CN102962087A - 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 potential application is arranged.CNT also is a kind of nano-carbon material.Since being found the carbon pipe by Iijima in 1991, this nano material with unique performances such as mechanics, calorifics and electricity has caused various countries researchers' very big research enthusiasm.The researcher finds, CNT has the 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 height of its specific area and pore-free exist, it or a kind of novel carbon-supported catalysts.Research finds that CNT shows preferably catalytic performance in the catalytic reactions such as oxidative dehydrogenation of ethylbenzene.Yet carbon nano-tube material is generally pulverous loose structure, produces inevitably Pressure Drop in the technical grade reactor, so hinder reaction species transmission, cause catalysqt deactivation.Practical nano-sized carbon catalysis material must possess enough mechanical strengths, unlimited macrostructure and long-term stability.The scientific research personnel finds that the ball of string macrostructure by a large amount of carbon nano-fibers form has certain compression strength.The people such as Van der Lee use Ni/SiO
2(20wt%) catalyst is at CO/H
2Prepared a carbon nano-fiber ball of string (van der Lee in the mixed atmosphere, 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 preferably bulk density and compression strength.But CNT has good carbonization structure, and its mechanical property generally is 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 macrostructure greatly.Simultaneously, 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 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 the span of CNT from the microcosmic to the macroscopic view, this composite has preferably mechanical strength simultaneously, can resist the Pressure Drop in the catalytic reactor, avoided the loose deficiency of carbon pipe aspect intensity, application in catalysis industry has important Research Significance for CNT 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 the Fe-Mg-Al composite catalyst, and with 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; The CNT average length is 1～200 μ m, and average diameter is 20～40nm.
Described CNT is a kind of in SWCN, double-walled carbon nano-tube or the multi-walled carbon nano-tubes.
The preparation method of above-mentioned CNT/foam silicon carbon catalytic composite materials may further comprise the steps:
(1) foam silicon carbon is carried out preliminary treatment;
(2) adopt coprecipitation that pretreated foam silicon carbon is loaded the Fe-Mg-Al composite catalyst;
(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 pretreated technical process: foam silicon carbon is successively put into respectively acetone, ethanolic solution, each ultrasonic cleaning 20～60min; Put into again deionized water and clean, the impurity of the silicon carbide that defoams; Then at 70～100 ℃ of lower dry 16～24h, collect and obtain 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 the 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, then 90～120 ℃ of constant temperature back flow reaction 2～12h stop to stir, and temperature are transferred to 100 ℃ again, constant temperature 4～20h;
(d) be down to room temperature after, take out reacted foam silicon carbon, put into baking oven in 70～100 ℃ of lower freeze-day with constant temperature 12～20h, 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, after furnace temperature rises to 650～750 ℃, pass 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 take out after the room temperature 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 the horizontal tube furnace.
Properties of SiC foam ceramics is a kind of high thermal conductance structural material, has network structure and the percent opening of macroscopic view.Nano-carbon material is immobilized on foam silicon carbon, can realize the compound of both macro and micro.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, behind this carrier surface loading catalyst, puts into tube furnace with the method for vapour deposition, has obtained a kind of novel CNT/foam silicon carbon catalytic composite materials.The present invention can be with the immobilized surface at carborundum of a large amount of CNTs, these carbon pipes are wound in network structure mutually, the surface of foam silicon carbon is covered fully, obtained a kind of macrostructure body of CNT, realized the span of CNT from the microcosmic to the macroscopic view.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, the CNT of preparation/foam silicon carbon catalytic composite materials has preferably mechanical strength, can resist the Pressure Drop in the catalytic reactor, avoid the loose deficiency of carbon pipe aspect intensity, can realize the industrial applications of carbon pipe aspect catalysis.
2, the carrier material among the present invention is preferably foam silicon carbon of thermal conductivity, is conducive to the heat conduction, and the loose structure that it has also is conducive to mass transfer.In addition, the method is simple, can be mass-produced.
3, it is controlled to load the amount of composite catalyst among the present invention on the foam silicon carbon, mainly is the quality of the foam silicon carbon of concentration by regulating the complex catalyst precursor liquid solution and adding; The load capacity of CNT is controlled on the foam silicon carbon, mainly is by changing the reaction condition of chemical vapour deposition (CVD).
Description of drawings
Fig. 1 is the ESEM picture of foam silicon carbon.
Fig. 2 is the ESEM picture of CNT of the present invention/foam silicon carbon catalytic composite materials; Wherein (b) is the scanned picture after (a) further amplified.
Fig. 3 is transmission electron microscope (TEM) picture of carbon pipe on CNT of the present invention/foam silicon carbon catalytic composite materials.
Fig. 4 is placed on CNT of the present invention/foam silicon carbon catalytic composite materials in the ethanolic solution of 50ml, and ultrasonic 30 minutes, the solution photo of ultrasonic front (a) and ultrasonic rear (b).
Fig. 5 is the SEM photo of the sample after the ultrasonic processing; Wherein (b) is the scanned picture after (a) further amplified.
The specific embodiment:
The invention will be further described below in conjunction with embodiment, is necessary to be pointed out that at this following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
(1) foam silicon carbon preliminary treatment: (a) foam silicon carbon is successively put into respectively acetone, ethanolic solution, each ultrasonic cleaning 20min.(b) foam silicon carbon with step (a) gained cleans in deionized water, and the impurity of the silicon carbide that defoams is for subsequent use with collecting behind the 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.With 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 ℃, carry out constant temperature back flow reaction 2h.Then stop to stir, temperature is elevated to 100 ℃ again, constant temperature 4h.After being down to room temperature, take out above-mentioned reacted foam silicon carbon, put into 90 ℃ of freeze-day with constant temperature 12h of baking oven, obtain the foam silicon carbon behind the loading catalyst, it is stand-by to collect product.
(3) immobilized CNT on the 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 ℃, passes into hydrogen reducing 10min again.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 take out after the room temperature just to have 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%.
Behind the composite catalyst of foam silicon carbon surface precipitation one deck iron content, cracking hydrocarbon gas in tube furnace again can be at a large amount of CNT carborundum surperficial immobilized with the method for above-mentioned co-precipitation.These carbon pipes have covered the surface of carborundum fully, present the knitting wool bulk, such as Fig. 2 (a).These knitting wool pieces are similar to the grain morphology of foam silicon carbon among Fig. 1.Fig. 2 (b) is the scanned picture after Fig. 2 (a) is further amplified, and shows among the figure that CNT is wound in network structure mutually, even thickness, and the surface is cleaner.
Fig. 3 is transmission electron microscope (TEM) picture of carbon pipe on CNT/foam silicon carbon catalytic composite materials.From TEM as can be known, immobilized CNT is multi-walled pipes, and caliber is less than 30nm.
The 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 a) and after ultrasonic the solution colour of (Fig. 4 b) significantly do not change, illustrate that the active force of CNT and Carboround is larger in the composite that the present invention prepares, do not come off from carrier, composite has extraordinary stability.
Fig. 5 is the SEM photo of the composite after the ultrasonic processing of process among Fig. 4, can find that from photo ultrasonic processing does not reduce the CNT coverage of silicon carbide, the pattern of CNT does not change yet, and further specifies the CNT of the present invention's preparation/carborundum catalytic composite materials and has preferably stability.
Embodiment 2
(1) foam silicon carbon preliminary treatment: (a) foam silicon carbon is successively put into respectively acetone, ethanolic solution, each ultrasonic cleaning 40min.(b) foam silicon carbon with step (a) gained cleans in deionized water, removes the impurity of silicon carbide, and is for subsequent use with collecting behind the 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.With 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 ℃, carry out constant temperature back flow reaction 10h.Then stop to stir, temperature is elevated to 100 ℃ again, constant temperature 12h.After being down to room temperature, the foam silicon carbon after take out soaking is put into 70 ℃ of freeze-day with constant temperature 15h of baking oven, obtains the foam silicon carbon behind the supported catalyst, and it is stand-by to collect product.
(3) immobilized CNT on the 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 ℃, passes into hydrogen reducing 5min again.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 take out after the room temperature just to have 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 are 1%.
Embodiment 3
(1) foam silicon carbon preliminary treatment: (a) foam silicon carbon is successively put into acetone, ethanolic solution, each ultrasonic cleaning 60min.(b) foam silicon carbon with step (a) gained cleans in deionized water, removes the impurity of silicon carbide, and is for subsequent use with collecting behind the 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.With 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 ℃, carry out constant temperature back flow reaction 12h.Then stop to stir, temperature is elevated to 100 ℃ again, constant temperature 20h.After being down to room temperature, the foam silicon carbon after take out soaking is put into 100 ℃ of freeze-day with constant temperature 20h of baking oven, obtains the foam silicon carbon behind the supported catalyst, and it is stand-by to collect product.
(3) immobilized CNT on the 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 ℃, passes into hydrogen reducing 30min again.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 take out after the room temperature just to have 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 (7)
1. CNT/foam silicon carbon catalytic composite materials, it is characterized in that: even carbon nanotube loads on the surface of the foam silicon carbon carrier that is loaded with the Fe-Mg-Al composite catalyst, and with its surface coverage, described CNT is wound in network structure mutually.
2. CNT according to claim 1/foam silicon carbon catalytic composite materials, it is characterized in that: the load capacity of described CNT is 0.6～10% of material gross mass, the load capacity of Fe-Mg-Al composite catalyst is 1～10% of material gross mass; The CNT average length is 1～200 μ m, and average diameter is 20～40nm.
3. CNT according to claim 1/foam silicon carbon catalytic composite materials is characterized in that: described CNT is a kind of in SWCN, double-walled carbon nano-tube or the multi-walled carbon nano-tubes.
4. the preparation method of CNT/foam silicon carbon catalytic composite materials is characterized in that as described in arbitrary such as claim 1-3, may further comprise the steps:
(1) foam silicon carbon is carried out preliminary treatment;
(2) adopt coprecipitation that pretreated foam silicon carbon is loaded the Fe-Mg-Al composite catalyst;
(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, after furnace temperature rises to 650～750 ℃, pass 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 take out after the room temperature 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.
5. preparation method according to claim 4 is characterized in that: foam silicon carbon is carried out pretreated technical process: foam silicon carbon is successively put into respectively acetone, ethanolic solution, each ultrasonic cleaning 20～60min; Put into again deionized water and clean, the impurity of the silicon carbide that defoams; Then at 70～100 ℃ of lower dry 16～24h, collect and obtain pretreated foam silicon carbon carrier.
6. preparation method according to claim 4 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 the 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, then 90～120 ℃ of constant temperature back flow reaction 2～12h stop to stir, and temperature are transferred to 100 ℃ again, constant temperature 4～20h;
(d) be down to room temperature after, take out reacted foam silicon carbon, put into baking oven in 70～100 ℃ of lower freeze-day with constant temperature 12～20h, obtain being loaded with the foam silicon carbon of catalyst.
7. preparation method according to claim 4, it is characterized in that: described tube furnace is the horizontal tube furnace.
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| CN110387482A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院金属研究所 | A kind of composite material and preparation method and application based on reverse foamed 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 |
| CN111377750A (en) * | 2020-04-15 | 2020-07-07 | 齐荟仟 | Carbon nanotube sponge reinforced silicon carbide ceramic matrix composite and preparation method thereof |
| CN112290021A (en) * | 2020-09-28 | 2021-01-29 | 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 |
| 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 |
| CN113145116A (en) * | 2021-01-20 | 2021-07-23 | 华东理工大学 | Integral TS-1 catalyst carrier and preparation and application thereof |
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