CN1261222C - Process for preparing Al2O3 aerogel carried catalyst and its application in preparing nano carbon tubes by catalytic cracking of methane - Google Patents
Process for preparing Al2O3 aerogel carried catalyst and its application in preparing nano carbon tubes by catalytic cracking of methane Download PDFInfo
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- CN1261222C CN1261222C CN 01144482 CN01144482A CN1261222C CN 1261222 C CN1261222 C CN 1261222C CN 01144482 CN01144482 CN 01144482 CN 01144482 A CN01144482 A CN 01144482A CN 1261222 C CN1261222 C CN 1261222C
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Abstract
The present invention relates to a method for preparing a functional material nanometer carbon tube and a preparation method of a novel used catalyst thereof, particularly to a method for preparing an Al2O3 aerogel supported catalyst, and a method for preparing a nanometer carbon tube by catalytic cracking of methane. The catalyst is prepared by a collosol-gel and supercritical drying method, and the preparation has the following main steps: (1) Al(OH)3 gel is prepared; (2) active constituents are deposited on the Al(OH)3 gel by a deposition-precipitation method; (3) obtained products are put in a high pressure reactor for supercritical drying; (4) products are dried and calcined; simultaneously, the present invention discloses a method for producing carbon nanometer tubes through catalytic cracking of methane by the catalyst of the present invention. The specific surface area of the typical sample of the catalyst prepared by the present invention is 380 m<2>/g, the pore volume is 1.84cm<3>/g, and the pore diameter is 25 nm; through reduction, about 10 nm of metal particles can be obtained. The nanometer carbon tube prepared by the catalyst of the present invention has the advantages of thin pipe diameter, easy configuration control and simple preparation process.
Description
Technical field
The present invention relates to the preparation of functional material CNT and the preparation method of used new catalyst, particularly be Al
2O
3The preparation of aerogel carried catalyst and the method for preparing nano carbon tubes by catalytic cracking of methane thereof.
Background technology
CNT is a kind of emerging material with carbon element, can be used for a plurality of fields such as material, electronics, chemical industry, machinery.
At present, the method for preparing CNT has: arc discharge plasma graphite evaporation, metal-graphite target laser evaporation and carbonaceous gas catalystic pyrolysis.Arc discharge method obtains the part CNT, also has graphite scrap, amorphous carbon and nano carbon particle etc., and reaction temperature is higher than 3000 ℃; The laser evaporation method is to prepare CNT with laser-impact graphite-metal target, and the form of the CNT that obtains is similar to arc discharge method, allows continued operation; The carbonaceous gas catalytic pyrolysis is lower than the above two reaction temperatures, and output is big, and CNT is longer, and process is simple, large-scale production relatively, and CNT content height in the product, but the CNT bending, the wall thickness that obtain based on multilayer pipe, come in every shape.
When using at present the carbonaceous gas catalystic pyrolysis to prepare CNT, mainly adopt infusion process, the precipitation method, ion-exchange etc. to carry out Preparation of Catalyst, the CNT that obtain this moment is thicker, generally about 20nm, and the form more complicated.Compare with other catalytic growth method, methane catalytic decomposition can obtain the nano-carbon material of extensive structure, and to 50 nanometers, that form has diameter is fibrous from 3 nanometers, tubulose, ring shape, octopus shape, graininess etc.; Graphite linings has coaxial circles, different oblique angles etc., and also form and structure are controlled, can form the series technique that is applicable to different needs.In the relevant article of delivering, introduced a kind of method for preparing catalyst that adopts sol-gel and supercritical drying in the recent period on Chem.Phys.Lett.322 (2000) 321, this method is a raw material with the organic alkoxide of metal, CO
2Be the supercritical drying medium, preparation process is consuming time, complicated, is difficult to realize mass preparation.
Summary of the invention
In order to solve the deficiency of above-mentioned technology, the invention provides a kind of Al
2O
3The preparation of aerogel carried catalyst and the method for preparing nano carbon tubes by catalytic cracking of methane thereof, it is with Al (OH)
3With slaine be raw material, be the supercritical drying medium with ethanol, preparation process is simple, can realize mass preparation.
1.Al
2O
3The aerogel carried catalyst preparation method:
(1) preparation gel aluminum hydroxide:
Under intense agitation, be the Al (NO of 0.1-2.0M to molar concentration
3)
3Drip the ammonia spirit of 0.2-10.0M in the solution, control endpoint pH 5-9 obtains Al (OH)
3Colloidal sol, stirring condition continue reaction down and obtain gel aluminum hydroxide.
(2) adopt the deposition-precipitation method that active component is deposited on the gel aluminum hydroxide:
Under intense agitation, be 0.1-6 by the M/Al mol ratio, wherein: M is Ni, Fe, Co or the wherein combination of two kinds of metals.Getting the M nitrate solution of 0.1-2.0M and ammoniacal liquor and stream joins in the gel aluminum hydroxide.The pH value that the control reaction ends under stirring condition is controlled between the 5-10.Gel that makes and active component deposit wore out 0.5-6 hour under stirring condition, left standstill aging 0.5-6 hour after stopping to stir.Use respectively behind the suction filtration distilled water and absolute ethyl alcohol cyclic washing to the gel water and absolute ethyl alcohol ratio less than 10%.
(3) place autoclave to carry out supercritical drying the product that obtains:
The gel deposit that washing is finished is transferred in the autoclave, and the absolute ethyl alcohol of adding is after stirring, at N
2Under the atmosphere, temperature programming is to the supercriticality of ethanol, and half an hour is made an appointment with in maintenance under this state.Under constant temperature, slowly release alcohol vapour to normal pressure, logical N
2Air-blowing is swept, and drives remaining alcohol vapour away, and is cooled to room temperature naturally.
(4) dry, calcining:
The aerogel catalyst that supercritical drying is made more than 0.5 hour, obtains the flocculence aeroge 300-600 ℃ of calcining in air.
Prepared catalyst is M, the Al composite oxides ultrafine particle of the about 10nm of particle diameter, and wherein the mass percent of M oxide is that 10%-90%, aluminium oxide quality percentage are 90%-10%.
In above preparation method, wherein prepare in the step of gel aluminum hydroxide Al (NO in (1)
3)
3The preferred 0.1M-0.3M of solution molar concentration, ammonia spirit is preferably 1.0-3.0M, the preferred 7-9 of control pH value;
Wherein adopt the deposition-precipitation method active component to be deposited in the step on the gel aluminum hydroxide in (2), preferred M/Al is than being 0.1-0.5, M nitrate solution concentration is preferably 0.1-0.3M, preferred pH value should be controlled between the 8.5-9.5, preferred wearing out 2-3 hour under the stirring condition left standstill preferred aging 3-5 hour after stopping to stir.
Wherein in the step of (4) drying, calcining, the aeroge that supercritical drying makes was preferably calcined about 10 hours at 300-600 ℃ under air atmosphere.
Described M, Al composite oxide catalysts, wherein: M is preferred Ni, the mass percent of corresponding oxide is that 10%-25%, aluminium oxide quality percentage are 90%-75%.
Adopting the specific area of the prepared catalyst typical sample of this technology of preparing is 380m
2/ g, pore volume 1.84cm
3/ g, most probable aperture 25nm can get metallic particles about 10nm through reduction, and its form is seen accompanying drawing 1, Fig. 2.
2. adopt the method for above-mentioned catalyst cracking methane production CNT:
With M, the Al composite oxide catalysts (plastic or not moulding, also can sieve is certain particle size) that adopts present technique to make, put into reactor, be warming up to reduction temperature 600-1000 ℃, after process to be restored is finished,, feed CH at intensification 400-800 ℃
4Content be the mixing carbon distribution gas of 10-100% (mol ratio), carry out the preparation of CNT.
Carry out catalytic cracking methane at above catalyst and produce in the method for CNT, process conditions are preferably: after reduction temperature is 800-900 ℃, and reaction temperature 450-750 ℃, CH wherein
4Content is 30-50%.
The active warm area of this catalyst long carbon under above experiment condition is 450-750 ℃, and the long carbon amount of catalyst and growth rate, long carbon life-span are relevant.Al
2O
3Aerogel carried Ni type carbon deposition quantity of catalyst can reach more than the 73.67gC/gNi.The CNT growth rate raises with reaction temperature and accelerates.The CNT bending that obtains, wall approach, and uniform diameter is smooth continuous, about diameter 10-20nm, about wall thickness 3-5nm.Form is seen accompanying drawing 3,4,5,6.
The present invention adopts the CNT caliber of this Preparation of Catalyst thinner, and form is easy to control, and preparation process is simple.
Description of drawings
Fig. 1: Q3 parent TEM photo in the table one
Fig. 2: 600 ℃ of calcinings of Q3 parent and the TEM photo after 850 ℃ of reduction in the table one
Fig. 3: Q3 catalyst in the table 1 (550 ℃ of reactions of 800 ℃ of reduction carbon distribution) is gone up the CNT TEM photo of preparation
Fig. 4: Q6 catalyst in the table 1 (600 ℃ of reactions of 800 ℃ of reduction carbon distribution) is gone up the CNT TEM photo of preparation
Fig. 5: Q8 catalyst in the table 1 (525 ℃ of reactions of 850 ℃ of reduction carbon distribution) is gone up the CNT TEM photo of preparation
Fig. 6: Q9 catalyst in the table 1 (520 ℃ of reactions of 850 ℃ of reduction carbon distribution) is gone up the CNT TEM photo of preparation
The specific embodiment
Embodiment 1:
Be that 1/9 supported ni catalyst is that example illustrates concrete preparation process now with the Ni/Al mol ratio:
Under intense agitation, be the Al (NO of 0.16M to molar concentration
3)
3Drip the ammonia spirit of 1.8M in the solution, control endpoint pH to 8 obtains Al (OH)
3Colloidal sol, stirring condition continue reaction down and obtain gel aluminum hydroxide.Get 0.15MNi (NO
3)
2Solution 34.92ml and certain amount of ammonia water under vigorous stirring, join two kinds of solution and stream in the gel aluminum hydroxide, behind reinforced the finishing, continue to stir, and reaction is at the end controlled the pH value 9.3.As if the preparation bimetallic catalyst, this moment, other condition was constant with in two kinds of metal-nitrate solutions and ammoniacal liquor and the stream adding gel aluminum hydroxide.
The gel that makes and active component sediment after under the stirring condition aging 3 hours, were left standstill aging 3 hours again.Gel solution after aging is carried out suction filtration, for several times earlier with the distilled water washing leaching cake, use again absolute ethyl alcohol cyclic washing filter cake to the gel water and the ratio of absolute ethyl alcohol less than 5% (being as the criterion) with chromatography.
The gel that washing is finished is transferred in the 330ml autoclave, adds the 25ml absolute ethyl alcohol, stirs, and feeds N then in autoclave
2Gas purges, and drives the air in the still away.After purging finished, temperature programming and kept this state 30min to the supercriticality of ethanol: T=260 ℃, P=7.5MPa under air-tight state.Heating-rate curve is: 20 minutes by 200 ℃ to 300 ℃ by 20 ℃ to 200 ℃ in 18 minutes.After drying is finished, under 260 ℃ of steady temperatures, slowly emit alcohol vapour to still internal pressure and reduce to normal pressure, logical N
2Air-blowing is swept, and drives remaining alcohol vapour away, makes autoclave be cooled to room temperature naturally, promptly obtains aerogel carried catalyst.
Aeroge with supercritical drying makes places muffle furnace, makes it reduce to room temperature naturally respectively at 300 ℃, 400 ℃, 500 ℃, 600 ℃ four temperature calcinings after 8 hours, obtains the flocculence aerogel catalyst.
Embodiment 2-8: preparation process is with embodiment 1, and running parameter sees Table 1.
Table 1 Preparation of Catalyst condition
| Embodiment | Sample | Form | Al(NO 3) 3And MNO 3Concentration | Endpoint pH | The supercritical drying condition |
| 1 2 3 4 5 6 | Q1 Q2 Q3 Q6 Q6 Q6 | Ni∶Al＝1∶9 Ni∶Al＝2∶9 Ni∶Al＝3∶9 Fe∶Al＝1∶9 Fe∶Al＝2∶9 Fe∶Al＝3∶9 | 0.16M and 0.15M 0.16M and 0.15M 0.16M and 0.15M 0.16M and 0.15M 0.16M and 0.15M 0.16M and 0.15M | 9.2 9.3 9.4 9.3 9.2 9.1 | Ethanol, 260 ℃, 7.5Mpa following 30min ethanol, 260 ℃, 7.5Mpa following 30min ethanol, 260 ℃, 7.5Mpa following 30min ethanol, 260 ℃, 7.5Mpa following 30min ethanol, 260 ℃, 7.5Mpa following 30min ethanol, 260 ℃ |
| 7 8 | Q8 Q9 | Co∶Al＝3∶9 Co∶Ni∶Al＝2∶2∶9 | 0.16M and 0.15M 0.16M and 0.15M | 9.1 9.2 | 7.5Mpa following 30min ethanol, 260 ℃, 7.5Mpa following 30min ethanol, 260 ℃, 30min under the 7.5Mpa |
Embodiment 9:
The CNT preparation process condition
Accurately take by weighing 260-270 purpose Q3 (600) catalyst granules 3.05mg and put into quartzy basket.With residual gas 10min in the nitrogen purging system; Feed nitrogen and hydrogen to system, be heated to 800 ℃ of reduction temperatures with the speed of 10 ℃/min, constant temperature is reduced to constant weight.Adjust the temperature to the differential responses temperature in high pure nitrogen, for example 550 ℃ of maintenances are constant, feed reacting gas and carry out the CNT preparation.Wherein:
(1) quartz reactor external diameter: 24mm; Internal diameter: 18mm;
(2) quartzy basket height: 12mm; External diameter: 14mm; Internal diameter: 12mm;
(3) reactor nitrogen envelope flow: 30ml/min (STP);
(4) reducing gas is formed and flow (STP): total flow 45ml/min, H
2: N
2Be 1: 3 (mol ratio).
(5) reaction gas is formed and flow (STP): total flow 45ml/min, CH
4: N
2Be 1: 2 (mol ratio).
(6) reaction pressure: normal pressure;
What adopt in the embodiments of the invention is quartz reactor, does not limit the use of other reactor, (as stainless steel reactor, also can reach similar effects).
Embodiment 10-14: preparation process is with embodiment 9, and parameter sees Table 2.
Table 2 CNT prepares the result
| Embodiment | Sample | Consumption (mg) | Reduction temperature (℃) and flow (ml/min) | Reducing gases is formed | The carbon distribution temperature (℃) and flow (ml/min) | Carbon distribution gas is formed | The unit carbon deposition quantity |
| 9 10 11 12 13 14 | Q3(600) Q6400) Q6400) Q8(500) Q8(500) Q9(600) | 3.05 3.00 2.97 2.93 2.96 3.02 | 800，45 800，45 800，45 850，45 850，45 850，45 | H 2/N 2＝1∶3 H 2/N 2＝1∶3 H 2/N 2＝1∶3 H 2/N 2＝1∶3 H 2/N 2＝1∶3 H 2/N 2＝1∶3 | 550，45 500，45 600，45 575，45 525，45 520，45 | CH 4/N 2＝1∶2 CH 4/N 2＝1∶2 CH 4/N 2＝1∶2 CH 4/N 2＝1∶2 CH 4/N 2＝1∶2 CH 4/N 2＝1∶2 | 52.4gC/gNi 39.4gC/gFe 42.1gC/gFe 43.6gC/gCo 70.2gC/gCo 113.2gC/gNi 112.1gC/gCo |
Symbol Q3 (600) expression: consist of Ni: Al=3: 9 catalyst is in 600 ℃ of calcinings down.Other are similar.
Claims (5)
1. Al
2O
3The preparation method of aerogel carried catalyst may further comprise the steps:
(1) preparation gel aluminum hydroxide:
Under intense agitation, be the Al (NO of 0.1-2.0M to molar concentration
3)
3Drip the ammonia spirit of 0.2-10.0M in the solution, control endpoint pH 5-9 obtains Al (OH)
3Colloidal sol, stirring condition continue reaction down and obtain gel aluminum hydroxide;
(2) adopt the deposition-precipitation method that active component is deposited on the gel aluminum hydroxide:
Under intense agitation, be 0.1-6 by the M/Al mol ratio, get the M nitrate solution of 0.1-2.0M and ammoniacal liquor and stream and join in the gel aluminum hydroxide; The pH value that the control reaction ends under stirring condition is between 5-10, gel that makes and active component deposit wore out 0.5-6 hour under stirring condition, left standstill after stopping to stir aging 0.5-6 hour, use respectively behind the suction filtration distilled water and absolute ethyl alcohol cyclic washing to the gel water and absolute ethyl alcohol ratio less than 10%;
(3) place autoclave to carry out supercritical drying the product that obtains:
The gel deposit that washing is finished is transferred in the autoclave, adds absolute ethyl alcohol, after stirring, at N
2Under the atmosphere, temperature programming is to the supercriticality of ethanol: and under this state, keep half an hour approximately, under constant temperature, slowly release alcohol vapour to normal pressure, logical N
2Air-blowing is swept, and drives remaining alcohol vapour away, and is cooled to room temperature naturally;
(4) dry, calcining:
The aerogel catalyst that supercritical drying is made more than 0.5 hour, obtains flocculence aeroge M, Al composite oxide catalysts 300-600 ℃ of calcining in air:
Wherein: M is Ni, Fe, Co or the composition of two kinds of metals wherein, and its oxide mass percentage is that 10%-90%, aluminium oxide quality percentage are 90%-10%.
2. a kind of Al as claimed in claim 1
2O
3The preparation method of aerogel carried catalyst is characterized by in the step of described (1) preparation gel aluminum hydroxide Al (NO
3)
3The solution molar concentration is 0.1M-0.3M, and ammonia spirit is 1.0-3.0M, control pH value 7-9.
3. a kind of Al as claimed in claim 1
2O
3The preparation method of aerogel carried catalyst, it is characterized by described (2) adopts the deposition-precipitation method that active component is deposited in the step on the gel aluminum hydroxide, M/Al is than being 0.1-0.5, and M nitrate solution concentration is 0.1-0.3M, and pH value should be controlled between the 8.5-9.5.
4. adopt as the method for the CNT of the catalyst cracking methane production of preparation method's preparation as described in each among the claim 1-3: the M, the Al composite oxide catalysts that make are fed reducing gases down at 600-1000 ℃ and reduce, treat to reduce fully the back in 400-800 ℃, feed CH
4Content is that 10-100% (mol ratio) mixes carbon distribution gas, carries out the preparation of CNT.
5. catalytic cracking methane as claimed in claim 4 is produced the method for CNT: it is characterized by described process conditions is: reduction temperature is 800-900 ℃, and reaction temperature is 450-750 ℃, and wherein CH4 content is 30-50%.
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| TW200307773A (en) * | 2002-05-22 | 2003-12-16 | Showa Denko Kk | Process for producing vapor-grown carbon fibers |
| CN100351012C (en) * | 2004-07-08 | 2007-11-28 | 武汉科技大学 | Cobalt/magnesium oxide aerogel catalyst, and method for producing nano-carbon tube therewith |
| CN100348315C (en) * | 2004-07-08 | 2007-11-14 | 武汉科技大学 | F2O3/Al2O3 aerogel catalyst, and method for producing single-wall nano-carbon tube therewith |
| CN100434359C (en) * | 2005-01-05 | 2008-11-19 | 中国科学院大连化学物理研究所 | Method and device for continuously producing nanometer carbon material |
| CN102659429B (en) * | 2012-05-02 | 2014-01-01 | 濮阳濮耐高温材料（集团）股份有限公司 | Ventilation functional element for carbon nanotube reinforced ventilation channel and preparation method thereof |
| IT201600125806A1 (en) | 2016-12-13 | 2018-06-13 | Pirelli | Tire for vehicle wheels |
| CN109200955B (en) * | 2018-11-14 | 2021-06-08 | 中国科学院兰州化学物理研究所 | Organic-inorganic dual-network structure phenolic aldehyde/alumina aerogel composite material and preparation method thereof |
| CN110744045A (en) * | 2019-09-06 | 2020-02-04 | 西安交通大学 | Method for in-situ synthesis of carbon nano tube on surface of aluminum alloy spherical powder |
| CN111495374B (en) * | 2020-05-13 | 2023-07-28 | 黄冈师范学院 | Coated CoNi/Al 2 O 3 Catalyst, preparation method and application thereof |
| CN115094544B (en) * | 2022-07-28 | 2023-03-14 | 中国人民解放军国防科技大学 | Lanthanum zirconate nano ceramic fiber and preparation method thereof |
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