CN1217737C - Metal oxide catalyst and method for preparing bundle-formed multiwall nano carbon tube - Google Patents
Metal oxide catalyst and method for preparing bundle-formed multiwall nano carbon tube Download PDFInfo
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- CN1217737C CN1217737C CN 03116522 CN03116522A CN1217737C CN 1217737 C CN1217737 C CN 1217737C CN 03116522 CN03116522 CN 03116522 CN 03116522 A CN03116522 A CN 03116522A CN 1217737 C CN1217737 C CN 1217737C
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- wall carbon
- magnesium
- metal oxide
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 13
- 229910021392 nanocarbon Inorganic materials 0.000 title 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002041 carbon nanotube Substances 0.000 claims description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical group [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005087 graphitization Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- 239000002048 multi walled nanotube Substances 0.000 abstract 6
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 238000009841 combustion method Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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Abstract
The present invention relates to a metal oxide catalyst and a method for preparing bunched multi-wall carbon nanotubes by using the metal oxide catalyst to catalytically crack methane. The metal oxide catalyst is oxide containing magnesium and molybdenum, wherein the molar ratio of the magnesium to the molybdenum is (0.5 to 2.0): (0.5 to 3.0), and the preparation of the bundled multi-wall carbon nanotubes is carried out on a fixed bed reaction furnace with gas continuously flowing. Furnace temperature is increased to be from 500 to 1100 DEG C; then, the catalyst is placed into a constant-temperature region in the middle section of the furnace; methane whose flow rate is from 50 to 1500 sccm and hydrogen gas or nitrogen gas or inert gas whose flow rate is from 50 to 500 sccm are filled, and the bundled multi-wall carbon nanotubes are prepared by reactions lasting for 5 to 120 minutes. By using the catalyst provided by the present invention to prepare the bundled multi-wall carbon nanotubes, all the bundled multi-wall carbon nanotubes are bundled in a self-assembling mode. The present invention has the advantages of simple process operation, good repeatability, high activity and utilization rate of the catalyst and high yield, high purity, small and uniform tube diameter and high graphitization degree of the bundled multi-wall carbon nanotubes.
Description
Technical field
The present invention relates to a kind of metal oxide catalyst and utilize this cracking catalyst methane to prepare the method for bunchy multiple-wall carbon nanotube.
Background technology
CNT (carbon nano-tube) is a kind of novel material of finding the beginning of the nineties in last century, can be seen as to be rolled by certain mode by graphene layer to form, and can be divided into Single Walled Carbon Nanotube and multiple-wall carbon nanotube by the number of plies of its formation.CNT (carbon nano-tube) is because its good electricity, mechanics and thermal property, and having well in a lot of fields to have prospect.Chemical Vapor deposition process is because its output is bigger, and purity is higher, most possibly realizes the industrial mass continuous production, thereby chemical Vapor deposition process has become the most popular method for preparing CNT (carbon nano-tube) at present, and multiple-wall carbon nanotube makes preparation in this way more.The solid catalyst of the common working load type of this method, organic gas reacts in its surface adsorption, and final product is from the catalyst surface desorption.The vapour deposition process of CNT (carbon nano-tube) mainly carries out on fixed reaction bed, but catalyzer is not added any control, and the multiple-wall carbon nanotube of this Preparation of Catalyst does not generally have orientation relationship, can the self-assembly bunchy.In addition, because attracting each other of action of gravity and catalyst particles intergranular always has the zone that granules of catalyst is piled up in the final crude product that generates, catalyst activity and utilization ratio are not high.
Summary of the invention
The method that the present invention is intended to develop a kind of metal oxide catalyst and prepares the bunchy multiple-wall carbon nanotube with this cracking catalyst methane.
Metal oxide catalyst of the present invention is made up of the oxide compound of magnesium and molybdenum, and the mol ratio of magnesium/molybdenum is (0.5～2.0): (0.5～3.0), best (0.8～1.2): (1～1.5).
Above-mentioned magnesium can be selected from magnesium nitrate, and magnesium chloride, the magnesium oxide that sal epsom or magnesium acetate form, molybdenum can be selected from the oxide compound of molybdenum or the molybdenum oxide that molybdate forms.
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 oxide compound or the metal-salt that contains 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 oxide compound or the metal-salt that contains 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.Furnace temperature is risen to 500～1100 ℃, preferably 800～1100 ℃, again catalyzer is put into flat-temperature zone, stove stage casing, feed the methane of certain flow rate, and with a certain amount of hydrogen or nitrogen or inert gas dilution.The methane air speed is 50～1500sccm, preferably 600～1200sccm; Hydrogen or nitrogen or rare gas element air speed are 50～500sccm, and 100～250sccm preferably reacts and stops after 5～120 minutes, collects product and is bunchy multiple-wall carbon nanotube of the present invention.
Preparing the bunchy multiple-wall carbon nanotube with catalyzer provided by the invention, all is the self-assembly bunchy, and process operation is simple, good reproducibility, activity of such catalysts and utilization ratio height, bunchy multiple-wall carbon nanotube output is big, the purity height, caliber is little and even, the degree of graphitization height.
Description of drawings
Fig. 1 is the transmission electron micrograph of gained bunchy multiple-wall carbon nanotube;
Fig. 2 is the TGA analysis chart of gained bunchy multiple-wall carbon nanotube.
Embodiment
Embodiment 1:
Mo: Mg is the citric acid of getting magnesium nitrate hexahydrate, ammonium molybdate at 1: 1 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 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.0.107 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 1.085 grams after 30 minutes.The transmission electron microscope photo of product as shown in Figure 1.
Embodiment 2:
Mo: Mg is the citric acid of getting magnesium nitrate hexahydrate, ammonium molybdate at 1: 1 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 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.0.099 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 1.765 grams after 30 minutes.
Embodiment 3:
Mo: Mg is the citric acid of getting magnesium nitrate hexahydrate, ammonium molybdate at 1: 1 and being equal to the ammonium molybdate amount of substance 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.0.092 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 2.758 grams after 60 minutes.Thermogravimetric analysis TGA curve as shown in Figure 2, illustrates that product is purity height, a degree of graphitization multiple-wall carbon nanotube preferably.
Claims (6)
1. metal oxide catalyst that is used to prepare the bunchy multiple-wall carbon nanotube is characterized in that it is made up of the oxide compound of magnesium and molybdenum, and the mol ratio of magnesium/molybdenum is (0.5～2.0): (0.5～3.0).
2. metal oxide catalyst as claimed in claim 1 is characterized in that the mol ratio of magnesium/molybdenum is (0.8～1.2): (1～1.5).
3. metal oxide catalyst as claimed in claim 1 is characterized in that magnesium is selected from magnesium nitrate, and magnesium chloride, the magnesium oxide that sal epsom or magnesium acetate form, molybdenum are selected from the oxide compound of molybdenum or the molybdenum oxide that molybdate forms.
4. the described metal oxide catalyst of claim 1 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.
5. the method for preparing the bunchy multiple-wall carbon nanotube according to claim 4 is characterized in that temperature of reaction is 850-1100 ℃.
6. the method for preparing the bunchy multiple-wall carbon nanotube according to claim 4 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 |
|---|---|---|---|
| CN 03116522 CN1217737C (en) | 2003-04-17 | 2003-04-17 | Metal oxide catalyst and method for preparing bundle-formed multiwall nano carbon tube |
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| CN 03116522 CN1217737C (en) | 2003-04-17 | 2003-04-17 | Metal oxide catalyst and method for preparing bundle-formed multiwall nano carbon tube |
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| CN1443709A CN1443709A (en) | 2003-09-24 |
| CN1217737C true CN1217737C (en) | 2005-09-07 |
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