mo: Mg=5 in molar ratio: 1: 40: 60, take by weighing nickelous sulfate, lanthanum carbonate, ammonium molybdate, magnesium sulfate, earlier magnesium sulfate is dissolved in an amount of distilled water, add nickelous sulfate, lanthanum carbonate and ammonium molybdate more successively, treat that it dissolves fully, 120 ℃ of oven dry, the time is 5 hours with solution.The product that obtains is calcined porphyrize after 20 minutes in 650 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Embodiment seven
A kind of preparation method who prepares the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter, Co: La: Mo: Mg=1 in molar ratio: 1: 25: 15, take by weighing cobalt acetate, lanthanum acetate, ammonium molybdate, magnesium acetate, earlier magnesium acetate is dissolved in an amount of distilled water, add cobalt acetate, lanthanum acetate 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 5 minutes in 750 ℃ of air, promptly obtain can be used to prepare the catalyst of CNT.
Claims (7)
1, a kind of lanthanum doping single-metal reforming catalyst for preparing carbon nano tube with uniform diameter, it is carrier with magnesia, load has single metal oxides 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 single metal oxides component is the oxide of iron, cobalt or nickel, and doping component is the oxide of lanthanum, promotes that catalyst component is the oxide of molybdenum.
2, the preparation method of the lanthanum doping single-metal reforming 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 single metal oxides 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 in 120～200 ℃ of oven dry 3～5 hours, in 550～850 ℃ of high-temperature calcinations 10～30 minutes, is taken out porphyrize under aerobic environment, promptly obtain to be used to prepare the catalyst of CNT.
3, the preparation method of the lanthanum doping single-metal reforming catalyst of preparation carbon nano tube with uniform diameter according to claim 2, 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.
4, the preparation method of the lanthanum doping single-metal reforming catalyst of preparation carbon nano tube with uniform diameter according to claim 2 is characterized in that described single metal oxides component salt comprises the one pack system salt of iron, cobalt or nickel.
5, the preparation method of the lanthanum doping single-metal reforming catalyst of preparation carbon nano tube with uniform diameter according to claim 4, 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.
6, the preparation method of the lanthanum doping single-metal reforming catalyst of preparation carbon nano tube with uniform diameter according to claim 2 is characterized in that described lanthanum doping component salt comprises lanthanum nitrate, lanthanum carbonate or lanthanum acetate.
7, the preparation method who is used to prepare the lanthanum doping single-metal reforming catalyst of carbon nano tube with uniform diameter according to claim 2 is characterized in that described promotion catalyst component salt is molybdate.
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| CN113148982B (en) * | 2021-03-11 | 2022-11-01 | 江西铜业技术研究院有限公司 | Preparation method of high-purity double-wall carbon nano tube |
| 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 |
| CN115532268A (en) * | 2022-09-24 | 2022-12-30 | 山东碳峰新材料科技有限公司 | Preparation and application of iron-based carbon nanotube catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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Effective date of registration: 20080404 Address after: A building, Xin Mei Industrial Zone, No. 260 Lian Cao Road, Shanghai, Minhang District Patentee after: Shanghai Huashi Nano Material Co., Ltd. Address before: No. 199 Lingyun Road, Ningbo science and Technology Park, Zhejiang Patentee before: Ningbo Huashi Nanomaterials Co., Ltd. |
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