CN100404130C - Method for preparing supported catalyst with single wall or double wall carbon nano tube - Google Patents
Method for preparing supported catalyst with single wall or double wall carbon nano tube Download PDFInfo
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- CN100404130C CN100404130C CNB2005100865430A CN200510086543A CN100404130C CN 100404130 C CN100404130 C CN 100404130C CN B2005100865430 A CNB2005100865430 A CN B2005100865430A CN 200510086543 A CN200510086543 A CN 200510086543A CN 100404130 C CN100404130 C CN 100404130C
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Abstract
The present invention relates to a method for preparing a supported catalyst for preparing single wall or double wall carbon nanometer tubes, which belongs to the technical field of catalyst preparation of carbon nanometer tubes. The present invention is characterized in that a supported catalyst is further calcined in high temperature, or hydrothermal treatment is made to the supported catalyst to obtain a supported catalyst which is evenly dispersed on a metal carrier; a range of the calcining temperature is 800 DEG C to 1100 DEG C, and the time span is 2h to 24h; a calcining environment is an inert gas environment or an air environment; a temperature range of the hydrothermal treatment is 70 DEG C to 600 DEG C. The present invention can prepare a catalyst which is evenly dispersed on a component metal carrier, and single wall or double wall carbon nanometer tubes obtained by further preparing has high productive rate and purity. Thus, a prospective purpose is obtained.
Description
Technical field:
A kind of preparation method who prepares the loaded catalyst of single wall or double-walled carbon nano-tube belongs to the catalyst preparation technical field of CNT.
Background technology:
Since Iijima found CNT (CNTs), because superior function that CNT has at physics, aspect chemical and potential application prospect, the theory of CNT and application study became a focus of World Science circle.Yet for a long time, made of carbon nanotubes, especially SWCN (SWNTs), output is lower, cost is higher, has limited the application study of CNT to a great extent.The preparation in enormous quantities, low-cost of multi-walled carbon nano-tubes (MWNTs) has at present realized [Wang Yao, Wei Fei, Luo Guohua smoothly, Yu Hao, Gu Guangshen, Chem.Phys.Lett.2002,364 (5-6): 568-572], and also there is certain difficulty in the prepared in batches of single wall.SWCN can be made into purposes such as ultra high strength fiber, conductive fiber, absorbing material, nano electron device, sensor.Wherein some needs SWCN in enormous quantities, low-cost preparation.
With the more Fe/MgO System Catalyst of present research is example, and Ago etc. point out, in the Fe/MgO catalyst, the Fe particle size can catalysis generate single wall or double-walled carbon nano-tube during less than 5nm; When the Fe particle is big, forms carbon-coating easily and coat, perhaps carbon fiber [Ago, H.et al.Phys.Chem.B2004,108,18908-18915].If can obtain metal component dispersiveness catalyst preferably on carrier, just can reduce impurity effectively and generate, obtain higher single wall or double-walled carbon nano-tube purity and productive rate [Coquay, P.et al.J.Phys.Chem.B2002,106,13199-13210].
Summary of the invention:
Target of the present invention is the method for the loaded catalyst of a kind of effective preparation single wall of exploitation or double-walled carbon nano-tube, the pattern and the caliber that utilize this method can control product distribute, utilize this catalyst can further prepare purity and higher single wall or the double-walled carbon nano-tube of productive rate, thereby be applied to the preparation of single wall in enormous quantities or double-walled carbon nano-tube.
The invention is characterized in, contain following steps:
1) the preparation metal component is distributed in the loaded catalyst on the carrier;
2) loaded catalyst that above-mentioned metal component is distributed on the carrier carries out further high-temperature calcination, obtains metal homodisperse loaded catalyst on carrier, and calcining heat is 800 ℃, and calcination environment is an inert gas environment, and calcination time is 8h; Or calcining heat is 950 ℃～1100 ℃, and calcination environment is inert gas environment or air ambient, and calcination time is 2h～24h.
Described loaded catalyst is with SiO
2, Al
2O
3Or MgO is carrier, is key component with Fe, Co or Ni, serves as to add component with Mo or Zr.
The described the 1st) step preparation metal component is distributed in loaded catalyst employing infusion process, coprecipitation, firing method or the citric acid method on the carrier.
The preparation method of the loaded catalyst of another kind of preparation single wall or double-walled carbon nano-tube is characterized in that, contains following steps:
1) the preparation metal component is distributed in the loaded catalyst on the carrier;
2) loaded catalyst that above-mentioned metal component is distributed on the carrier carries out further hydrothermal treatment consists, and the temperature range of hydrothermal treatment consists is 70 ℃～600 ℃.
Described loaded catalyst is with SiO
2, Al
2O
3Or MgO is carrier, is key component with Fe, Co or Ni, serves as to add component with Mo or Zr.
The described the 1st) step preparation metal component is distributed in loaded catalyst employing infusion process, coprecipitation, firing method or the citric acid method on the carrier.
Experimental results show that: utilize method proposed by the invention, can prepare metal component homodisperse catalyst on carrier, the single wall/double-walled carbon nano-tube that further prepares has higher productive rate and purity, has reached its intended purposes.
Description of drawings
Fig. 1 adopts the transmission electron microscope picture (a) of the Fe/MgO catalyst of high-temperature calcination processing, is made ESEM picture (b), transmission electron microscope picture (c) and the thermogravimetric analysis curve (d) of product by this catalyst.
The Fe/MgO catalyst of Fig. 2 immersion process for preparing without hydrothermal treatment consists figure (a) and hydrothermal treatment consists after the TEM picture of (b).
Fig. 3 adopts the ESEM picture (a) and the Raman spectrogram (c) of product of the Fe/MgO Preparation of Catalyst of immersion process for preparing, the ESEM picture (b) of gained sample and thermogravimetric analysis curve (d) behind the pickling purifying.
The specific embodiment:
Being used to prepare the loaded catalyst of single wall or double-walled carbon nano-tube, is with SiO
2, Al
2O
3, MgO or its compound etc. are carrier, it is key component that load has Fe, Co, Ni, with metals such as Mo, Zr, Cu, Zn, rare earths as the catalyst that adds component.The present invention is that the metal component that will prepare with existing method loads on SiO
2, Al
2O
3, supported catalysts such as MgO or its compound, further the method by high-temperature calcination or hydrothermal treatment consists obtains the homodisperse catalyst of metal component.These catalyst are applied to prepare single wall or double-walled carbon nano-tube, can obtain higher purity and productive rate.
The temperature range that high-temperature calcination is handled is 800-1100 ℃, and time span is 2h-24h, and calcining can be carried out in Ar atmosphere or air atmosphere.After the high-temperature calcination processing, power spectrum (EDS) is analyzed and high-resolution-ration transmission electric-lens (HRTEM) observation shows: metal component has good dispersion on carrier.
The temperature range of hydrothermal treatment consists is 70-600 ℃.After hydrothermal treatment consists, power spectrum (EDS) is analyzed and high-resolution-ration transmission electric-lens (HRTEM) observation shows: metal component has good dispersion on carrier.
The process of preparation single wall or double-walled carbon nano-tube can be carried out in dissimilar reactor such as fixed bed, fluid bed, moving bed, a certain amount of above-mentioned catalyst is warming up to 500-1000 ℃ under inert gas atmosphere, feed reacting gas, reaction time is 5-60 minute, be cooled to room temperature under the inert gas atmosphere then, obtain carbon nanotube product.
Method provided by the invention is easy and simple to handle, with low cost, and catalyst is used to prepare single wall or double-walled carbon nano-tube, can obtain the high-purity carbon nano tube that caliber is 1-5nm, and productive rate is also higher.
Below in conjunction with accompanying drawing, the present invention will be further described by embodiment and comparative example, and content of the present invention comprises but is not limited only to the following examples.
Embodiment 1
In this example, the Fe/MgO catalyst of immersion process for preparing is carried out high-temperature calcination handle.Has good catalytic performance in order to preparation single wall or double-walled carbon nano-tube through the catalyst after the calcination processing.
At first adopt immersion process for preparing Fe/MgO catalyst.The MgO carrier is by 500 ℃ of calcining basic magnesium carbonate preparations down, according to the analytically pure Fe (NO of the proportioning weighing of Fe: MgO=0.01 (mol ratio)
3)
3.9H
2O and MgO powder, the ultrasonic dispersion of the aqueous solution of then the MgO support powder being put into ferric nitrate, fine powder is dried, ground to form to the gained gel, at last 650 ℃ of calcinings down, so just obtained the Fe/MgO catalyst of immersion process for preparing.The Fe/MgO catalyst of immersion process for preparing is put into quartz ampoule, in the argon gas atmosphere, calcine this catalyst 8h down for 800 ℃, cool to room temperature obtains the catalyst after high-temperature calcination is handled then.Get about 100mg catalyst and pack in the fixed bed reactors, under Ar atmosphere, be heated to 800 ℃, feed methane then, reacted 20 minutes, under argon gas atmosphere, be cooled to room temperature at last, just obtain carbon nanotube product.
Transmission electron microscope picture as shown in Figure 1a shows, there is not the poly-group of tangible Fe component in Fe component favorable dispersibility in MgO in the catalyst that said method obtains, and the electron diffraction pattern in the illustration shows that catalyst has formed single crystal grain.ESEM picture (Fig. 1 b) shows, single wall and double-walled carbon nano-tube are very abundant in the product, the carbon impurity that does not have other types in the very wide visual field, transmission electron microscope picture (Fig. 1 c) show the caliber of CNT at 1-5nm, by thermogravimetric analysis (Fig. 1 d) as can be known productive rate can reach 10.2wt%.
In this example, adopt Al
2O
3/ SiO
2Complex carrier prepares catalyst by infusion process load Ni, Co bimetallic component, and adds rare-earth metal La as co-catalyst.Al wherein
2O
3/ SiO
2Complex carrier is by adding Al in Ludox
2O
3Method preparation, be exactly particularly, with Al
2O
3Nanoparticulate dispersed stir to form uniform suspension in ethanol, add tetraethyl orthosilicate salt then and stir, and adds low amounts of water at last and is hydrolyzed, thereby obtain Al
2O
3/ SiO
2Complex carrier.Above-mentioned catalyst was calcined 24 hours under 950 ℃ in air atmosphere.In the catalyst after the calcining heat treatment, metal component is uniformly dispersed, and the obviously not poly-group of electron microscopic observation exists, and catalyst has good catalytic performance in order to preparation single wall or double-walled carbon nano-tube.The productive rate that can obtain single wall and double-walled carbon nano-tube by ethene or acetylene cracking process is 21% product.
Embodiment 3
Adopt coprecipitation to prepare the Fe catalyst of MgO load, and adopt Cu and Zn as adding component.With Fe (NO
3)
3, Cu (NO
3)
2, Zn (NO
3)
2And Mg (NO
3)
2According to Fe: Cu: Zn: Mg=2: the proportioning of 0.1: 0.1: 100 (mol ratio) is dissolved in the ethanol, in ethanolic solution, drip concentration then and be 1: 1 ammoniacal liquor, up to pH value is 10, filtering precipitate is also used the ethanol rinsing then, and the pressed powder that obtains oven dry, grinding just obtain the FeCuZn/MgO catalyst.
FeCuZn/MgO 1100 ℃ of following high-temperature calcinations in air atmosphere to above-mentioned coprecipitation preparation were handled 2 hours, had good catalytic performance in order to preparation single wall or double-walled carbon nano-tube through the catalyst after the calcination processing.Through similar among the feature of the CNT that makes of FeCuZn/MgO catalyst of calcining and the embodiment 1, productive rate can reach 18wt%.
Embodiment 4
In this example, the Fe/MgO catalyst of immersion process for preparing is carried out hydrothermal treatment consists, obtained the catalyst of the function admirable of preparation single wall or double-walled carbon nano-tube.
At first by immersion process for preparing Fe/MgO catalyst, then the Fe/MgO catalyst fines is dispersed in the deionized water, carrying out constant pressure hydro-thermal handles: adopt beaker to heat and boil (about 100 ℃), about 20 minutes with the water evaporate to dryness, just obtains the catalyst fines after the hydrothermal treatment consists.The catalyst for preparing is above packed in the fixed bed reactors, under Ar atmosphere, be heated to 800 ℃, feed the gaseous mixture of methane and hydrogen then, reacted 20 minutes, under Ar atmosphere, be cooled to room temperature at last, just obtain carbon nanotube product.
The catalyst XRD analysis that said method obtains shows that MgO combines with water and has formed Mg (OH)
2, as shown in Figure 2, (Fig. 2 a) changes laminar (Fig. 2 b) into to catalyst, and the iron component is evenly dispersed in laminar Mg (OH) very much by graininess
2In, do not observe any particle aggregation, the EDS spectrogram shows and looking that very the proportioning of the mol ratio of Fe and Mg in the thin slice uniformly and catalyst is in full accord, and The above results illustrates that the iron component has been evenly dispersed on the laminar carrier very much in the catalyst after hydrothermal treatment consists.Flaky texture has bigger specific area, and this dispersion to the iron component provides advantage.
Adopt in the product of above-mentioned Preparation of Catalyst, CNT is very abundant, does not observe the carbon impurity of other types such as tangible carbon fiber in the very big visual field, and single wall and double-walled carbon nano-tube caliber are 1-5nm, and productive rate can reach 22wt%.
Embodiment 5
Adopt firing method to prepare the CoMo/MgO catalyst.With Co (NO
3)
2.6H
2O, (NH
4)
6Mo
7O
24.4H
2O, urea, Mg (NO
3)
2.6H
2O is 0.07: 0.017: 0.42 according to mass ratio: 1 proportioning is mixed, and adds low amounts of water, grinds to form uniform solution, then mortar is directly put into 550 ℃ muffle furnace, take out after 5 minutes, just available after the solid sample that is expanded, loosens, grind into powder.
CoMo/MgO catalyst to above-mentioned firing method preparation carries out low-pressure water heat treatment: catalyst fines is dispersed in the deionized water, adopt the glass closed container to be heated to 70 ℃, utilize vavuum pump to keep being in the low pressure condition in the container, until with the water evaporate to dryness, obtain the catalyst fines after the hydrothermal treatment consists.CoMo/MgO catalyst after the employing hydrothermal treatment consists has good catalytic performance in order to preparation single wall or double-walled carbon nano-tube, can obtain SWCN productive rate 25%, does not contain the carbon impurity of other types in the product.
Embodiment 6
In this example, at first adopting citric acid method to prepare the NiZr/MgO catalyst, the slaine of Ni, Zr and Mg and citric acid are mixed according to certain proportioning, add low amounts of water, form uniform solution, is colloid 70 ℃ of water-soluble dryings down then.After oven dry, the grinding, in 500 ℃ of air, calcine, obtain pulverous catalyst.The above-mentioned catalyst fines that obtains is carried out hydrothermal treatment consists under 600 ℃ in high-pressure closed vessel, obtained Ni, Zr metal component at Mg (OH)
2Equally distributed catalyst on the lamellar structure has good performance for preparation single wall or double-walled carbon nano-tube.Can obtain single wall and the double-walled carbon nano-tube product that productive rate reaches 30wt% by ethanol and liquefied gas cracking.
In this example, adopt the FeCo/MgO catalyst after the hydrothermal treatment consists under the normal pressure, in the fluidized-bed reactor of pilot-scale, prepared single wall and double-walled carbon nano-tube product.
Adopt fluidized-bed reactor in the pilot experiment, the internal diameter of vertical quartz glass pipe reactor is 45mm.In the experiment, will place on the gas distribution grid in the reactor argon gas of feeding through the Fe/MgO catalyst of hydrothermal pretreatment, be warming up to 850 ℃, feed the gaseous mixture of methane and hydrogen then, reaction is closed methane and hydrogen behind the 20min, takes out product be cooled to room temperature under argon gas atmosphere after.
The product of get on the distribution grid respectively, collecting position such as reactor wall carries out productive rate analysis and electron microscopy observation.The product yield that each sample point obtains is in 18wt% to 22wt% scope, SEM observes and shows, contains abundant SWCN in the product, as seen, the product basically identical for preparing in product that pilot-scale prepares and the front microreactor, and uniform in quality in the reactor.The pure SWCN that once prepares can reach 20g, is to calculate in one hour according to the time before and after the each reaction, and production capacity can reach 20g/h in the preparation of pilot-scale.
Comparative Examples 1
In this example, directly adopt Fe/MgO catalyst (without calcining or hydrothermal treatment consists) the preparation carbon nanotube product of immersion process for preparing.
The Fe/MgO catalyst of immersion process for preparing evenly is tiled in the aluminium oxide porcelain boat, again porcelain boat is put into horizontal pipe furnace.Under the Ar protection, join 800 ℃, fed then hydrogen reducing 10-30 minute, feed reacting gas (gaseous mixture of methane or methane and hydrogen) reaction 30 minutes again.At last, cool to room temperature under the Ar protection takes out product and characterizes.In said process, keep argon stream always.
The ESEM picture of said method products obtained therefrom (Fig. 3 a) and Raman spectrogram (Fig. 3 c) show that single wall and double-walled carbon nano-tube are abundanter in the sample, but also can observe impurity such as containing a certain amount of carbon fiber.Behind the overpickling purifying, contain abundant SWCN (Fig. 3 b) in the sample, thermogravimetric analysis (Fig. 3 d) shows that carbon content total in the product is 81.3wt%, weightless peak occurs at 329.6 ℃, 542.5 ℃ and 595 ℃ in the weight-loss curve, correspond respectively to the amorphous carbon of 2.7wt%, the SWCN of 50.8wt% and multi-walled carbon nano-tubes or the carbon fiber of 27.8wt%.As seen the major impurity in the product is many walls carbon pipe or carbon fiber.
Claims (4)
1. a preparation method who prepares the loaded catalyst of single wall or double-walled carbon nano-tube is characterized in that, contains following steps:
1) the preparation metal component is distributed in the loaded catalyst on the carrier;
2) loaded catalyst that above-mentioned metal component is distributed on the carrier carries out further high-temperature calcination, obtain metal homodisperse loaded catalyst on carrier, calcining heat is 950 ℃～1100 ℃, and calcination environment is an air ambient, and calcination time is 2h～24h;
Described loaded catalyst is with SiO
2, Al
2O
3Or MgO is carrier, is key component with Fe, Co or Ni, serves as to add component with Mo or Zr.
2. a kind of preparation method who prepares the loaded catalyst of single wall or double-walled carbon nano-tube as claimed in claim 1, it is characterized in that the described the 1st) loaded catalyst that is distributed on the carrier of step preparation metal component adopts infusion process, coprecipitation, firing method or citric acid method.
3. a preparation method who prepares the loaded catalyst of single wall or double-walled carbon nano-tube is characterized in that, contains following steps:
1) the preparation metal component is distributed in the loaded catalyst on the carrier;
2) loaded catalyst that above-mentioned metal component is distributed on the carrier carries out further hydrothermal treatment consists, and the temperature range of hydrothermal treatment consists is 70 ℃～600 ℃;
Described loaded catalyst is with SiO
2, Al
2O
3Or MgO is carrier, is key component with Fe, Co or Ni, serves as to add component with Mo or Zr.
4. a kind of preparation method who prepares the loaded catalyst of single wall or double-walled carbon nano-tube as claimed in claim 3, it is characterized in that the described the 1st) loaded catalyst that is distributed on the carrier of step preparation metal component adopts infusion process, coprecipitation, firing method or citric acid method.
Priority Applications (1)
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| CN103058164A (en) * | 2011-10-20 | 2013-04-24 | 苏州捷迪纳米科技有限公司 | Preparation method of single-walled carbon nanotube |
| KR102560964B1 (en) * | 2016-07-18 | 2023-07-28 | 에스케이이노베이션 주식회사 | Catalyst of synthesis of multi-walled carbon nanotube and multi-walled carbon nanotube using the same and method of manufacturing multi-walled carbon nanotube |
| CN109399611A (en) * | 2017-08-16 | 2019-03-01 | 东北林业大学 | A kind of preparation method of carbon nanotube |
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| CN110801843B (en) * | 2019-11-11 | 2022-07-01 | 内蒙古骏成新能源科技有限公司 | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof |
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| CN114515578B (en) * | 2021-12-31 | 2023-05-23 | 佛山市格瑞芬新能源有限公司 | Catalyst for preparing carbon nano tube and preparation method and application thereof |
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