CN102962087B - Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof - Google Patents
Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon nanotube/silicon carbide foam catalytic composite material and a preparation method thereof, and belongs to the technical field of composite materials and preparation thereof. The preparation method of the invention comprises the following steps: firstly pretreating the silicon carbide foam; then loading a Fe-Mg-Al composite catalyst on the pretreated silicon carbide foam by a coprecipitation method; performing in-situ growth of carbon nanotubes on the silicon carbide foam surface loaded with the catalyst by a chemical vapor deposition method. According to the composite material prepared by the method, carbon nanotubes are uniformly loaded on the silicon carbide carrier surface loaded with the composite catalyst, and cover the surface; the carbon nanotubes wind with each other to form a reticulate structure. The invention realizes macroscopic assembly of carbon nanotubes; the prepared composite material has good mechanical strength, can resist pressure drop in a catalytic reactor, prevent deficiency in strength of loose carbon tubes, and realize industrial application of carbon tubes with respect to catalysis.
Description
Technical field
The invention belongs to composite and preparing technical field thereof, be specifically related to a kind of CNT/foam silicon carbon catalytic composite materials and preparation method thereof.
Background technology
Nano-sized carbon is a kind of novel material with carbon element, in a lot of fields, has potential application.CNT is also a kind of nano-carbon material.Since within 1991, being found carbon pipe by Iijima, this nano material with performances such as unique mechanics, calorifics and electricity has caused various countries researchers' very big research enthusiasm.Researcher finds, CNT has potential application except aspects such as being on the scene effect transistor, storage hydrogen device, ultracapacitor and engineering materials, because large, the surperficial degree of graphitization of its specific area is high and pore-free exists, it or a kind of novel carbon-supported catalysts.Research discovery, CNT shows good catalytic performance in the catalytic reactions such as oxidative dehydrogenation of ethylbenzene.But carbon nano-tube material is generally pulverous loose structure, in technical grade reactor, inevitably produce Pressure Drop, and then hinder reaction species transmission, cause catalysqt deactivation.Practical nano-sized carbon catalysis material must possess enough mechanical strengths, unlimited macrostructure and long-term stability.Scientific research personnel's discovery, the ball of string macrostructure being made up of a large amount of carbon nano-fibers, has certain compression strength.The people such as Van der Lee use Ni/SiO
2(20wt%) catalyst, at CO/H
2in mixed atmosphere, prepare a carbon nano-fiber ball of string (van der Lee, et al., Catalytic growth of macroscopic carbon nanofiber bodies with high bulk density and high mechanical strength, Carbon 2006,44 (4), 629-637).This carbon nano-fiber ball of string has good bulk density and compression strength.But CNT has good carbonization structure, its mechanical property is generally higher than carbon nano-fiber, and the CNT ball of string density that same procedure obtains is lower, needs after-treatment, and this has increased the difficulty that CNT is formed to macrostructure greatly.Meanwhile, carbon nano tube line unity structure also can face the difficulty of separation in liquid phase reactor.
Porous structure material is a kind of structure carrier material of excellence, and it has excellent mechanical strength and open large hole path.CNT and this loose structure vehicle group are dressed up to a kind of novel structural composite material, be expected to realize the commercial Application of CNT in catalytic field.
Summary of the invention
The object of the present invention is to provide a kind of CNT/foam silicon carbon catalytic composite materials and preparation method thereof, composite provided by the invention has been realized CNT from microcosmic to macroscopical span, this composite has good mechanical strength simultaneously, can resist the Pressure Drop in catalytic reactor, avoided the loose carbon pipe deficiency aspect intensity, for CNT, the application in catalysis industry has important Research Significance for this.
Technical scheme of the present invention is:
A kind of CNT/foam silicon carbon catalytic composite materials, even carbon nanotube loads on the surface of the Carboround that is loaded with Fe-Mg-Al composite catalyst, and by its surface coverage, described CNT is wound in network structure mutually.
The load capacity of described CNT is 0.6～10% of material gross mass, and the load capacity of Fe-Mg-Al composite catalyst is 1～10% of material gross mass; CNT average length is 1～200 μ m, and average diameter is 20～40nm.
Described CNT is the one in SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
The preparation method of above-mentioned CNT/foam silicon carbon catalytic composite materials, comprises the following steps:
(1) foam silicon carbon is carried out to pretreatment;
(2) adopt coprecipitation to load Fe-Mg-Al composite catalyst to pretreated foam silicon carbon;
(3) method of employing chemical vapour deposition (CVD), makes the foam silicon carbon surface in situ that is loaded with catalyst grow CNT.
Foam silicon carbon is carried out to pretreated technical process: foam silicon carbon is successively put into respectively to acetone, ethanolic solution, each ultrasonic cleaning 20～60min; Put into again deionized water and clean, the impurity of the silicon carbide that defoams; Then dry 16～24h at 70～100 DEG C, collects and obtains pretreated foam silicon carbon carrier.
The technical process of foam silicon carbon surface loading catalyst:
(a) ferric nitrate, magnesium nitrate, aluminum nitrate, urea and deionized water are put into there-necked flask, stir into solution;
(b) pretreated foam silicon carbon carrier in step (1) is put into the solution of above-mentioned there-necked flask; Wherein, the part by weight of ferric nitrate, magnesium nitrate, aluminum nitrate, urea, deionized water and foam silicon carbon is (0.2～6): (0.1～15): (2～12): (10～100): (150～500): (1～40);
(c) there-necked flask in (b) is put into oil bath pan, stir with the rotating speed of 20～50rpm, 90～120 DEG C of constant temperature back flow reaction 2～12h, then stop stirring, then temperature are adjusted to 100 DEG C, constant temperature 4～20h;
(d) be down to after room temperature, take out reacted foam silicon carbon, put into baking oven freeze-day with constant temperature 12～20h at 70～100 DEG C, obtain being loaded with the foam silicon carbon of catalyst.
Be loaded with the technical process of load CNT on the foam silicon carbon of catalyst: get the foam silicon carbon that is loaded with catalyst and put into tube furnace, pass into argon gas or nitrogen is done carrier gas, furnace temperature rises to after 650～750 DEG C, passes into hydrogen reducing 5～30min; Pass into again ethene, be loaded with the foam silicon carbon surface catalysis carbon nano-tube of catalyst; Then close rapidly hydrogen and ethene, keep carrier gas flux constant, be down to after room temperature and take out and just made CNT/foam silicon carbon catalytic composite materials; It is 10～300ml/min that ethene passes into speed, and growth time is 5～60min.
Above-mentioned tube furnace is horizontal tube furnace.
Properties of SiC foam ceramics is a kind of high thermal conductance structural material, has macroscopical network structure and percent opening.On foam silicon carbon, can realize the compound of both macro and micro by immobilized nano-carbon material.The high opening rate of foam silicon carbon can make reactive material mix, and has high reaction rate and null-rate.Immobilized nano-carbon material, can make the specific area of composite and the ratio of volume improve, and the unfavorable factor of avoiding Pressure Drop to bring.Meanwhile, the heat energy that the high-termal conductivity of carborundum can make carbon catalysis produce transmits rapidly, avoids the overheated catalysqt deactivation that makes.
The present invention selects foam silicon carbon as carrier material, after this carrier surface loading catalyst, puts into the method for tube furnace vapour deposition, has obtained a kind of novel CNT/foam silicon carbon catalytic composite materials.The present invention can be by the immobilized a large amount of CNTs surface at carborundum, these carbon pipes are wound in network structure mutually, the surface of foam silicon carbon is covered completely, obtained a kind of macrostructure body of CNT, realized CNT from microcosmic to macroscopical span.This macroscopic view for CNT is being assembled with important Research Significance.
Beneficial effect of the present invention is:
1, the present invention has realized the macroscopic view assembling of CNT, CNT/foam silicon carbon catalytic composite materials of preparation has good mechanical strength, can resist the Pressure Drop in catalytic reactor, avoid the loose carbon pipe deficiency aspect intensity, can realize the industrial applications of carbon pipe aspect catalysis.
2, the carrier material in the present invention is the good foam silicon carbon of thermal conductivity, is conducive to heat conduction, and the loose structure that it has, is also conducive to mass transfer.In addition, the method is simple, can be mass-produced.
3, in the present invention, on foam silicon carbon, loading the amount of composite catalyst controlled, is mainly the quality of the concentration by regulating complex catalyst precursor liquid solution and the foam silicon carbon that adds; On foam silicon carbon, the load capacity of CNT is controlled, is mainly the reaction condition by changing chemical vapour deposition (CVD).
Brief description of the drawings
Fig. 1 is the ESEM picture of foam silicon carbon.
Fig. 2 is the ESEM picture of CNT/foam silicon carbon catalytic composite materials of the present invention; Wherein (b) is the scanned picture after (a) further amplified.
Fig. 3 is transmission electron microscope (TEM) picture of carbon pipe on CNT/foam silicon carbon catalytic composite materials of the present invention.
Fig. 4 is placed on CNT/foam silicon carbon catalytic composite materials of the present invention in the ethanolic solution of 50ml, ultrasonic 30 minutes, ultrasonic before (a) and ultrasonic after the solution photo of (b).
Fig. 5 is the SEM photo of ultrasonic sample after treatment; Wherein (b) is the scanned picture after (a) further amplified.
Detailed description of the invention:
Below in conjunction with embodiment, the invention will be further described, is necessary to be pointed out that at this following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
(1) foam silicon carbon pretreatment: (a) foam silicon carbon is successively put into respectively to acetone, ethanolic solution, each ultrasonic cleaning 20min.(b) foam silicon carbon of step (a) gained is cleaned in deionized water, the impurity of the silicon carbide that defoams, for subsequent use by collecting after sample drying.Figure (1) is the ESEM picture of foam silicon carbon.
(2) foam silicon carbon surface loading catalyst: according to the precursor solution of catalyst proportion preparation composite catalyst, ferric nitrate, magnesium nitrate, aluminum nitrate, urea and deionized water are put into there-necked flask according to the ratio of 0.2g: 0.1g: 2g: 10g and 150ml, stir into uniform solution.By the foam silicon carbon 1g of step (1), put into the solution of above-mentioned there-necked flask.Then this there-necked flask is put into oil bath pan, stir with the rotating speed of 20rpm, and temperature is elevated to 90 DEG C, carry out constant temperature back flow reaction 2h.Then stop stirring, then temperature is elevated to 100 DEG C, constant temperature 4h.Be down to after room temperature, take out above-mentioned reacted foam silicon carbon, put into 90 DEG C of freeze-day with constant temperature 12h of baking oven, obtain the foam silicon carbon after loading catalyst, collect product stand-by.
(3) immobilized CNT on foam silicon carbon: the foam silicon carbon of getting step (2) is put into tube furnace, passes into argon gas or nitrogen is done carrier gas, and furnace temperature is risen to 650 DEG C, then passes into hydrogen reducing 10min.And then pass into ethene, and it is 200ml/min that ethene passes into speed, at silicon carbide catalytic growth CNT, growth time is 60min.Then close rapidly hydrogen and ethene, carrier gas flux is constant, is down to after room temperature and takes out and just made CNT/foam silicon carbon catalytic composite materials.In CNT/foam silicon carbon catalytic composite materials, the load capacity of catalyst is 4%, and the load capacity of CNT is 9%.
By the method for above-mentioned co-precipitation after the composite catalyst of foam silicon carbon surface precipitation one deck iron content, then in tube furnace cracking hydrocarbon gas, can be immobilized on the surface of carborundum a large amount of CNTs.These carbon pipes have covered the surface of carborundum completely, present knitting wool bulk, as Fig. 2 (a).These knitting wool pieces are similar to the grain morphology of foam silicon carbon in Fig. 1.Fig. 2 (b) is the scanned picture after Fig. 2 (a) is further amplified, and shows that CNT is wound in network structure mutually in figure, even thickness, and surface is cleaner.
Fig. 3 is transmission electron microscope (TEM) picture of carbon pipe on CNT/foam silicon carbon catalytic composite materials.From TEM, immobilized CNT is multi-walled pipes, and caliber is less than 30nm.
CNT/foam silicon carbon catalytic composite materials of preparation is placed in the ethanolic solution of 50ml, ultrasonic 30 minutes, the photo of the solution of ultrasonic front and back as shown in Figure 4, as seen from the figure, before ultrasonic, (Fig. 4 is a) and after ultrasonic, and (Fig. 4 solution colour b) does not significantly change, and illustrates that in composite prepared by the present invention, the active force of CNT and Carboround is larger, do not come off from carrier, composite has extraordinary stability.
Fig. 5 is the SEM photo through ultrasonic composite after treatment in Fig. 4, from photo, can find that ultrasonic processing does not reduce the CNT coverage of silicon carbide, the pattern of CNT does not also change, and further illustrates CNT/carborundum catalytic composite materials prepared by the present invention and has good stability.
Embodiment 2
(1) foam silicon carbon pretreatment: (a) foam silicon carbon is successively put into respectively to acetone, ethanolic solution, each ultrasonic cleaning 40min.(b) foam silicon carbon of step (a) gained is cleaned in deionized water, remove the impurity of silicon carbide, for subsequent use by collecting after sample drying.
(2) foam silicon carbon catalyst supported on surface: according to the precursor solution of catalyst proportion preparation composite catalyst, ferric nitrate, magnesium nitrate, aluminum nitrate, urea and deionized water are put into there-necked flask according to the ratio of 2g: 6g: 4g: 45g and 250ml, stir into uniform solution.By the foam silicon carbon 10g of step (1), the solution of putting into above-mentioned there-necked flask soaks.Then this there-necked flask is put into oil bath pan, stir with the rotating speed of 30rpm, and temperature is elevated to 100 DEG C, carry out constant temperature back flow reaction 10h.Then stop stirring, then temperature is elevated to 100 DEG C, constant temperature 12h.Be down to after room temperature, take out the foam silicon carbon after soaking, put into 70 DEG C of freeze-day with constant temperature 15h of baking oven, obtain the foam silicon carbon after supported catalyst, collect product stand-by.
(3) immobilized CNT on foam silicon carbon: the foam silicon carbon of getting step (2) is put into tube furnace, passes into argon gas or nitrogen is done carrier gas, and furnace temperature is risen to 750 DEG C, then passes into hydrogen reducing 5min.Then pass into ethene, it is 60ml/min that ethene passes into speed, and at silicon carbide catalytic growth CNT, growth time is 5min.Then close rapidly hydrogen and ethene, carrier gas flux is constant, is down to after room temperature and takes out and just made CNT/foam silicon carbon catalytic composite materials.In CNT/foam silicon carbon catalytic composite materials, the load capacity 1% of catalyst, the load capacity of CNT is 1%.
Embodiment 3
(1) foam silicon carbon pretreatment: (a) foam silicon carbon is successively put into acetone, ethanolic solution, each ultrasonic cleaning 60min.(b) foam silicon carbon of step (a) gained is cleaned in deionized water, remove the impurity of silicon carbide, for subsequent use by collecting after sample drying.
(2) foam silicon carbon catalyst supported on surface: according to the precursor solution of catalyst proportion preparation composite catalyst, ferric nitrate, magnesium nitrate, aluminum nitrate, urea and deionized water are put into there-necked flask according to the ratio of 6g: 15g: 12g: 100g and 500ml, stir into uniform solution.By the foam silicon carbon 20g of step (1), the solution of putting into above-mentioned there-necked flask soaks.Then this there-necked flask is put into oil bath pan, stir with the rotating speed of 50rpm, and temperature is elevated to 120 DEG C, carry out constant temperature back flow reaction 12h.Then stop stirring, then temperature is elevated to 100 DEG C, constant temperature 20h.Be down to after room temperature, take out the foam silicon carbon after soaking, put into 100 DEG C of freeze-day with constant temperature 20h of baking oven, obtain the foam silicon carbon after supported catalyst, collect product stand-by.
(3) immobilized CNT on foam silicon carbon: the foam silicon carbon of getting step (2) is put into tube furnace, passes into argon gas or nitrogen is done carrier gas, and furnace temperature is risen to 700 DEG C, then passes into hydrogen reducing 30min.Then pass into ethene, it is 100ml/min that ethene passes into speed, and at silicon carbide catalytic growth CNT, growth time is 30min.Then close rapidly hydrogen and ethene, carrier gas flux is constant, is down to after room temperature and takes out and just made CNT/foam silicon carbon catalytic composite materials.In CNT/foam silicon carbon catalytic composite materials, the load capacity of catalyst is 2%, the load capacity 5% of CNT.
Claims (3)
1. a preparation method for CNT/foam silicon carbon catalytic composite materials, even carbon nanotube loads on the surface of the foam silicon carbon carrier that is loaded with Fe-Mg-Al composite catalyst, and by its surface coverage, described CNT is wound in network structure mutually;
The load capacity of described CNT is 0.6～10% of material gross mass, and the load capacity of Fe-Mg-Al composite catalyst is 1～10% of material gross mass; CNT average length is 1～200 μ m, and average diameter is 20～40nm;
Described CNT is the one in SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes,
It is characterized in that, comprise the following steps:
(1) foam silicon carbon is carried out to pretreatment: foam silicon carbon is successively put into respectively to acetone, ethanolic solution, each ultrasonic cleaning 20～60min; Put into again deionized water and clean, the impurity of the silicon carbide that defoams; Then dry 16～24h at 70～100 DEG C, collects and obtains pretreated foam silicon carbon carrier;
(2) adopt coprecipitation to load Fe-Mg-Al composite catalyst to pretreated foam silicon carbon;
(3) method of employing chemical vapour deposition (CVD), makes the foam silicon carbon surface in situ that is loaded with catalyst grow CNT;
The technical process of step (3): get the foam silicon carbon that is loaded with catalyst and put into tube furnace, pass into argon gas or nitrogen is done carrier gas, furnace temperature rises to after 650～750 DEG C, passes into hydrogen reducing 5～30min; Pass into again ethene, be loaded with the foam silicon carbon surface catalysis carbon nano-tube of catalyst; Then close rapidly hydrogen and ethene, keep carrier gas flux constant, be down to after room temperature and take out and just made CNT/foam silicon carbon catalytic composite materials; It is 20～300ml/min that ethene passes into speed, and growth time is 5～60min.
2. preparation method according to claim 1, is characterized in that: the technical process of foam silicon carbon surface loading catalyst:
(a) ferric nitrate, magnesium nitrate, aluminum nitrate, urea and deionized water are put into there-necked flask, stir into solution;
(b) pretreated foam silicon carbon carrier in step (1) is put into the solution of above-mentioned there-necked flask; Wherein, the part by weight of ferric nitrate, magnesium nitrate, aluminum nitrate, urea, deionized water and foam silicon carbon is (0.2～6): (0.1～15): (2～12): (10～100): (150～500): (1～40);
(c) there-necked flask in (b) is put into oil bath pan, stir with the rotating speed of 20～50rpm, 90～120 DEG C of constant temperature back flow reaction 2～12h, then stop stirring, then temperature are adjusted to 100 DEG C, constant temperature 4～20h;
(d) be down to after room temperature, take out reacted foam silicon carbon, put into baking oven freeze-day with constant temperature 12～20h at 70～100 DEG C, obtain being loaded with the foam silicon carbon of catalyst.
3. preparation method according to claim 1 and 2, is characterized in that: described tube furnace is horizontal tube furnace.
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| CN104624216A (en) * | 2013-11-12 | 2015-05-20 | 中国科学院金属研究所 | Palladium/carbon nanotube-foam silicon carbide integrated composite material and preparation method and application of composite material |
| CN103754878B (en) * | 2014-01-06 | 2015-10-14 | 上海交通大学 | The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ |
| CN106565263B (en) * | 2016-11-05 | 2019-07-30 | 天津大学 | A kind of preparation method of carbon nanotube/silicon carbide heat-conductive composite material |
| CN108217818B (en) * | 2018-01-04 | 2020-09-01 | 北京科技大学 | Method for removing hexavalent chromium by using carbon-silicon-aluminum composite material |
| CN110387482B (en) * | 2018-04-16 | 2021-05-28 | 中国科学院金属研究所 | Composite material based on reverse-mold foam material and preparation method and application thereof |
| CN109665512A (en) * | 2019-01-21 | 2019-04-23 | 中国科学院成都有机化学有限公司 | A kind of preparation method of multi-walled carbon nanotube |
| CN111377750B (en) * | 2020-04-15 | 2022-06-24 | 齐荟仟 | Carbon nanotube sponge reinforced silicon carbide ceramic matrix composite and preparation method thereof |
| CN112290021B (en) * | 2020-09-28 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube conductive agent for lithium ion battery |
| CN113145116B (en) * | 2021-01-20 | 2022-12-20 | 华东理工大学 | Integral TS-1 catalyst carrier and preparation and application thereof |
| CN113398965B (en) * | 2021-05-28 | 2022-11-29 | 山东第一医科大学(山东省医学科学院) | Heat-conducting reversed-loading catalyst, and preparation method and application thereof |
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| CN102021817B (en) * | 2010-11-11 | 2012-03-21 | 中国人民解放军国防科学技术大学 | Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof |
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