CN1446628A - Transition metals catalyst and its usage in the method for preparing fishbone type nano carbon fiber - Google Patents

Transition metals catalyst and its usage in the method for preparing fishbone type nano carbon fiber Download PDF

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CN1446628A
CN1446628A CN 03114990 CN03114990A CN1446628A CN 1446628 A CN1446628 A CN 1446628A CN 03114990 CN03114990 CN 03114990 CN 03114990 A CN03114990 A CN 03114990A CN 1446628 A CN1446628 A CN 1446628A
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catalyst
transition
fiber
carbon nano
product
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CN1282501C (en
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赵铁均
顾雄毅
戴迎春
袁渭康
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

A transition metal catalyst contains the transition metal oxide (10-90 wt.%) and alumina (10-90 wt.%). A process for preparing the fish bone-shaped nano-class carbon fibres includes loading the catalyst in continuous flowing fixed-bed reactor, reducing in hydrogen, introducing the mixture of carbon-source gas and hydrogen gas, collecting the resultant on catalyst and purifying. Its advantages are uniform distribution of active centers, high output rate, and uniform diameter and high graphitized level of nano carbon fibres.

Description

The method of transition-metal catalyst and this Preparation of Catalyst plshy bone open carbon nano-fiber
Technical field
The present invention relates to a kind of transition-metal catalyst and be used to prepare the method for homogeneous diameter plshy bone open carbon nano-fiber.
Background technology
At present the plshy bone open carbon nano-fiber demonstrates good prospect in the application as fields such as the electrode material of composite reinforcing agent, battery, novel hydrogen storage material and catalyst carriers, and the prerequisite of using to obtain high-quality, high yield and plshy bone open carbon nano-fiber with economy.
From the production method of plshy bone open carbon nano-fiber, think that at present chemical vapour deposition (CVD) under catalyst action (CCVD) method has the potentiality of large-scale production.Its principle roughly is, vapor-phase reactant such as methane, ethene, through after the preheating by being equipped with the prereduction catalyst layer, as corronil, under temperature 673～1073K, vapor-phase reactant decomposes, constantly generate carbon nano-fiber on catalyst layer, catalyst layer constantly expands, along with the carrying out of reaction, continuous inactivation (the Baker of catalyst, Rodriguez, J.Mater.Res.Vol.8 (2), 3233-50 (1993); Langmuir, 11,3862 (1995), Cata.Today, 37,295 (1997)).
The catalyst method of the method for another kind of vapor phase growth for flowing, promptly use methane, ethane, the metallo-organic compound that carbon compounds such as benzene carry iron nickel enters reactor, metallo-organic compound is under the situation about 500K, decompose the ultra-fine nano-level iron particle of generation, the iron particle collides the iron catalyst that forms nanoscale size in reactor, and carbon source at high temperature, under 1173K, constantly be deposited on the iron powder catalyst, form plshy bone open carbon nano-fiber (Tibbets, Endo, Cheng Huiming, Appli.Phys.Lett., 72 (25), 3282 (1998), J.Cryst.Growth66,632 (1984), J.Appl.Phys.64,2995 (1988)).Different by the carbon nano-fiber that above flowing catalyst method is produced with the internal structure of the carbon nano-fiber of loaded catalyst formation, the carbon nano-fiber graphite linings that the former forms is parallel with the axle of fiber to be so-called tubular type carbon nano-fiber, and the graphite linings in the plshy bone open carbon nano-fiber that forms under the catalysis of corronil is so-called plshy bone open carbon nano-fiber with axle at angle, and angle is relevant with carbon source, catalyst and reaction temperature.
Experimental results show that, the diameter of the carbon nano-fiber that obtains by CVD method depends on the diameter of activated centre particle in the corresponding catalyst, particle diameter wider distribution owing to the monel that generates by coprecipitation method, particularly liquid deposition has formed big alloying pellet, the carbon nano-fiber diameter wider distribution that makes generation, the carbon nano-fiber quality instability of this wide distribution, for example there are uncertainty in specific area, pore-size distribution thereby make application go up.Additive method such as infusion process are though it is less hour to obtain narrower activated centre distribution output in load capacity.
In sum, preparation method before exists complicated operation, cost height, the low defective of resulting carbon nano-fiber degree of graphitization.
Summary of the invention
Technical problem to be solved by this invention provides the method for a kind of transition-metal catalyst and this Preparation of Catalyst plshy bone open carbon nano-fiber, to overcome above many disadvantages of the prior art.The present invention is intended to obtain to have the catalyst of higher yields and the method for producing the uniform plshy bone open carbon nano-fiber of diameter.
The weight percent content of catalyst of the present invention comprises:
Transition metal oxide 10-90%
Aluminium oxide 10-90%.
Said transition metal oxide is one or more among Fe, Ni, Cu, Co, Mo or the Cr.
Aluminium oxide is the carrier of this catalyst.
Preferred weight percent content comprises:
Transition metal oxide 30-70%
Aluminium oxide 30-70%.
The performance of catalyst of the present invention also has very confidential relation with its preparation method except its specific prescription.The present invention generates at carrier, the activated centre presoma is all different with above-described infusion process and coprecipitation on preparing.
Preparation of catalysts of the present invention is preparation like this:
With one or more transition metal and soluble aluminum salt according to the aforementioned proportion mixed dissolution in water, said soluble-salt comprises and a kind of in sulfate, acetate or the nitrate etc. forms solution A that the weight concentration 10%-50% of this solution is for suitable;
NaOH and sodium carbonate mixed dissolution in water, are formed mixed solution B, solution concentration with 10%-30% for suitable;
With solution A and solution B hybrid reaction, form precipitation, reaction temperature is 20～80 ℃, under 50～95 ℃ condition, leave standstill the collecting precipitation thing, in temperature is 70 ℃, pressure is crystallization under the condition of 1.0-10Kpa, calcines under the condition of 773-1073K 2～8 hours then, promptly obtains said catalyst of the present invention.
Catalyst of the present invention can be used for preparing the plshy bone open carbon nano-fiber, and concrete preparation method comprises the steps:
(1) place continuous flow reactor of fixed bed to reduce at hydrogen atmosphere described catalyst, reduction temperature is 773-1073K, and the recovery time is 1-6 hour.
(2) mixture of feeding carbon-source gas and hydrogen, reaction temperature is 573-1073K, preferably 673-973K, especially 773-873K, the air speed of hydrocarbon gas ethene is 600-10000/h, 1200-6000/h preferably, especially 2000-4000/h, the reaction time is 1～72 hour, the product on the collection catalyst, purifying obtains pure plshy bone open carbon nano-fiber.Preferred carbon-source gas comprises C 1～C 4Hydro carbons, as methane and ethene, CO 2Or a kind of among the CO.
Carbon-source gas: hydrogen=4: 1-1: 4 mol ratios.
According to the present invention, product is collected purifying and is comprised the steps: catalyst product is placed 1.0-4.0M hydrochloric acid or nitric acid, filters and washes through distillation, places and carries out drying under the 373-390K condition, and product purged 2-5 hour with the argon gas of 473-573K.
The pattern available electron transmission electron microscope of plshy bone open carbon nano-fiber is observed.
Catalyst provided by the invention has the distribution of more uniform activated centre than conventional infusion process or DNAcarrier free alloy catalyst, preparation method's simple possible of the present invention, and cost is low, the productive rate height.The plshy bone open carbon nano-fiber diameter that is obtained is even, the degree of graphitization height.
Description of drawings
Fig. 1 is a gained carbon nano-fiber pattern.
Fig. 2 is a gained carbon nano-fiber pattern
Fig. 3 is a gained carbon nano-fiber microstructure.
Fig. 4 is that gained carbon nano-fiber degree of graphitization characterizes.
The specific embodiment
Embodiment 1
Take by weighing 48.87gNi (NO 3) 26H 2O, 13.12gCu (NO 3) 23H2O, 28.14gAl (NO 3) 39H 2O adds an amount of distilled water and forms mixed solution A; Weighing sodium hydroxide 24g mixes with sodium carbonate 7.95g and adds a certain amount of water, form mixed solution B, B is placed a there-necked flask, and under stirring condition, dropwise add A and form precipitation, reaction temperature is 50 ℃, leaves standstill two hours, moves to then in 80 ℃ the thermostat to spend the night, cooling, with the gained dope filtration, washing obtains being precipitated as C, C is 70 ℃ in temperature, pressure is to spend the night in the vacuum drying chamber of 5Kpa to obtain crystal D, and D carries out calcination in muffle furnace, and temperature is 900K, stablized 5 hours, the product of gained is the catalyst that is obtained.
The preparation of plshy bone open carbon nano-fiber is carried out in continuous flow reactor of fixed bed, takes by weighing the catalyst samples of 100mg, reduces in hydrogen atmosphere, reduction temperature is 900K, stablized 3 hours, and be adjusted to needed reaction temperature, reaction temperature can be 810K.The air speed that feeds ethene can be 3000/h, and the mol ratio of ethene and hydrogen is 4: 1, collects product through 8 hours reaction backs, and weighing is about about 12g.Product purification is that product was placed 2.5M hydrochloric acid 72 hours, filter and wash through distillation, place and carry out drying under the 382K condition, product purges with the argon gas of 500K can obtain pure plshy bone open carbon nano-fiber in 3.5 hours, and the pattern available electron transmission electron microscope of plshy bone open carbon nano-fiber is observed.As Fig. 1.
Embodiment 2
Take by weighing 28.87gNi (NO 3) 26H2O, 13.12gFeCl 27H2O, 48.14gAl (NO 3) 39H2O adds an amount of distilled water and forms mixed solution A; Weighing sodium hydroxide 40g mixes with sodium carbonate 10.6g and adds a certain amount of water, forms mixed solution B, is a kind of active catalyst that is obtained as embodiment 1 by precipitation, heating, filtration, product dry, the calcination gained.
Embodiment 3
Take by weighing 60.05gNi (NO 3) 26H2O, 4.82gCu (NO 3) 23H2O, 9.375gAl (NO 3) 39H 2O adds an amount of distilled water and forms mixed solution A; Weighing sodium hydroxide 20g mixes with sodium carbonate 1.325g and adds a certain amount of water, form mixed solution B, put 200ml distilled water in a there-necked flask, and under stirring condition, dropwise add simultaneously A and B, reaction temperature be 50 ℃ for well, the dropping process was finished in two hours, moved to then in 80 ℃ the thermostat to spend the night, cooling, with the gained dope filtration, washing obtains being precipitated as C, C is 70 ℃ in temperature, pressure is to spend the night in the vacuum drying chamber of 10Kpa to obtain crystal D, and D carries out calcination in muffle furnace, and temperature is 800K, stablized 5 hours, the product of gained is the catalyst that is obtained.
Embodiment 4
Take by weighing 33.92gNi (NO 3) 26H2O, 11.62gCu (NO 3) 23H2O, 46.9gAl (NO 3) 39H 2O adds an amount of distilled water and forms mixed solution A; Weighing sodium hydroxide 20g mixes a certain amount of water of adding with sodium carbonate 6.625g, form mixed solution B, is a kind of active catalyst that is obtained as embodiment 3 by precipitation, heating, filtration, drying, calcination products therefrom.
Embodiment 5
Take by weighing 92.65gNi (NO 3) 26H2O, 13.12gFeSO 47H2O, 28.14gAl (NO 3) 39H2O adds an amount of distilled water and forms mixed solution A; Weighing sodium hydroxide 60g mixes with sodium carbonate 7.95g and adds a certain amount of water, forms mixed solution B, is a kind of active catalyst that is obtained as embodiment 3 by precipitation, heating, filtration, product dry, the calcination gained.
Embodiment 6
As the catalyst samples of embodiment 1 gained, take by weighing 100mg and place continuous flow reactor of fixed bed, feed the mixture of ethene and hydrogen, air speed is 4000/h, and the mol ratio of hydrogen and ethene is 1: 4, and temperature is 870K, reacted 25 hours, and obtained solid product 15g.As Fig. 2.
Embodiment 7
As the catalyst samples of embodiment 4 gained, take by weighing 100mg and place continuous flow reactor of fixed bed, feed methane, air speed is 4000/h, temperature is 773-873K, reacts 16 hours, obtains solid product 8g.Its microstructure as shown in Figure 3.
Embodiment 8
As the catalyst samples of embodiment 2 gained, take by weighing 100mg and place continuous flow reactor of fixed bed, feed ethene, hydrogen, the ethene air speed is 4000/h, and the ratio of ethene and hydrogen is 1: 1, and temperature is 775K, reacts 24 hours, obtains solid product 20g.Adopt document Baker, Rodriguez, J.Mater.Res.Vol.8 (2), the method that 3233-50 (1993) provides is carried out degree of graphitization to it and is characterized, and the result is as shown in Figure 4.
Embodiment 9
As the catalyst samples of embodiment 2 gained, take by weighing 100mg and place continuous flow reactor of fixed bed, feed ethene, hydrogen, the ethene air speed is 4000/h, and the ratio of ethene and hydrogen is 4: 1, and temperature is 790K, reacts 16 hours, obtains solid product 30g.

Claims (10)

1. transition-metal catalyst is characterized in that weight percent content comprises:
Transition metal oxide 10-90%
Aluminium oxide 10-90%.
2. transition-metal catalyst according to claim 1 is characterized in that said transition metal oxide is one or more among Fe, Ni, Cu, Co, Mo or the Cr.
3. transition-metal catalyst according to claim 1 is characterized in that weight percent content comprises:
Transition metal oxide 30-70%
Aluminium oxide 30-70%
Said transition metal oxide is one or more among Fe, Ni, Cu, Co, Mo or the Cr.
4. according to claim 1,2 or 3 described transition-metal catalysts, it is characterized in that being preparation like this:
With one or more transition metal and soluble aluminum salt according to the aforementioned proportion mixed dissolution in water, form solution A;
With NaOH or/and the sodium carbonate mixed dissolution in water, forms mixed solution B;
With solution A and solution B hybrid reaction, form precipitation, reaction temperature is 20～80 ℃, under 50～95 ℃ condition, leave standstill, the collecting precipitation thing is 50～85 ℃ in temperature, and pressure is crystallization under the condition of 1.0-10Kpa, under the condition of 773-1073K, calcined 2～8 hours then, promptly obtain said catalyst.
5. transition-metal catalyst according to claim 4 is characterized in that being preparation like this: said soluble-salt comprises a kind of in sulfate, acetate or the nitrate etc.
6. a method for preparing the plshy bone open carbon nano-fiber is characterized in that comprising the steps:
(1) place continuous flow reactor of fixed bed to reduce at hydrogen atmosphere each described catalyst of claim 1～5, reduction temperature is 773-1073K, and the recovery time is 1-6 hour.
(2) mixture of feeding carbon-source gas and hydrogen, reaction temperature is 573-1073K, and the air speed of hydrocarbon gas is 600-10000/h, and the reaction time is 1～72 hour, the product on the collection catalyst, purifying obtains pure plshy bone open carbon nano-fiber.
7. method according to claim 6 is characterized in that carbon-source gas comprises C 1～C 4Hydro carbons, CO 2Or among the CO one or more.
8. method according to claim 6 is characterized in that hydrocarbon gas: hydrogen=4: 1-1: 4, and mol ratio.
9. method according to claim 6 is characterized in that, reaction temperature is 673-973K, and the air speed of hydrocarbon gas is 1200-6000/h.
10. method according to claim 6, it is characterized in that, product is collected purifying and is comprised the steps: catalyst product is placed 1.0-4.0m hydrochloric acid or nitric acid, filter and wash through distillation, place and carry out drying under the 373-390K condition, product purged 2-5 hour with the argon gas of 473-573K.
CN 03114990 2003-01-20 2003-01-20 Transition metals catalyst and its usage in the method for preparing fishbone type nano carbon fiber Expired - Fee Related CN1282501C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1292984C (en) * 2004-12-17 2007-01-03 南京大学 Process and device for producing nano carbon fiber
CN100406596C (en) * 2005-08-29 2008-07-30 天津大学 Vapour deposition in situ reaction method for preparing carbon nanotube reinforced aluminium matrix composite material
CN103447097A (en) * 2012-06-04 2013-12-18 中国科学院大连化学物理研究所 Preparation method of novel nano carbon composite material of SiC base
US8696943B2 (en) 2008-06-18 2014-04-15 Showa Denko K.K. Carbon nanofiber, producing method and use of the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1292984C (en) * 2004-12-17 2007-01-03 南京大学 Process and device for producing nano carbon fiber
CN100406596C (en) * 2005-08-29 2008-07-30 天津大学 Vapour deposition in situ reaction method for preparing carbon nanotube reinforced aluminium matrix composite material
US8696943B2 (en) 2008-06-18 2014-04-15 Showa Denko K.K. Carbon nanofiber, producing method and use of the same
CN103447097A (en) * 2012-06-04 2013-12-18 中国科学院大连化学物理研究所 Preparation method of novel nano carbon composite material of SiC base

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