CN1438072A - Catayst for preparing carbon-nano tube - Google Patents

Catayst for preparing carbon-nano tube Download PDF

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Publication number
CN1438072A
CN1438072A CN 03105056 CN03105056A CN1438072A CN 1438072 A CN1438072 A CN 1438072A CN 03105056 CN03105056 CN 03105056 CN 03105056 A CN03105056 A CN 03105056A CN 1438072 A CN1438072 A CN 1438072A
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catalyst
cnt
preparation
solution
prepare
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CN1199727C (en
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赵芸
李春华
梁吉
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Tsinghua University
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Tsinghua University
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Abstract

The present invention relates to a catalyst for preparing carbon nano tube. Said catalyst is a compound oxide obtained by calcining multicomponent hydrotalcite containing iron, cobalt and nickel at high temperature. Said synthesis method is simple, convenient in operation and low in cost. Said compound oxide can be reduced by using hydrogen gas under the condition of a certain temp., and the carbon source gas can be decomposed, and the carbon nano tube whose outer diameter of the tube is 15-70 nm can be prepared out. Said catalyst is dissolved in common acid, and is easily separated from carbon nano tube.

Description

Be used to prepare the catalyst of CNT
Technical field
The invention belongs to range of catalysts, particularly a kind of catalyst that is used to prepare CNT.
Background technology
CNT is since 1991 are found by Iijima, its distinctive mechanics, electricity and chemical property and unique accurate one dimension tracheary element structure, in following high-tech area, demonstrate many potential using values, become the research focus in fields such as chemistry, physics and material science.People are striving to find that output is big, purity is high, defective is few, with low cost, the carbon nanotube production process with preparation of industrialization prospect.Just present, the preparation method of bibliographical information mainly contains arc discharge method, plasma method, laser method and chemical vapour deposition technique.Arc discharge method, plasma method and laser method all exist equipment and complex technical process, energy consumption is big, cost is high shortcoming; Equipment is simple, easy and simple to handle, the product purity advantages of higher and chemical vapour deposition technique has, and is a kind of method of tool large-scale industrial production.The key that chemical vapour deposition technique is produced CNT is a catalyst, the catalyst that bibliographical information adopts this legal system to be equipped with CNT is generally support type, carrier comprises silica gel, molecular sieve, aluminium oxide etc., and also having with organo-metallic compound or composite oxides is catalyst.There is the disadvantage of product postprocessing complexity in the supported catalyst preparation CNT.
CN1335257A and CN1170631A disclose a kind of composite oxide catalysts for preparing CNT respectively, and catalyst adopts the citric acid complex method preparation, and cost of material is higher, complex operation step, and energy consumption is big.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that is used to prepare CNT, it is characterized in that: the coprecipitation reaction that adopts metal salt solution and aqueous slkali earlier, preparation contains the polynary hydrotalcite precursor of iron, cobalt, nickel, obtains composite oxide catalysts again after high-temperature roasting.
Described metal salt solution is the mixed aqueous solution of the nitrate of magnesium, aluminium or sulfate or hydrochloride and transition metal nitrate or sulfate or hydrochloride or alcoholic solution or with the lysigenous solution of mixed solvent of water and alcohol.Described transition metal is iron, cobalt, nickel or its mixture, and wherein the molar content of transition metal in all metallic elements of catalyst is 1.7-25%.
Described aqueous slkali is the aqueous solution of NaOH or ammoniacal liquor and sodium carbonate or ammonium carbonate.
Described preparation catalyst concrete steps are: salting liquid and aqueous slkali are under agitation mixed, and at 40-90 ℃ of crystallization 0.5-6h, filtration, washing, drying obtain the polywater talcum then, in 500-700 ℃ of roasting 3-5h, then obtain prepared catalyst again.
The application of described catalyst in the preparation CNT, this technology is to carry out in fixed bed reactors; With a certain amount of catalyst at H 2Be warming up to 500-950 ℃ under the atmosphere, feed carbon-source gas, react and stopped in 20-120 minute, argon shield is cooling down, the collection product; Product purification is immersed in product in the salpeter solution of 1.0N, and ultrasonic processing 15 minutes after filtration, washing, the drying, is prepared into CNT, and by the transmission electron microscopy observation pattern.
The method for preparing catalyst that beneficial effect of the present invention provides is simple, and cost is low, uses the CNT that this catalyst can make a large amount of uniform diameter.
The specific embodiment
The present invention is a kind of catalyst that is used to prepare CNT.It adopts the coprecipitation reaction of metal salt solution and aqueous slkali earlier, and preparation contains the polynary hydrotalcite precursor of iron, cobalt, nickel, obtains composite oxide catalysts again after high-temperature roasting.Preparation catalyst concrete steps are: salting liquid and aqueous slkali are under agitation mixed, and at 40-90 ℃ of crystallization 0.5-6h, filtration, washing, drying obtain the polywater talcum then, in 500-700 ℃ of roasting 3-5h, then obtain prepared catalyst again.Above-mentioned metal salt solution is the mixed aqueous solution of magnesium, aluminium nitrate or sulfate or hydrochloride and transition metal nitrate or sulfate or hydrochloride or alcoholic solution or with the lysigenous solution of mixed solvent of water and alcohol.Above-mentioned aqueous slkali is the aqueous solution of NaOH or ammoniacal liquor and sodium carbonate or ammonium carbonate.
For embodiment the present invention is illustrated again below.
Embodiment 1
Solid MgSO with 18.92g (0.0767mol) 47H 2The solid CoSO of O and 3.73g (0.0133mol) 47H 2The solid Al of O and 14.99g (0.0225mol) 2(SO 4) 3-18H 2(Mg: Co: Al=1.7: 0.3: 1 mol ratio) be dissolved in the 100ml deionized water, be made into mixing salt solution, other takes by weighing 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na to O 2CO 3Be dissolved in the 100ml deionized water and be made into mixed ammonium/alkali solutions.Under vigorous stirring salting liquid is added drop-wise in the aqueous slkali, is warming up to 60 ℃, reaction 0.5h generates the pink colour precipitation, after filtration, washing and drying make nano-scale cobalt magnalium hydrotalcite Mg 3.4Co 0.6Al 2(OH) 12CO 34H 2O got nano-scale cobalt Mg-Al composite oxide in 3 hours in 600 ℃ of following roastings.
The preparation of CNT is carried out in fixed bed reactors.With 200mg cobalt Mg-Al composite oxide catalyst at H 2Be warming up to 800 ℃ under the atmosphere, the feeding flow is that propane and the flow of 52ml/min is the hydrogen of 200ml/min, reacts to stop in 90 minutes, and argon shield is cooling down, collects product.Product is purified, washing, drying, obtains pure nano-carbon tube 530mg.The CNT external diameter 30-60nm that makes by this method.
Embodiment 2
Solid Mg (NO with 20.77g (0.081mol) 3) 26H 2Solid Ni (the NO of O and 2.62g (0.009mol) 3) 26H 2Solid Al (the NO of O and 16.88g (0.045mol) 3) 39H 2(Mg: Ni: Al=1.8: 0.2: 1 mol ratio) be dissolved in wiring solution-forming in the 100ml ethanol, other takes by weighing 90ml ammoniacal liquor and 7.68g (0.08mol) (NH to O 4) 2CO 3Be dissolved in the 30ml deionized water and be made into mixed ammonium/alkali solutions.Under vigorous stirring salting liquid is added in the aqueous slkali fast, is warming up to 60 ℃, reaction 1.5h generates green precipitate, after filtration, washing and drying make nano-scale nickel magnalium hydrotalcite Mg 3.6Ni 0.4Al 2(OH) 12CO 34H 2O got nano-scale nickel Mg-Al composite oxide in 5 hours in 500 ℃ of following roastings.
The preparation of CNT is carried out in fixed bed reactors.200mg nickel Mg-Al composite oxide catalyst is warming up to 700 ℃ under H2 atmosphere, the feeding flow is that methane and the flow of 45ml/min is the hydrogen of 200ml/min, reacts to stop in 60 minutes, and argon shield is cooling down, collects product.Product is purified, washing, drying, obtains pure nano-carbon tube 300mg.The CNT external diameter 15-35nm that makes by this method.
Embodiment 3
Solid Mg (NO with 23.08g (0.09mol) 3) 26H 2Solid Fe (the NO of O and 1.82g (0.0045mol) 3) 39H 2Solid Al (the NO of O and 15.19g (0.0405mol) 3) 39H 2Its Mg of O: Fe: Al=2: 0.1: 0.9 (mol ratio) is dissolved in wiring solution-forming in the mixed solvent of 60ml ethanol and 60ml deionized water, and other takes by weighing 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na 2CO 3Be dissolved in the 120ml deionized water and be made into mixed ammonium/alkali solutions.Under vigorous stirring salting liquid is added in the aqueous slkali fast, is warming up to 40 ℃, reaction 0.5h generates the khaki precipitation, after filtration, washing and drying make nano-scale iron magnalium hydrotalcite Mg 4Fe 0.2Al 1.9(OH) 12CO 34H 2O got nano-scale iron Mg-Al composite oxide in 4 hours in 700 ℃ of following roastings.
The preparation of CNT is carried out in fixed bed reactors.With 200mg iron Mg-Al composite oxide catalyst at H 2Be warming up to 500 ℃ under the atmosphere, the feeding flow is that ethene and the flow of 45ml/min is the hydrogen of 205ml/min, reacts to stop in 120 minutes, and argon shield is cooling down, collects product.Product is purified, washing, drying, obtains pure nano-carbon tube 380mg.The CNT external diameter 15-30nm that makes by this method.
Embodiment 4
Solid MgCl by 7.70g (0.081mol) 2, the solid NiCl of 1.17g (0.009mol) 2And the solid FeCl of 0.73g (0.0045mol) 3And the solid AlCl of 5.41g (0.0405mol) 3The aqueous solution, Mg: Ni: Fe: Al=1.8 wherein: 0.2: 0.1: 0.9 (mol ratio) and 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na 2CO 3Aqueous slkali prepares ferronickel magnalium hydrotalcite presoma Mg in 90 ℃ of reaction 6h 3.6Ni 0.4Fe 0.2Al 1.8(OH) 12CO 34H 2O.600 ℃ of following roastings got nano-scale ferronickel Mg-Al composite oxide in 3 hours.
The preparation of CNT is under 700 ℃, is that the acetylene of 75ml/min and the hydrogen feeding 200mg catalyst reaction of 150ml/min stopped in 20 minutes with flow, collects product, obtains CNT 600mg behind the purifying.The CNT external diameter 40-70nm that makes by this law.
Embodiment 5
Solid Mg (NO by 20.77g (0.081mol) 3) 26H 2O, the solid Co (NO of 2.62g (0.009mol) 3) 26H 2Solid Fe (the NO of O and 1.21g (0.003mol) 3) 39H 2Solid Al (the NO of O and 10.13g (0.027mol) 3) 39H 2Its Mg of O: Co: Fe: Al=2.7: the aqueous solution of 0.3: 0.1: 0.9 (mol ratio), with 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na 2CO 3Aqueous slkali prepares ferro-cobalt magnalium hydrotalcite presoma Mg in 80 ℃ of reaction 4h 6.4Co 0.6Fe 0.2Al 0.8(OH) 16CO 34H 2O.600 ℃ of following roastings got nano-scale ferro-cobalt Mg-Al composite oxide in 3 hours.
The preparation of CNT is under 600 ℃, is that the propane of 100ml/min and the hydrogen feeding 200mg catalyst reaction of 150ml/min stopped in 40 minutes with flow, collects product, obtains CNT 580mg behind the purifying.The CNT external diameter 25-55nm that makes by this law.
Embodiment 6
Solid Mg (NO by 20.77g (0.081mol) 3) 26H 2O, the solid Ni (NO of 2.62g (0.009mol) 3) 26H 2Solid Fe (the NO of O and 1.82g (0.0045mol) 3) 39H 2Solid Al (the NO of O and 6.75g (0.018mol) 3) 39H 2Its Mg of O: Ni: Fe: Al=3.6: the aqueous solution of 0.4: 0.2: 0.8 (mol ratio), with 8.64g (0.216mol) NaOH and 4.77g (0.045mol) Na 2CO 3Aqueous slkali prepares ferronickel magnalium hydrotalcite presoma Mg in 70 ℃ of reaction 3h 7.2Ni 0.8Fe 0.4Al 1.6(OH) 20CO 34H 2O.600 ℃ of following roastings got nano-scale ferronickel Mg-Al composite oxide in 3 hours.
The preparation of CNT is under 950 ℃, is that the propane of 200ml/min and the hydrogen feeding 200mg catalyst reaction of 100ml/min stopped in 30 minutes with flow, collects product, obtains CNT 630mg behind the purifying.The CNT external diameter 30-70nm that makes by this law.

Claims (7)

1. a catalyst that is used to prepare CNT is characterized in that: adopt the coprecipitation reaction of metal salt solution and aqueous slkali earlier, prepare the polynary hydrotalcite precursor that contains iron, cobalt, nickel, obtain composite oxide catalysts again after high-temperature roasting.
2. according to the described a kind of catalyst that is used to prepare CNT of claim 1, it is characterized in that: described metal salt solution is the mixed aqueous solution of magnesium, aluminium nitrate or sulfate or hydrochloride and transition metal nitrate or sulfate or hydrochloride or alcoholic solution or with the lysigenous solution of mixed solvent of water and alcohol.
3. according to claim 1 or 2 described a kind of catalyst that are used to prepare CNT, it is characterized in that: described transition metal is iron-cobalt-nickel or its mixture, and wherein the molar content of transition metal in all metallic elements is 1.7-25%..
4. according to the described a kind of catalyst that is used to prepare CNT of claim 1, it is characterized in that: described aqueous slkali is the aqueous solution of NaOH or ammoniacal liquor and sodium carbonate or ammonium carbonate.
5. according to the described a kind of catalyst that is used to prepare CNT of claim 1, it is characterized in that: described preparation catalyst concrete steps are: salting liquid and aqueous slkali are under agitation mixed, then at 40-90 ℃ of crystallization 0.5-6h, filtration, washing, drying obtain the polywater talcum, in 500-700 ℃ of roasting 3-5h, then obtain prepared catalyst again.
6. the application of catalyst in the preparation CNT, it is characterized in that: described preparation CNT technology is carried out in fixed bed reactors, described catalyst is put into fixed bed reactors, under H2 atmosphere, be warming up to 500-950 ℃, feed carbon-source gas, react and stopped cooling under the argon shield, collection product in 20-120 minute; Product purification is that product is immersed in the salpeter solution of 1.0N, and ultrasonic processing 15 minutes promptly gets CNT after filtration, washing, the drying.
7. according to the application of the described catalyst of claim 6 in the preparation CNT, it is characterized in that: the carbon-source gas in this Preparation of Catalyst CNT of described use can be a methane, propane, ethene, acetylene.
CN 03105056 2003-03-03 2003-03-03 Catayst for preparing carbon-nano tube Expired - Fee Related CN1199727C (en)

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