CN1724345A - Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof - Google Patents
Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof Download PDFInfo
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- CN1724345A CN1724345A CN 200510049901 CN200510049901A CN1724345A CN 1724345 A CN1724345 A CN 1724345A CN 200510049901 CN200510049901 CN 200510049901 CN 200510049901 A CN200510049901 A CN 200510049901A CN 1724345 A CN1724345 A CN 1724345A
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Abstract
A metallic oxide catalyst Fe/Mo/MgO for preparing single-wall carbon nano-tubes is proportionally composed of MgO as carrier, oxide of Fe as primary catalyzing component and Mo as co-catalyst. Its preparing process includes such steps as proportionally mixing the Fe salt, Mo salt (or oxide) and Mg salt in de-ionized water or alcohol solution, freezing at -100--40 deg. C, drying at -40--10 deg. C for 12-48 hr, and drying again at 20-60 deg. C for 6-12 hr. Its advantage is high catalytic activity.
Description
Technical field
The present invention relates to a kind of metal oxide catalyst for preparing Single Walled Carbon Nanotube and preparation method thereof.
Background technology
Single Walled Carbon Nanotube is seamless, the hollow tube that is curled into by hexagonal carbon atom looped network lattice, and each is reined in by half richness that face carbon ball forms end to end, similar graphite, the electronics that existence can move freely in the carbon valence link of carbon nanotube.Relative multiple-wall carbon nanotube, Single Walled Carbon Nanotube has the material behavior of many excellences.Among all preparation methods, chemical Vapor deposition process (CVD) is because its equipment, simple to operate, less investment, and characteristics such as temperature of reaction is low are considered to the method for tool Commercial Prospect.Present Single Walled Carbon Nanotube is produced required Preparation of catalysts method and is emerged in an endless stream, but because its utilization ratio and catalytic efficiency are not high, thereby the Single Walled Carbon Nanotube output that obtains is not high, and impurities is more in the primary products.
Summary of the invention
The purpose of this invention is to provide a kind of highly active metal oxide catalyst that is used for the mass production Single Walled Carbon Nanotube and preparation method thereof.
Metal oxide catalyst of the present invention is to be carrier with magnesium oxide, the oxide compound that forms with iron is the main catalytic composition, with molybdenum is the Fe/Mo/MgO three-phase metal oxide catalyst that helps catalyst component to form, and iron in the catalyzer: molybdenum: the mol ratio of magnesium is 0.5～5: 0.01～0.5: 10～30.Optimum mole ratio is for being 1～2: 0.01～0.2: 10～20.
In this metal oxide catalyst, select magnesium nitrate for use, magnesium acetate, magnesium chloride, sal epsom, magnesium oxalate or magnesium ethylate are as the raw material that forms magnesium oxide carrier, select iron nitrate for use, iron acetate, iron(ic) chloride, ferric sulfate or ironic oxalate form the oxide compound of main catalytic composition iron, and molybdenum is selected from the oxide compound of molybdate or molybdenum.
The preparation process of metal oxide catalyst of the present invention is as follows: get the metal-salt of iron, metal-salt or the oxide compound of molybdenum and the metal-salt of magnesium of molybdenum in molar ratio, uniform mixing is in deionized water or ethanolic soln, under-100～-40 ℃ that above-mentioned solution is freezing, carry out the primary drying processing of 12～48h then in-40～-10 ℃ of solids, under 20～60 ℃, carry out the redrying of 6～12h again and handle freezing formation.
Need not the preparation that calcination processing promptly can be used for Single Walled Carbon Nanotube through above-mentioned cryodesiccated catalyzer.
Metal oxide catalyst of the present invention is used to prepare Single Walled Carbon Nanotube to carry out on fixed bed gas continuous flow Reaktionsofen.A certain amount of catalyzer is placed on places fixed bed gas continuous flow Reaktionsofen on the quartz boat, feed methane and hydrogen or the nitrogen or the rare gas element of certain flow, methane flow is 25～500sccm, be preferably 50～100sccm, hydrogen or nitrogen or inert gas flow are 50～400sccm, be preferably 200～400sccm, temperature of reaction is controlled at 800～1200 ℃, be preferably 900～1000 ℃, reacted 10～60 minutes, the product of collection is the Single Walled Carbon Nanotube of metal oxide catalyst preparation of the present invention.
Metal oxide catalyst provided by the invention is active strong, and utilization ratio is higher, with the Single Walled Carbon Nanotube diameter homogeneous of this Preparation of Catalyst, is 0.88 ± 0.1nm.And this catalyst preparation process process is simple and easy, and good reproducibility need not calcination processing.Synthetic Single Walled Carbon Nanotube output height, purity is higher, and degree of graphitization is very high.
Description of drawings
Fig. 1 is the SEM photo of the Single Walled Carbon Nanotube that makes with catalyzer of the present invention;
Fig. 2 is the TEM photo of the Single Walled Carbon Nanotube that makes with catalyzer of the present invention.
Fig. 3 is the TG curve of the Single Walled Carbon Nanotube that makes with catalyzer of the present invention.
Embodiment
Embodiment 1
Get molybdenum oxide and join deionized water solution,, dissolve up to complete reaction 80 ℃ of heated and stirred 0.5 hour.Nine nitric hydrate iron, magnesium ethylate are dissolved in respectively in the above-mentioned solution that contains molybdenum, stirred 1 hour, uniform mixing, iron in the solution: molybdenum: the mol ratio of magnesium is 2: 0.5: 15.Again with above-mentioned mixing solutions in-60 ℃ freezing, the primary drying that carries out 36h in-30 ℃ of solids with freezing formation is handled then, to remove the crystal water in the lyophilized solid, handles 30 ℃ of redryings of carrying out 6h again.Promptly can be used for the preparation of Single Walled Carbon Nanotube through above-mentioned cryodesiccated catalyzer.
The preparation of Single Walled Carbon Nanotube is carried out on fixed bed gas continuous flow Reaktionsofen.0.112 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow of 70sccm is the hydrogen of 300sccm, and control reaction temperature is 1000 ℃, reacts to make bunchy Single Walled Carbon Nanotube 0.165 gram after 30 minutes.The stereoscan photograph of product as shown in Figure 1, transmission electron microscope photo is as shown in Figure 2.
Embodiment 2
Get molybdenum acid ammonia and join deionized water solution,, dissolve up to complete reaction 80 ℃ of heated and stirred 0.5 hour.Nine nitric hydrate iron, magnesium ethylate are dissolved in respectively in the above-mentioned solution that contains molybdenum, stirred 1 hour, uniform mixing, iron in the solution: molybdenum: the mol ratio of magnesium is 1: 0.1: 15, again with above-mentioned mixing solutions in-40 ℃ freezing, the primary drying that carries out 24h in-30 ℃ of solids with freezing formation is handled then, to remove the crystal water in the lyophilized solid, handle 40 ℃ of redryings of carrying out 6h again.Promptly can be used for the preparation of Single Walled Carbon Nanotube through above-mentioned cryodesiccated catalyzer.
The preparation of carbon pipe is carried out on fixed bed gas continuous flow Reaktionsofen.0.103 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow velocity of 75sccm is the hydrogen of 200sccm, and control reaction temperature is 1000 ℃, reacts to make Single Walled Carbon Nanotube 0.176 gram after 30 minutes.The TG curve of product as shown in Figure 3.
Claims (4)
1. metal oxide catalyst for preparing Single Walled Carbon Nanotube, it is characterized in that it is is carrier with magnesium oxide, the oxide compound that forms with iron is the main catalytic composition, with molybdenum is the Fe/Mo/MgO three-phase metal oxide catalyst that helps catalyst component to form, and iron in the catalyzer: molybdenum: the mol ratio of magnesium is 0.5～5: 0.01～0.5: 10～30.
2. the metal oxide catalyst of preparation Single Walled Carbon Nanotube according to claim 1 is characterized in that iron in the catalyzer: molybdenum: the mol ratio of magnesium is 1～2: 0.01～0.2: 10～20.
3. the metal oxide catalyst of preparation Single Walled Carbon Nanotube according to claim 1, it is characterized in that selecting for use magnesium nitrate, magnesium acetate, magnesium chloride, sal epsom, magnesium oxalate or magnesium ethylate are as the raw material that forms magnesium oxide carrier, select iron nitrate for use, iron acetate, iron(ic) chloride, ferric sulfate or ironic oxalate form the oxide compound of the iron of main catalytic composition, and molybdenum is selected from the oxide compound of molybdate or molybdenum.
4. the preparation method of metal oxide catalyst according to claim 1, it is characterized in that step is as follows: get the metal-salt of iron, metal-salt or the oxide compound of molybdenum and the metal-salt of magnesium of molybdenum in molar ratio, uniform mixing is in deionized water or ethanolic soln, under-100～-40 ℃ that above-mentioned solution is freezing, carry out the primary drying processing of 12～48h then in-40～-10 ℃ of solids, under 20～60 ℃, carry out the redrying of 6～12h again and handle freezing formation.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100499010A CN1318135C (en) | 2005-06-01 | 2005-06-01 | Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof |
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| CNB2005100499010A CN1318135C (en) | 2005-06-01 | 2005-06-01 | Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof |
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| CN1724345A true CN1724345A (en) | 2006-01-25 |
| CN1318135C CN1318135C (en) | 2007-05-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731433A (en) * | 2021-08-30 | 2021-12-03 | 福建海梵领航科技有限公司 | Trace molybdenum-doped iron-based catalyst and preparation method and application thereof |
| CN115403029A (en) * | 2022-08-31 | 2022-11-29 | 聚源材料科技(遵义)有限公司 | Preparation method of single-walled carbon nanotube |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476929A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Denitration catalyst using CeTi2Ob as carrier and its preparation method |
| CN1212189C (en) * | 2003-07-08 | 2005-07-27 | 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731433A (en) * | 2021-08-30 | 2021-12-03 | 福建海梵领航科技有限公司 | Trace molybdenum-doped iron-based catalyst and preparation method and application thereof |
| CN113731433B (en) * | 2021-08-30 | 2024-02-02 | 福建海梵领航科技有限公司 | Trace molybdenum doped iron-based catalyst and preparation method and application thereof |
| CN115403029A (en) * | 2022-08-31 | 2022-11-29 | 聚源材料科技(遵义)有限公司 | Preparation method of single-walled carbon nanotube |
| CN115403029B (en) * | 2022-08-31 | 2024-01-30 | 聚源材料科技(遵义)有限公司 | Preparation method of single-walled carbon nanotube |
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Granted publication date: 20070530 Termination date: 20100601 |