CN1443708A - Method oxide catalyst and method for preparing bundled multiwall nano carbon tube - Google Patents
Method oxide catalyst and method for preparing bundled multiwall nano carbon tube Download PDFInfo
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- CN1443708A CN1443708A CN 03116514 CN03116514A CN1443708A CN 1443708 A CN1443708 A CN 1443708A CN 03116514 CN03116514 CN 03116514 CN 03116514 A CN03116514 A CN 03116514A CN 1443708 A CN1443708 A CN 1443708A
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Abstract
The present invention relates to a metal oxide catalyst and a method for preparing bundled multiwall nano carbon tube by using said metal oxide catalyst and catalytic cracking methane, said metal oxide catalyst is the Fe/Mo/MgO and Ni/Mo/MgO catalyst formed from oxide of magnesium and molybdenum as main catalyst and iron or nickel as auxiliary catalyst. Said catalyst is placed in the fixed bed gas continuously-flowing reaction furnace, and the methane whose introduced flow rate is 50-1500 sccm and the hydrogen gas or nitrogen gas or inert gas whose flow rate is 50-300 sccm are reacted for 10-100 min. at 750-1200 deg.C so as to form the invented bundled multiwall nano carbon tube.
Description
Technical field
The present invention relates to a kind of metal oxide catalyst and prepare the method for bunchy multiple-wall carbon nanotube with this metal oxide catalyst catalytic cracking methane.
Background technology
CNT (carbon nano-tube) is a kind of novel material of finding the nineties in 20th century, is typical case's representative of one-dimentional structure material and nano material.Chemical Vapor deposition process (CVD) is because its output height is simple to operate, and less investment is the method that promises to be the industrial mass production CNT (carbon nano-tube) at present most, thereby has also become the most popular method of current preparation CNT (carbon nano-tube).This method is used the solid catalyst of metal load type usually, by cracking organic gas such as methane on fixed bed, acetylene, ethene and third rare, carries out gas-solid phase inhomogeneous reaction, obtains CNT (carbon nano-tube) at last.But this method exists catalyst utilization and catalytic efficiency not high, thereby problem such as the carbon pipe that obtains is of low quality, and the primary products impurities is more.
Summary of the invention
The purpose of this invention is to provide a kind of metal oxide catalyst and utilize this catalyst development high-level efficiency and high utilization rate, catalytic cracking methane simple to operate prepare the method for bunchy multiple-wall carbon nanotube.
Metal oxide catalyst of the present invention is that the oxide compound that forms with magnesium and molybdenum is a Primary Catalysts, is Fe/Mo/MgO and the Ni/Mo/MgO catalyzer that promotor forms with iron or nickel.
In this metal oxide catalyst, magnesium is selected from magnesium nitrate, magnesium acetate, and magnesium chloride, sal epsom, molybdenum can be selected from the oxide compound of molybdate and molybdenum, and iron can be selected from iron nitrate, iron acetate, iron(ic) chloride, ferric sulfate, nickel can be selected from nickelous nitrate, nickel acetate, nickelous chloride, single nickel salt.Iron or nickel in the catalyzer: molybdenum: the mol ratio of magnesium is (0.1～1): (0.5～2): (0.8～3), optimum mole ratio are (0.05～0.8): (1～2): (1～2).
Metal oxide catalyst of the present invention can adopt sol-gel method or combustion method to be prepared from.Prepared by Sol Gel Method catalyzer method is as follows: get the metal-salt that contains iron or nickel, magnesium, molybdenum in molar ratio and be equal to magnesium or the citric acid of the mole number of molybdenum, mixed dissolution forms clear solution in distilled water, put into drying baker, under 100 ℃～150 ℃, normal atmosphere, evaporate, until forming a kind of foam, at last, with this foam in retort furnace, 500 ℃～750 ℃, roasting is 10～30 minutes under the air atmosphere, takes out the catalyzer that porphyrize promptly obtains being used to prepare the bunchy multiple-wall carbon nanotube.
The method that combustion method prepares catalyzer is as follows: get the metal-salt that contains iron or nickel, magnesium, molybdenum in molar ratio and be equal to magnesium or the citric acid of the mole number of molybdenum, mixed dissolution forms clear solution in distilled water, heated and stirred is inserted porcelain boat after forming gel, 500～800 ℃ were heated 5～30 minutes in retort furnace, and the powder cooling back of formation is taken out porphyrize and promptly be can be used for being prepared into the bundle multiple-wall carbon nanotube.
The preparation of bunchy multiple-wall carbon nanotube is carried out on fixed bed gas continuous flow Reaktionsofen.A certain amount of catalyzer is put into fixed bed gas continuous flow Reaktionsofen, feed methane and hydrogen or the nitrogen or the rare gas element of certain flow rate, methane flow rate is 50～1500sccm, be preferably 500～1200sccm, hydrogen or nitrogen or rare gas element flow velocity are 50～300sccm, are preferably 75～200sccm, temperature of reaction is controlled at 750 ℃～1200 ℃, be preferably 800～1100 ℃, react and stop after 10～100 minutes, collect product and be bunchy multiple-wall carbon nanotube of the present invention.
Metal oxide catalyst provided by the invention is active strong, the utilization ratio height, CNT (carbon nano-tube) with this Preparation of Catalyst, the overwhelming majority is the self-assembly bunchy all, uniform diameter, and technological process is simple, good stability, bunchy CNT (carbon nano-tube) output very high (20～80 times to catalyzer), purity height (more than 95%), degree of graphitization is good.
Description of drawings
Fig. 1 is the transmission electron micrograph of the bunchy multiple-wall carbon nanotube that makes of the inventive method;
Fig. 2 is the TGA analysis chart of bunchy multiple-wall carbon nanotube.
Embodiment
Embodiment 1
Fe: Mo: Mg is the citric acid of getting nine nitric hydrate iron, magnesium nitrate hexahydrate, ammonium molybdate at 1: 10: 10 and being equal to the magnesium nitrate hexahydrate mole number in molar ratio, mixed dissolution forms clear solution in distilled water, put into porcelain boat after forming colloidal sol, adopt combustion method, colloidal sol is heated down in 700 ℃ in retort furnace, porphyrize after the solid cooled that forms is taken out in roasting 10 minutes under this temperature again.The preparation of carbon pipe is carried out on fixed bed gas continuous flow Reaktionsofen.0.105 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow velocity of 900sccm is the hydrogen of 50sccm, and control reaction temperature is 1000 ℃, reacts to make bunchy multiple-wall carbon nanotube 2.876 grams after 30 minutes.The transmission electron microscope photo of product as shown in Figure 1.
Embodiment 2
Ni: Mo: Mg is the citric acid of getting Nickelous nitrate hexahydrate, magnesium nitrate hexahydrate, ammonium molybdate at 1: 10: 10 and being equal to the magnesium nitrate hexahydrate mole number in molar ratio, mixed dissolution forms clear solution in distilled water, put into porcelain boat after forming colloidal sol, adopt combustion method, colloidal sol is heated down in 700 ℃ in retort furnace, porphyrize after the solid cooled that forms is taken out in roasting 10 minutes under this temperature again.The preparation of carbon pipe is carried out on fixed bed gas continuous flow Reaktionsofen.0.145 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow velocity of 900sccm is the hydrogen of 50sccm, and control reaction temperature is 1000 ℃, reacts to make bunchy multiple-wall carbon nanotube 3.442 grams after 30 minutes.
Embodiment 3
Fe: Mo: Mg is the citric acid of getting nine nitric hydrate iron, magnesium nitrate hexahydrate, ammonium molybdate at 1: 10: 10 and being equal to the magnesium nitrate hexahydrate mole number in molar ratio, mixed dissolution forms clear solution in distilled water, adopt sol-gel method, it is following 2 hours to put into 120 ℃ of drying bakers behind the formation colloidal sol, change porcelain boat over to after waiting to foam, then in retort furnace 750 ℃ of following roastings 30 minutes, porphyrize after the solid cooled that take out to form.The preparation of carbon pipe is carried out on fixed bed gas continuous flow Reaktionsofen.0.091 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow velocity of 900sccm is the hydrogen of 50sccm, and control reaction temperature is 1000 ℃, reacts to make bunchy multiple-wall carbon nanotube 2.866 grams after 45 minutes.Thermogravimetric analysis TGA curve as shown in Figure 2, illustrates the multiple-wall carbon nanotube that product is the purity height, degree of graphitization is good.
Claims (7)
1. being used to prepare the metal oxide catalyst of bunchy multiple-wall carbon nanotube, it is characterized in that it is that the oxide compound that forms with magnesium and molybdenum is a Primary Catalysts, is Fe/Mo/MgO and the Ni/Mo/MgO catalyzer that promotor forms with iron or nickel.
2. metal oxide catalyst according to claim 1 is characterized in that iron or nickel in this metal oxide catalyst: molybdenum: the mol ratio of magnesium is (0.1～1): (0.5～2): (0.8～3).
3. metal oxide catalyst according to claim 1 is characterized in that iron or nickel in this metal oxide catalyst: molybdenum: the mol ratio of magnesium is (0.05～0.8): (1～2): (1～2).
4. metal oxide catalyst according to claim 1 is characterized in that magnesium is selected from magnesium nitrate, magnesium acetate, magnesium chloride, sal epsom, molybdenum is selected from the oxide compound of molybdate and molybdenum, and iron is selected from iron nitrate, iron acetate, iron(ic) chloride, ferric sulfate, nickel is selected from nickelous nitrate, nickel acetate, nickelous chloride, single nickel salt.
5. metal oxide catalyst is used to prepare the method for bunchy multiple-wall carbon nanotube, it is characterized in that a certain amount of catalyzer is put into fixed bed gas Continuous Flow Reaktionsofen, feed methane and hydrogen or the nitrogen or the rare gas element of certain flow rate, methane flow rate is 50～1500sccm, hydrogen or nitrogen or rare gas element flow velocity are 50～300sccm, temperature of reaction is controlled at 750 ℃～1200 ℃, reacts to stop after 10～100 minutes, collects product.
6. the method for preparing the bunchy multiple-wall carbon nanotube according to claim 5 is characterized in that temperature of reaction is 800～1100 ℃.
7. the method for preparing the bunchy multiple-wall carbon nanotube according to claim 5 is characterized in that methane flow rate is 500～1200sccm, and hydrogen or nitrogen or rare gas element flow velocity are 75～200sccm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03116514 CN1226085C (en) | 2003-04-17 | 2003-04-17 | Method oxide catalyst and method for preparing bundled multiwall nano carbon tube |
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| CN 03116514 CN1226085C (en) | 2003-04-17 | 2003-04-17 | Method oxide catalyst and method for preparing bundled multiwall nano carbon tube |
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| CN1226085C CN1226085C (en) | 2005-11-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9050572B2 (en) | 2006-04-15 | 2015-06-09 | Bayer Materialscience Ag | Process for the production of carbon nanotubes in a fluidized bed |
| WO2015101917A1 (en) | 2013-12-30 | 2015-07-09 | Indian Oil Corporation Limited | Process for simultaneous production of carbon nanotube and a product gas from crude oil and its products |
| CN105565292A (en) * | 2014-10-29 | 2016-05-11 | 北京大学 | Ultra-high-density single-walled carbon nanotube horizontal array and controllable preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371110C (en) * | 2006-02-20 | 2008-02-27 | 浙江大学 | Method for synthesizing carbon covered stannum nanowire |
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2003
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9050572B2 (en) | 2006-04-15 | 2015-06-09 | Bayer Materialscience Ag | Process for the production of carbon nanotubes in a fluidized bed |
| WO2015101917A1 (en) | 2013-12-30 | 2015-07-09 | Indian Oil Corporation Limited | Process for simultaneous production of carbon nanotube and a product gas from crude oil and its products |
| CN105565292A (en) * | 2014-10-29 | 2016-05-11 | 北京大学 | Ultra-high-density single-walled carbon nanotube horizontal array and controllable preparation method thereof |
| CN105565292B (en) * | 2014-10-29 | 2018-04-06 | 北京大学 | A kind of VHD single-walled carbon nanotube horizontal array and its controllable method for preparing |
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| CN1226085C (en) | 2005-11-09 |
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