CN1244405C - Transition metals catalyst and method for preparing tubular type nano carbon fiber with even diameter - Google Patents
Transition metals catalyst and method for preparing tubular type nano carbon fiber with even diameter Download PDFInfo
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- CN1244405C CN1244405C CN 03114991 CN03114991A CN1244405C CN 1244405 C CN1244405 C CN 1244405C CN 03114991 CN03114991 CN 03114991 CN 03114991 A CN03114991 A CN 03114991A CN 1244405 C CN1244405 C CN 1244405C
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Abstract
The present invention discloses a transition metal catalyst and a method for preparing tubular type nanometer carbon fiber with even diameter. The components and the contents of weight percentage of the catalyst in the present invention comprises 1 to 95% transition metal oxide and 5 to 99% of alumina carriers. The present invention is different from an immersion method and a co-precipitation method in the preparation of a predecessor body with an active center, and thus, the effect which is completely different from the effect of the prior art is obtained. The catalyst of the present invention can be used for preparing the tubular type nanometer carbon fiber, and the catalyst provided by the present invention has more even distribution of active centers than the catalyst of the conventional immersion method. The preparation method of the present invention has the advantages of simplicity, feasibility, low cost and high yield, and the diameter of the obtained tubular type nanometer carbon fiber is even.
Description
Technical field
The present invention relates to a kind of catalyst for preparing the tubular type carbon nano-fiber, and the method for preparing homogeneous diameter tubular type carbon nano-fiber with the carbon monoxide for the carbon source disproportionation.
Background technology
At present the tubular type 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 tubular type carbon nano-fiber with economy.
From the production method of tubular type 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 tubular type carbon nano-fiber (Tibbets, Endo, Cheng Huiming, Appli.Phys.Lett., 72 (25), 3282 (1998), J.Cryst.Growth 66,632 (1984), J.Appl.Phys.64,2995 (1988)).Different with the internal structure of the carbon nano-fiber of loaded catalyst formation by the carbon nano-fiber that above flowing catalyst method is produced, 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 carbon nano-fiber that forms under the catalysis of corronil is so-called plshy bone open carbon nano-fiber with axle at angle.
In sum, the catalyst that technology provided in the past exists the activated centre skewness, preparation method's complexity, and the cost height, productive rate is low, the uneven defective of tubular type carbon nano-fiber diameter that is obtained.
Summary of the invention
The technical issues that need to address of the present invention are the methods that disclose a kind of transition-metal catalyst and adopt this Preparation of Catalyst homogeneous diameter tubular type carbon nano-fiber, and the present invention is intended to obtain to have the catalyst of higher yields and the method for producing the uniform tubular type carbon nano-fiber of diameter.
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, therefore, the space in activated centre evenly and in reduction process not the catalyst of sintering will help generating the uniform carbon nano-fiber of diameter.Less and comparatively even in order to obtain in the loaded catalyst grain diameter in activated centre, the ratio that requires active component simultaneously is high catalyst as far as possible, the present invention proposes the catalyst generation method of the uniform tubular type carbon nano-fiber of a kind of novel particle diameter, on fixed bed reactors, carried out active review, found that tubular type carbon nano-fiber productive rate is higher; By the pattern of high-resolution transmission electron microscope (HRTEM) observation tubular type carbon nano-fiber, the diameter of tubular type carbon nano-fiber is even.
The component of catalyst of the present invention and weight percent content are:
Transition metal oxide 1-95%
Alumina support 5-99%
Said transition metal is one or more among Fe, Ni or the Co;
Preferred ingredients and weight percent content comprise:
Transition metal oxide 10-30%
Alumina support 70-90%
The present invention is different with infusion process and coprecipitation in the preparation of activated centre presoma, has obtained thus and the diverse effect of prior art, and concrete method comprises the steps:
With one or more transition metal solubility salt mixed dissolutions in water, said soluble-salt comprises sulfate, acetate, nitrate and hydrochloride, the alumina support that adds metering, form aaerosol solution A, stirred 2～6 hours, the molar concentration of transition metal soluble-salt is suitable with 0.012～0.024mol/l;
Ferricyanate, ferrocyanic acid salt or nitroferrocyanic acid salt is soluble in water, form solution B, its molar concentration is suitable with 0.01～0.05mol/l;
B is slowly injected A, carry out violent stirring simultaneously, time is 2～4 hours, and operating temperature is 30～60 ℃, stirs then 2～15 hours, the gained dope filtration, washing, dry under 100～130 ℃, calcination is 2～7 hours under 573-1073K, promptly obtain catalyst of the present invention, wherein B is for suitable according to corresponding ferricyanate, ferrocyanic acid salt or nitroferrocyanic acid salt chemistry physical measurement ratio with the weight ratio of A.
Catalyst of the present invention can be used for preparing the tubular type carbon nano-fiber, and concrete method comprises the steps:
(1) above-mentioned catalyst is placed continuous flow reactor of fixed bed, reduce in hydrogen atmosphere, reduction temperature is 773-1073K, and the time is 1～5 hour;
(2) mixture of feeding carbon monoxide and hydrogen, the air speed of carbon monoxide is 800-10000/h, especially 1000-8000/h, after reaction in 1～72 hour, adopt conventional method to collect purified product, promptly obtain the said tubular type carbon nano-fiber of the present invention from catalyst.Reaction temperature is 573-1073K, preferably 673-973K, especially 773-873K.
Carbon monoxide: hydrogen=4: 1～1: 4, mol ratio
According to the present invention, product purification comprises the steps:
Reacted catalyst is placed 1.0-4.0M hydrochloric acid or nitric acid, filter, washing places and carries out drying under the 373-390K condition, and product purged 2-5 hour with the argon gas of 473-573K, can obtain pure tubular type carbon nano-fiber.
Catalyst provided by the invention has more uniform activated centre than conventional infusion process and distributes, preparation method's simple possible of the present invention, and cost is low, the productive rate height.The tubular type carbon nano-fiber diameter that is obtained is even.
Description of drawings
Fig. 1 is the uniform tubular type carbon nano-fiber of a diameter of the present invention pattern.
Fig. 2 is the uniform tubular type carbon nano-fiber of an another kind of diameter of the present invention pattern.
Fig. 3 is a tubular type carbon nano-fiber microscopic appearance.
Fig. 4 is a catalyst agent TEM photo.
The specific embodiment
Embodiment 1
Take by weighing 2.54gNi (NO3) 6H2O, 4.00g activated alumina and adding? gram distilled water forms aaerosol solution A; Stirred 6 hours; Take by weighing the nitroferrocyanic acid sodium of metering, be dissolved in? gram water forms solution B, B slowly injects A by measuring pump, carries out violent stirring simultaneously, and the time is 4 hours, form slurries C, operating temperature be 50 ℃ for well, and under stirring condition, spend the night, with the gained dope filtration, washing, dried overnight obtains powder D in 120 ℃ of drying boxes, D carries out calcination in muffle furnace, temperature is 573-1073K, stablizes 5 hours, and the product of gained is the catalyst that is obtained.
The preparation of tubular type carbon nano-fiber is carried out in continuous flow reactor of fixed bed, take by weighing the catalyst samples of 1g, in hydrogen atmosphere, reduce, reduction temperature is 873K, stablizes 3 hours, switches to the gaseous mixture of carbon monoxide and hydrogen, the air speed of carbon monoxide is 8000/h, the ratio of carbon monoxide and hydrogen is 4: 1, collects product through 16 hours reaction backs, and weighing is about about 10g.Product purification is that product was placed 1.0-4.0M hydrochloric acid 72 hours, filter and wash through distillation, place and carry out drying under the 380K condition, product purges with the argon gas of 520K can obtain pure tubular type carbon nano-fiber in 3.5 hours, the pattern available electron transmission electron microscope of tubular type carbon nano-fiber is observed, and its result as shown in Figure 1.
Embodiment 2
Take by weighing 2.36gFeCl
2, 4.00g activated alumina and add an amount of distilled water and form aaerosol solution A; Stirred 6 hours; Take by weighing potassium ferricyanate 3.13g, be dissolved in a certain amount of water, form solution B, B slowly injects A by measuring pump, carries out violent stirring simultaneously, and the time is 4 hours, form slurry C, operating temperature be 50 ℃ for well, after under stirring condition, spending the night, with the gained dope filtration, washing is that dried overnight obtains powder D in 120 ℃ of drying boxes in temperature, D carries out calcination in muffle furnace, temperature is 573-1073K, stablizes 5 hours, the product of gained is the catalyst that is obtained, its electromicroscopic photograph such as Fig. 4.
Embodiment 3
Take by weighing 1.77gFeCl
2, 4.00g activated alumina and add an amount of distilled water and form aaerosol solution A; Stirred 6 hours; Take by weighing nitroferrocyanic acid sodium 3.325g, be dissolved in a certain amount of water, form solution B, B slowly injects A by measuring pump, carries out violent stirring simultaneously, and the time is 4 hours, form deposit C, operating temperature be 50 ℃ for well, spend the night under the stirring condition, with gained slurries C, through filtering washing, in temperature is that dried overnight obtains powder D in 120 ℃ of drying boxes, and D carries out calcination in muffle furnace, and temperature is 573-1073K, stablized 5 hours, the product of gained is the catalyst that is obtained.
Embodiment 4
The preparation of tubular type carbon nano-fiber is carried out in continuous flow reactor of fixed bed, take by weighing catalyst samples among the embodiment 3 of 1g, in hydrogen atmosphere, reduce, reduction temperature is 873K, stablizes 3 hours, switches to the gaseous mixture of carbon monoxide and hydrogen, the air speed of carbon monoxide is 8000/h, the ratio of carbon monoxide and hydrogen is 4: 1, collects product through 16 hours reaction backs, and weighing is about about 11g.Product purification is that product was placed 1.0-4.0M hydrochloric acid 72 hours, filter and wash through distillation, place and carry out drying under the 373-390K condition, product purges with the argon gas of 473-573K can obtain pure tubular type carbon nano-fiber in 2-5 hour, and the pattern available electron transmission electron microscope of tubular type carbon nano-fiber is observed.See Fig. 2.
Embodiment 5
The preparation of tubular type carbon nano-fiber is carried out in continuous flow reactor of fixed bed, take by weighing catalyst samples among the embodiment 1 of 1g, in hydrogen atmosphere, reduce, reduction temperature is 873K, stablizes 3 hours, switches to the gaseous mixture of carbon monoxide and hydrogen, the air speed of carbon monoxide is 8000/h, the ratio of carbon monoxide and hydrogen is 4: 1, collects product through 48 hours reaction backs, and weighing is about about 24g.Product purification is that product was placed 1.0-4.0M hydrochloric acid 72 hours, filter and wash through distillation, place and carry out drying under the 373-390K condition, product purges with the argon gas of 473-573K can obtain pure tubular type carbon nano-fiber in 2-5 hour, and the pattern available electron transmission electron microscope of tubular type carbon nano-fiber is observed.See Fig. 3.
Embodiment 6
The preparation of tubular type carbon nano-fiber is carried out in continuous flow reactor of fixed bed, take by weighing catalyst samples among the embodiment 3 of 1g, in hydrogen atmosphere, reduce, reduction temperature is 873K, stablizes 3 hours, switches to the gaseous mixture of carbon monoxide and hydrogen, the air speed of carbon monoxide is 8000/h, the ratio of carbon monoxide and hydrogen is 1: 1, collects product through 16 hours reaction backs, and weighing is about about 9g.Product purification is that product was placed 1.0-4.0 hydrochloric acid 72 hours, filter and wash through distillation, place and carry out drying under the 373-390K condition, product purges with the argon gas of 473-573K can obtain pure tubular type carbon nano-fiber in 2-5 hour, and the pattern available electron transmission electron microscope of tubular type carbon nano-fiber is observed.
Claims (2)
1. transition-metal catalyst is characterized in that being preparation like this:
One or more transition metal solubility salt mixed dissolutions in water, are added alumina support, form aaerosol solution A;
Ferricyanate, ferrocyanic acid salt or nitroferrocyanic acid salt is soluble in water, form solution B;
B is injected A, stir, the time is 2～4 hours, stirred then 2～15 hours, and the gained dope filtration, washing, dry under 100～130 ℃, calcination is 2～7 hours under 573-1073K, promptly obtains catalyst of the present invention, and wherein, weight percent content is:
Transition metal oxide 1-95%, alumina support 5-99%;
Said transition metal is one or more in iron, cobalt or the nickel.
2. catalyst according to claim 1 is characterized in that said soluble-salt comprises sulfate, acetate, nitrate or hydrochloride.
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