CN1476930A - Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled - Google Patents
Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled Download PDFInfo
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- CN1476930A CN1476930A CNA03141575XA CN03141575A CN1476930A CN 1476930 A CN1476930 A CN 1476930A CN A03141575X A CNA03141575X A CN A03141575XA CN 03141575 A CN03141575 A CN 03141575A CN 1476930 A CN1476930 A CN 1476930A
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Abstract
The invention bimetal oxide catalyst is the Fe/Mo/MgO catalyst formed by using magnesium oxide as carrier, using iron oxide as main catalyst and using molybdenum as cocatalyst, in which the mole ratio of Fe:Mo:Mg is 0.5-5:0.01-3:8-30. The catalyst is used for preparing single-wall nano carbon tube, and the preparation is implemented on the fixed bed gas continuous flow reactor furnace. The present invention also can use regulation of mixing ratio of active components of catalyst to control the diameter of grown single-wall nano carbon tube.
Description
Technical field
The present invention relates to a kind of bi-metal oxide catalyst and prepare the method for the Single Walled Carbon Nanotube of controllable diameter with this bi-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).And the Single Walled Carbon Nanotube that adopts chemical Vapor deposition process to prepare does not at present exist productive rate high and contain a large amount of problems such as multiple-wall carbon nanotube.And the diameter that how to reduce production costs, effectively control Single Walled Carbon Nanotube also is puzzlement CNT (carbon nano-tube) investigators' a difficult problem.
Summary of the invention
The purpose of this invention is to provide a kind of bi-metal oxide catalyst and utilize the method for the Single Walled Carbon Nanotube of this Preparation of Catalyst controllable diameter.
Bi-metal oxide catalyst of the present invention is to be carrier with magnesium oxide, and the oxide compound that forms with iron is a Primary Catalysts, is the Fe/Mo/MgO catalyzer that promotor forms with the molybdenum, and iron in the catalyzer: molybdenum: the mol ratio of magnesium is 0.5～5: 0.01～3: 8～30.Optimum mole ratio is 1～3: 0.05～2: 10～20.
Magnesium oxide is selected from magnesia crystal in this bi-metal oxide catalyst, magnesium nitrate, and magnesium acetate, oxalic acid does not have, magnesium chloride, sal epsom, molybdenum are selected from the oxide compound of molybdate and molybdenum, and iron is selected from iron nitrate, iron acetate, iron(ic) chloride, ferric sulfate, ironic oxalate.
Bi-metal oxide catalyst of the present invention can adopt sol-gel method or combustion method preparation.Prepared by Sol Gel Method catalyzer method is as follows: get the metal-salt that contains iron, magnesium, molybdenum in molar ratio and be equal to the citric acid of the amount of substance of magnesium, mixed dissolution forms clear solution in distilled water, put into drying baker, under 100 ℃～150 ℃, normal atmosphere, evaporate, until forming a kind of foam, 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 Single Walled Carbon Nanotube.
The method that combustion method prepares catalyzer is as follows: get the metal-salt that contains iron, magnesium, molybdenum in molar ratio and be equal to the citric acid of the amount of substance of magnesium, mixed dissolution forms clear solution in distilled water, heated and stirred is inserted porcelain boat after forming gel, 500～750 ℃ were heated 5～30 minutes in retort furnace, porphyrize is taken out in the powder cooling back that forms, and promptly can be used for preparing Single Walled Carbon Nanotube.
The preparation of Single Walled 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, methane flow is 20～200sccm, be preferably 25～75sccm, hydrogen or nitrogen or inert gas flow are 100～500sccm, are preferably 200～400sccm, temperature of reaction is controlled at 850～1200 ℃, be preferably 950～1100 ℃, reacted 10～100 minutes, collect product and be Single Walled Carbon Nanotube of the present invention.
The most important point of the present invention is and can comes the diameter of the Single Walled Carbon Nanotube of control growing by the proportioning of regulating the catalyst activity component.By regulating catalyst proportion, both can the single Single Walled Carbon Nanotube of growth diameter, also can grow the Single Walled Carbon Nanotube that diameter has certain distribution range.The diameter of the Single Walled Carbon Nanotube of single diameter is 0.87 ± 0.05nm, and the diameter with CNT (carbon nano-tube) of diameter Distribution is 0.75～1.3 ± 0.1nm.And the metal oxide catalyst activity that provides is stronger, and technological process is simple, good stability, and Single Walled Carbon Nanotube output is higher, and purity is better, the degree of graphitization height.
Description of drawings
Fig. 1 is the Raman spectrogram of Single Walled Carbon Nanotube;
Fig. 2 is the stereoscan photograph of Single Walled 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: 0.1: 13 and being equal to the magnesium nitrate hexahydrate amount of substance 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 550 ℃ 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.0.103 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow is that methane and the flow of 75sccm is the hydrogen of 300sccm, and control reaction temperature is 1000 ℃, reacts to make Single Walled Carbon Nanotube 0.165 gram after 30 minutes.The Single Walled Carbon Nanotube Raman spectrum curve of preparation illustrates that product is that degree of graphitization is good as shown in Figure 1, calculates to show that the diameter of the Single Walled Carbon Nanotube that makes is very even, is about 0.87nm.
Embodiment 2:
Fe: Mo: Mg is the citric acid of getting Nickelous nitrate hexahydrate, magnesium nitrate hexahydrate, ammonium molybdate at 2: 0.1: 13 and being equal to the magnesium nitrate hexahydrate amount of substance in molar ratio, mixed dissolution forms clear solution in distilled water, put into porcelain boat after forming colloidal sol, 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 550 ℃ 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.0.100 gram catalyzer is put into flat-temperature zone, stove stage casing, and the feeding flow is that methane and the flow of 75sccm is the hydrogen of 300sccm, and control reaction temperature is 1000 ℃, reacts to make Single Walled Carbon Nanotube 0.110 gram after 30 minutes.The transmission electron microscope photo of product as shown in Figure 2, the diameter Distribution of the Single Walled Carbon Nanotube for preparing under this proportioning is 0.75～1.3nm
Embodiment 3:
Fe: Mo: Mg is the citric acid of getting nine nitric hydrate iron, magnesium nitrate hexahydrate, ammonium molybdate at 1: 0.5: 13 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 650 ℃ 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.0.108 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 300sccm, and control reaction temperature is 1000 ℃, reacts to make Single Walled Carbon Nanotube 0.181 gram after 30 minutes.The diameter Distribution of the Single Walled Carbon Nanotube for preparing under this proportioning is 0.85～1.02nm.
Claims (6)
1. bi-metal oxide catalyst, it is characterized in that it is is carrier with magnesium oxide, the oxide compound that forms with iron is a Primary Catalysts, is the Fe/Mo/MgO catalyzer that promotor forms with the molybdenum, and iron in the catalyzer: molybdenum: the mol ratio of magnesium is 0.5～5: 0.01～3: 8～30.
2. bi-metal oxide catalyst according to claim 1 is characterized in that iron in the catalyzer: molybdenum: the mol ratio of magnesium is 1～3: 0.05～2: 10～20.
3. bi-metal oxide catalyst according to claim 1 is characterized in that magnesium oxide is selected from magnesia crystal, magnesium nitrate, magnesium acetate, magnesium oxalate, magnesium chloride, sal epsom, molybdenum are selected from the oxide compound of molybdate and molybdenum, and iron is selected from iron nitrate, iron acetate, iron(ic) chloride, ferric sulfate, ironic oxalate.
4. the described bi-metal oxide catalyst of claim 1 is used to prepare the method for the Single Walled Carbon Nanotube of controllable diameter, 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 is 20～200sccm, hydrogen or nitrogen or inert gas flow are 100～500sccm, temperature of reaction is controlled at 850～1200 ℃, reacts 10～100 minutes, collects product.
5. bi-metal oxide catalyst according to claim 4 is used to prepare the method for the Single Walled Carbon Nanotube of controllable diameter, it is characterized in that temperature of reaction is 950～1100 ℃.
6. bi-metal oxide catalyst according to claim 4 is used to prepare the method for the Single Walled Carbon Nanotube of controllable diameter, it is characterized in that methane flow is 25～75sccm, and hydrogen or nitrogen or inert gas flow are 200～400sccm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318135C (en) * | 2005-06-01 | 2007-05-30 | 浙江大学 | Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof |
| CN1326613C (en) * | 2004-11-11 | 2007-07-18 | 宁波华实纳米材料有限公司 | Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process |
| CN102757033A (en) * | 2012-07-03 | 2012-10-31 | 清华大学 | Method for preparing carbon nanotube with specific quantities of walls and specific diameters |
| CN108786885A (en) * | 2018-06-13 | 2018-11-13 | 北京工业大学 | A kind of bimetallic oxide/carbon nitrogen/carbon mano-tube composite and application |
| CN111326726A (en) * | 2020-03-06 | 2020-06-23 | 厦门海麒新能源科技有限公司 | Single-walled carbon nanotube-silicon carbon composite material and preparation method and application thereof |
| 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 |
-
2003
- 2003-07-08 CN CN 03141575 patent/CN1212189C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326613C (en) * | 2004-11-11 | 2007-07-18 | 宁波华实纳米材料有限公司 | Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process |
| CN1318135C (en) * | 2005-06-01 | 2007-05-30 | 浙江大学 | Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof |
| CN102757033A (en) * | 2012-07-03 | 2012-10-31 | 清华大学 | Method for preparing carbon nanotube with specific quantities of walls and specific diameters |
| CN108786885A (en) * | 2018-06-13 | 2018-11-13 | 北京工业大学 | A kind of bimetallic oxide/carbon nitrogen/carbon mano-tube composite and application |
| CN108786885B (en) * | 2018-06-13 | 2021-03-30 | 北京工业大学 | Bimetal oxide/carbon nitride/carbon nano tube compound and application thereof |
| CN111326726A (en) * | 2020-03-06 | 2020-06-23 | 厦门海麒新能源科技有限公司 | Single-walled carbon nanotube-silicon carbon composite material and preparation method and application thereof |
| 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 |
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| CN1212189C (en) | 2005-07-27 |
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