CN1057940C - Transition metal catalyst and its use method in preparing uniform-caliber nanometre carbon pipe - Google Patents
Transition metal catalyst and its use method in preparing uniform-caliber nanometre carbon pipe Download PDFInfo
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- CN1057940C CN1057940C CN96110252A CN96110252A CN1057940C CN 1057940 C CN1057940 C CN 1057940C CN 96110252 A CN96110252 A CN 96110252A CN 96110252 A CN96110252 A CN 96110252A CN 1057940 C CN1057940 C CN 1057940C
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- transition metal
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- metal oxide
- air speed
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Abstract
The present invention relates to a transition metal catalyst and a method for preparing a carbon nanometer tube with a uniform tube diameter by the catalytic pyrolysis of methane or carbon monoxide on the catalyst. The catalyst is composed of at least one transition metal oxide and one alkaline earth / rare earth oxide, wherein the content of the transition metal oxides is from 1.0 to 70.0%. The methane with the air speed of 600 to 6000/h and the carbon monoxide with the air speed of 400 to 4000/h are introduced on the alkaline earth / rare earth catalyst at 573 to 1073K for reacting for 10 to 40 min, and products are collected. The products are soaked by acid and dried to obtain a pure carbon nanometer tube. The outer diameter of the pipe is from 10 to 50 nm. The present invention has the advantages simple operation and low cost.
Description
The present invention relates to a kind of transition-metal catalyst and utilization on this catalyst, methane or catalyzing carbon monoxide cracking prepare the new method of carbon nano tube with uniform diameter.
At present, the suitability for industrialized production of carbon fiber comprises two processes: the one, pitch through melt, after hot candied, oxidation and the carbonization thick carbon fiber in a large number, preparation or post-processing temperature at 1273 ° of its diameters more than the K in the millimeter level, (JP 62,298,618[87,289,618]; JP 01,69,692[89,69,692]; JP 01,141,984[89,141,984]); Other be by benzene on catalyst such as iron in 1323 ° of K cracking, can make diameter about 0.7 μ m, long carbon fiber about 200 μ m, (JP 01,260,019[89,260,019]).More than two kinds of carbon fiber output height that method makes, but preparation or post-processing temperature be at 1273 ° more than the K, caliber is thick.Have two kinds in order to the method for preparing nanoscale caliber carbon fiber in the laboratory: a kind of is to make (lijima S.Nature by arc discharge method on graphite, 352 (1991) 56), product is quite straight and caliber is less (～10nm) the product productive rate is lower, and separation and purification is difficulty all; Another kind method is to pass through C
2H
2In granularity catalytic pyrolysis preparation on the Ni-Cu alloy about 10nm through specially treated, (R.T.K.Baker waits Carbon, and 27 (1989) 315; Motojima S, Kawaguchi M, Nozaki K waits Appi.Phys.Lett.56 (1990) 32).The raw materials used gas of this method is acetylene, catalyst need adopt the specific process preliminary treatment so that catalyst granules about 10nm, reaction temperature is generally at 873 ° more than the K.
Purpose of the present invention is intended to develop a kind of low temperature, low cost, productive rate height, simple to operate decomposes new method for preparing CNT and the catalyst of transition metal oxide that is used for this method by methane or carbon monoxide on catalyst.
The used catalyst of the present invention contains at least a transition metal oxide and a kind of alkaline earth oxide or a kind of rare-earth oxide, and wherein transition metal oxide can be selected from: NiO, CoO, CuO etc., alkaline earth oxide can be selected from MgO, CaO etc., and rare-earth oxide can be selected from La
2O
3, CeO
2Deng.
Each component metal oxide molar content is:
Transition metal oxide: 1.0%～70.0%, be 10.0%～60.0% at last, especially 30.0%～50.0%;
Alkaline earth or rare-earth oxide: 30.0%～99.0%, preferably 40.0%～90.0%,
Especially 50.0%～70.0%.
Catalyst adopts the citric acid method preparation.The corresponding soluble-salt of transition metal oxide, alkaline earth oxide or the rare-earth oxide of metering is mixed and be dissolved in a certain amount of distilled water, soluble-salt is selected from nitrate or acetate, adds the citric acid of about 50% weight, makes solution A; With solution A reduction vaporization under 333～393 ° of K temperature, remove moisture until becoming pastel B; B is moved in the vacuum drying chamber in 373～423 ° of K, dry under 1.0～10KPa paulin pine body C; Thereafter C is moved in the Muffle furnace under 923～1173 ° of K, calcination 3～7 hours, then prepared catalyst samples.
The preparation of CNT is carried out on fixed bed gas continuous flow reactor device.With a certain amount of catalyst at H
2Be warming up to 773～1073 ° of K under the atmosphere, stablize 5～30 minutes after, be transferred to desired reaction temperature, reaction temperature is 573～1073 ° of K, preferably 673～1073 ° of K, especially 773～973 ° of K.Feed the methane or the carbon monoxide of certain air speed, the methane air speed is 600～6000/h, preferably 1200～6000/h, especially 2000～5000/h; The carbon monoxide air speed is 400～4000/h, preferably 600～3000/h, especially 1000～2400ml/h; React and stop the collection product after 10～40 minutes.Product purification is that product is immersed in the salpeter solution of 1.0～4.0N, slowly stirred 2～10 hours down in 303～373 ° of K, filter, the distillation washing, 353～423 ° of K were dried 2～5 hours down, can get pure CNT again after 473～673 ° of K purge 1～5 hour with high-purity He down.The pattern of CNT is by transmission electron microscope(TEM) and electron scanning electron microscopy observation.By CO on Ni-Mg or the Li-La catalyst is the CNT that unstripped gas makes, and external diameter of pipe is about 10～14nm, and pipe range is greater than 2 μ m; Methane is that unstripped gas can make the CNT of outer tube diameter at 15～20nm on Ni-Mg or the Co-La catalyst, pipe range is greater than 0.5 μ m, on Ni-La or the Ni-Ca catalyst be with methane unstripped gas can to get outer tube diameter be CNT about 50nm, pipe range is greater than 0.5 μ m.
Prepare carbon nano tube with uniform diameter with catalyst provided by the invention, easy and simple to handle, cost of manufacture is low.Gained CNT pipe is more straight, and caliber is little, and crystallinity is better.
The present invention is further described by embodiment below:
Embodiment 1
With 2.90 gram Ni (NO
3)
26H
2O and 2.56 gram Mg (NO
3)
26H
2O and 3 gram citric acids are dissolved in the 20.0ml distilled water, make solution A, move at the bottom of A to the 100ml garden in the flask with the decompression heater heating evaporation under 353 ° of K that circles round and take out most of moisture and get a pastel B, B is moved in the vacuum drying chamber in 373 ° of K, 1.0KPa under dry paulin pine thing C, thereafter C is moved in the Muffle furnace under 1023 ° of K temperature calcination 5 hours, and promptly got prepared catalyst samples.The preparation of CNT is carried out on fixed bed gas continuous flow reactor device.With the catalyst of 20mg at H
2Be warming up to 873 ° of K under the atmosphere, stablize 20 minutes after, feeding air speed is the methane of 2400/h, react to stop after 20 minutes the collection product.Product purification is that product is immersed in the salpeter solution of 1.0N, stirs 5 hours in 333 ° of K are slow down, filter, and the distillation washing, oven dry is 2 hours under 373 ° of K, can get the pure CNT of 33mg again after 573 ° of K purge 2 hours with high-purity He down.The pattern of CNT is by transmission electron microscope(TEM) and electron scanning electron microscopy observation.By the CNT that this method makes, external diameter of pipe 15～20nm.
Embodiment 2
Method is with embodiment 1
To feed air speed under 873 ° of K by embodiment 1 prepared 20mg Ni-Mg catalyst is the CO of 1200/h, reacts to stop after 30 minutes, collects product.Product is immersed in the salpeter solution of 2.0N 3 hours, after the washing drying the pure CNT of 40mg.By the CNT that this method makes, external diameter of pipe 10～14nm.
Embodiment 3
Catalyst is by 2.49 gram Ni (CH
3COO)
24H
2O and 4.20 gram La (NO
3)
35H
2O and 4.0 gram citric acids are made solution, find time, dry, calcination makes, and calcination temperature is 1023 ° of K, and the time is 5 hours.Concrete preparation method is with embodiment 1.The preparation of CNT is under 823 ° of K, is the CH of 3000/h with air speed
4Feed to react after 30 minutes on the 30mg catalyst and stop the collection product.Product is immersed in the salpeter solution of 1.0N after 2 hours washing dryings the pure CNT of 30mg.By the CNT that this method makes, external diameter of pipe 40～60nm.
Embodiment 4
With the Ni-La catalyst 30mg among the embodiment 3, be that the CO reaction of 1000/h stopped after 20 minutes feeding air speed under 573 ° of K, collect product.Product is immersed in the salpeter solution of 1.0N after 2 hours washing dryings the pure CNT of 5mg.Concrete preparation method and purification condition are with embodiment 1.By the CNT that this method makes, external diameter of pipe 10～14nm.
Embodiment 5
Catalyst is by 2.91 gram Co (NO
3)
26H
2O and 4.20 gram La (NO
3)
35H
2O and 3.0 gram citric acids are made solution, find time, dry, calcination makes, and calcination temperature is 1073 ° of K, and the time is 4 hours.The preparation of CNT is under 773 ° of K, is the CH of 2000/h with air speed
4Feed to react after 30 minutes on the 30mg catalyst and stop the collection product.Product is immersed in the salpeter solution of 2.0N after 2 hours washing dryings the pure CNT of 10mg.Concrete preparation method and purification condition are with embodiment 1.By the CNT that this method makes, the about 20nm of external diameter of pipe.
Embodiment 6
Catalyst is by 2.46 gram Cu (NO
3)
23H
2O and 236 gram Ca (NO
3)
25H
2O and 3.0 gram citric acids are made solution, find time, dry, calcination makes, and calcination temperature is 1000 ° of K, and the time is 5 hours.The preparation of CNT is under 1073 ° of K, is the CH of 2400/h with air speed
4Feed to react after 30 minutes on the 20mg catalyst and stop the collection product.Product is immersed in the salpeter solution of 1.0N after 2 hours washing dryings the pure CNT of 53mg.Concrete preparation method and purification condition are with embodiment 1.By the CNT that this method makes, external diameter of pipe 40～60nm.
Claims (8)
1. catalyst of transition metal oxide that is used to prepare CNT, contain at least a transition metal oxide and a kind of alkaline earth oxide or rare-earth oxide, it is characterized in that transition metal oxide can be selected from NiO, CoO, CuO, alkaline earth oxide can be selected from MgO, CaO, and rare-earth oxide can be selected from La
2O
3, CeO
2Each component metal oxide molar content is a transition metal oxide 1.0%～70.0%, alkaline-earth metal or rare-earth oxide 30.0%～99.0%.
2. a kind of catalyst of transition metal oxide that is used to prepare CNT as claimed in claim 1, it is characterized in that each component metal oxide molar content is a transition metal oxide 10.0%～60.0%, alkaline earth/rare-earth oxide 40.0%～90.0%.
3. a kind of catalyst of transition metal oxide that is used to prepare CNT as claimed in claim 1, it is characterized in that each component metal oxide molar content is a transition metal oxide 30.0%～50.0%, alkaline earth/rare-earth oxide 50.0%～70.0%.
4. catalyst of transition metal oxide is used to prepare the method for carbon nano tube with uniform diameter, it is characterized in that a certain amount of catalyst at H
2Be warming up to 773～1073 ° of K under the atmosphere, after stablizing 5～30 minutes, reaction temperature is controlled at 573～1073 ° of K, feed the methane or the carbon monoxide of certain air speed, the methane air speed is 600～6000/h, the carbon monoxide air speed is 400～4000/h, react and stop after 10～40 minutes, collect product, product is soaked in 1.0～4.0N salpeter solution, stirred 2～10 hours down in 303～373 ° of K, filter, washing was dried 2～5 hours down in 353～423 ° of K, purged 1～5 hour with high-purity He down in 473～673 ° of K again.
5. catalyst of transition metal oxide as claimed in claim 4 is used to prepare the method for carbon nano tube with uniform diameter, it is characterized in that reaction temperature is 673～1073 ° of K.
6. catalyst of transition metal oxide as claimed in claim 4 is used to prepare the method for carbon nano tube with uniform diameter, it is characterized in that reaction temperature is 773～973 ° of K.
7. catalyst of transition metal oxide as claimed in claim 4 is used to prepare the method for carbon nano tube with uniform diameter, it is characterized in that the methane air speed is 1200～6000/h, and the carbon monoxide air speed is 600～3000/h.
8. catalyst of transition metal oxide as claimed in claim 4 is used to prepare the method for carbon nano tube with uniform diameter, it is characterized in that the methane air speed is 2000～5000/h, and the carbon monoxide air speed is 1000～2400/h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96110252A CN1057940C (en) | 1996-07-17 | 1996-07-17 | Transition metal catalyst and its use method in preparing uniform-caliber nanometre carbon pipe |
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|---|---|---|---|
| CN96110252A CN1057940C (en) | 1996-07-17 | 1996-07-17 | Transition metal catalyst and its use method in preparing uniform-caliber nanometre carbon pipe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1170631A CN1170631A (en) | 1998-01-21 |
| CN1057940C true CN1057940C (en) | 2000-11-01 |
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| CN96110252A Expired - Fee Related CN1057940C (en) | 1996-07-17 | 1996-07-17 | Transition metal catalyst and its use method in preparing uniform-caliber nanometre carbon pipe |
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Families Citing this family (13)
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|---|---|---|---|---|
| CN1111177C (en) * | 1998-10-19 | 2003-06-11 | 中国科学院化学研究所 | Disperser for nm-class carbon tubes and its preparing process |
| US6333016B1 (en) * | 1999-06-02 | 2001-12-25 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes |
| CN1083800C (en) * | 1999-06-04 | 2002-05-01 | 北京大学 | Method for preparing mono-layer nano-pipe |
| CN1100154C (en) * | 2000-01-20 | 2003-01-29 | 南开大学 | Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material |
| CN1113990C (en) * | 2000-06-07 | 2003-07-09 | 华侨大学 | High elastic screw carbon fibre and its preparing method |
| WO2006007760A1 (en) * | 2004-07-19 | 2006-01-26 | Lingyong Kong | Double-walled carbon nanotubes and the preparing method of same |
| CN100335170C (en) * | 2004-12-31 | 2007-09-05 | 厦门大学 | Promoting cobalt-copper base catalyst for preparation of low carbon mixed alcohol-carbon nano tube from synthetic gas and preparing method thereof |
| CN100348316C (en) * | 2005-05-30 | 2007-11-14 | 浙江大学 | Catalyst mixed with copper and alkali metal, and process for preparing one dimensional nano carbon material using same thereof |
| DE102008023229B4 (en) | 2008-05-02 | 2013-06-27 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | A method for producing carbon nanotubes on a carrier substrate, carbon nanotubes produced by the method and their use |
| JP6028189B2 (en) | 2011-09-30 | 2016-11-16 | 三菱マテリアル株式会社 | A method for producing carbon nanofibers containing metallic cobalt. |
| CN104254394A (en) * | 2012-03-12 | 2014-12-31 | 南洋理工大学 | Methods of preparing catalysts for the chirally selective synthesis of single-walled carbon nanotubes |
| CN107195542A (en) * | 2017-05-31 | 2017-09-22 | 中山大学 | A kind of method of the direct epitaxial growth CNT of metal substrate |
| CN108404587A (en) * | 2018-02-13 | 2018-08-17 | 南京师范大学 | A kind of system and method for coupling utilization of new energy resources carbon dioxide |
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| JPS61161144A (en) * | 1985-01-08 | 1986-07-21 | Matsushita Electric Ind Co Ltd | Oxidizing catalyst for burning catalyst |
| JPS61222926A (en) * | 1985-03-29 | 1986-10-03 | Dainichi Seika Kogyo Kk | Production of perovskite-type fine powder |
| US4977123A (en) * | 1988-06-17 | 1990-12-11 | Massachusetts Institute Of Technology | Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength |
| CN1018984B (en) * | 1989-05-17 | 1992-11-11 | 中国科学技术大学 | Catalyzer for waste gas purification of copper, lanthanum-bearing oxidate and its producing method |
| EP0513369A1 (en) * | 1990-11-08 | 1992-11-19 | Fanuc Ltd. | Numerically controlled device with working simulation function |
| EP0468127B1 (en) * | 1990-07-26 | 1994-05-11 | Peking University | Perovskite-type rare earth complex oxide combustion catalysts |
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1996
- 1996-07-17 CN CN96110252A patent/CN1057940C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61161144A (en) * | 1985-01-08 | 1986-07-21 | Matsushita Electric Ind Co Ltd | Oxidizing catalyst for burning catalyst |
| JPS61222926A (en) * | 1985-03-29 | 1986-10-03 | Dainichi Seika Kogyo Kk | Production of perovskite-type fine powder |
| US4977123A (en) * | 1988-06-17 | 1990-12-11 | Massachusetts Institute Of Technology | Preparation of extrusions of bulk mixed oxide compounds with high macroporosity and mechanical strength |
| CN1018984B (en) * | 1989-05-17 | 1992-11-11 | 中国科学技术大学 | Catalyzer for waste gas purification of copper, lanthanum-bearing oxidate and its producing method |
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| EP0513369A1 (en) * | 1990-11-08 | 1992-11-19 | Fanuc Ltd. | Numerically controlled device with working simulation function |
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| CN1170631A (en) | 1998-01-21 |
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