CN105439116A - Carbon nanotube catalyst self-cycle utilization method - Google Patents
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Abstract
The present invention discloses a carbon nanotube catalyst self-cycle utilization method, and belongs to the technical field of new material preparation. The method is as follows: a catalyst containing a transition metal and a magnesium oxide support is used for growth of carbon nanotubes, and a solid-phase carbon nanotube product and a catalyst-component-containing liquid can be obtained by chemical purification; and ethylenediamine tetraacetic acid disodium salt and an alkaline substance are used for the catalyst cycle and regeneration to obtain a self-cycle carbon nanotube catalyst used for green cyclic growth of the carbon nanotubes. The catalyst self-cycle utilization method avoids catalyst-component-containing waste liquid emissions in the purification process of the carbon nanotubes and potential environmental pollution caused by the waste liquid emissions, and a new method for green macroscopic quantity preparation of the carbon nanotubes is provided.
Description
Technical field
The invention belongs to type material preparing technical field, be specifically related to a kind of method that carbon nano-tube catalyst self-circulation utilizes.
Background technology
The high speed development of nanometer science and technology be not only we better the knowledge of natural environment open the new visual field, simultaneously also for we bring multi-functional, the diversified nano material that Future Society Sustainable development needs badly.Carbon nanotube wherein one of most important advanced material just.The intrinsic performance of its excellence makes it all there is application prospect widely in a lot of fields, as nesa coating, nano-complex filler, can the electrode materials etc. of energy storage.Want better broadly to realize these application possibilities, controlled carbon nanotube preparation in macroscopic quantity is a prerequisite.
Generally speaking, compared to arc discharge method and laser ablation method, chemical Vapor deposition process is acknowledged as a kind of growth method that most probable realizes the production of carbon nanotube magnanimity.In chemical vapor deposition processes, often use transition metal as catalyst activity component, aluminum oxide, magnesium oxide etc. as support of the catalyst (as WO200294713A, CN1327943A, CN101049927A, CN1884058A, CN1948144A, CN101348249A, CN101665249, CN101665248, WO2003002456-A, US2006039849-A1, ChemSusChem2011,4,864-889; Small2013,9,1237 – 1265).But the actual carbon nanotube used often proposes higher requirement to its purity, catalyst residue content.So this just needs to adopt purifying, be namely further purified carbon nanotube (as CN1436722, CN03150121.4, US531504P, CN202898036-U, CN102442661-A, CN201310298689.6 etc.) by methods such as acid treatment, selective oxidation, vacuum high-temperature process.The solution containing catalyst elements can be produced by purifying, if directly discharge not only can cause the waste of material, and can environmental pollution be caused.If the method for catalyzer self-circulation can be developed, namely pass through aftertreatment further by catalyst regeneration, the recycling of catalyzer can be realized, and then improve efficiency and the economy of carbon nanotube production process.
Therefore, the very corn of a subject is: develop a kind of simple, optionally reclaims the method for the magnesium ion in solution, to realize the recycle of material, makes technique more energy-conserving and environment-protective simultaneously.
Summary of the invention
The problems such as the material waste that the waste liquid containing catalyst elements that the purge process that the object of the invention is to overcome producing Nano carbon tubes continuously produces causes and latency environment pollution, by the method that catalyzer self-circulation utilizes, realize carbon nanotube green, efficient preparation in macroscopic quantity.
For achieving the above object, technology contents of the present invention is:
The method that carbon nano-tube catalyst self-circulation utilizes, the method comprises the following steps:
1) using transition metal as catalyst activity component, magnesium oxide, as support of the catalyst, passes through chemical vapor deposition for carbon nanotubes;
2) above-mentioned carbon nano tube products is transported to purifying plant, adds acid and react;
3) carry out solid-liquor separation, collect solid and liquid; Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process or vacuum high-temperature process, and encapsulation is preserved; Liquid transfer is to catalyst recovery devices;
4) in the liquid of catalyst separating gained, disodium EDTA is added with the metal ion in complex solution, add basic cpd and the pH of mixing solutions is adjusted to 7-10, carry out liquid phase coprecipitation reaction, reaction times 1-24 hour, obtain the mixture containing solid phase precipitation;
5) carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse;
6) Solid Conveying and Melting separation obtained, to catalyst cupport device, adds the solid holdup of water to 1%-40% wherein, then adds catalyst activity component, prepare appropriate carbon nanotube growth catalysts; Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst;
7) carbon nano-tube catalyst for subsequent use is returned step 1), carry out the growth of carbon nanotube.
Described transition metal is more than one in Fe, Co, Ni, Mo, W.
Step 2) described in acid be more than one in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid, formic acid.
Step 2) in temperature of reaction be 0-100 DEG C, the reaction times is 0.1-24 hour.
Step 4) described in basic cpd be more than one in volatile salt, sodium carbonate, bicarbonate of ammonia, sodium bicarbonate, ammoniacal liquor, potassium hydroxide, salt of wormwood.
Described catalyst recovery devices be stirring tank, slurry bed system, bubbling bed more than one.
Described catalyst cupport device is more than one in stirring tank, water heating kettle, slurry bed system.
The present invention compared to existing technology, tool has the following advantages and high-lighting effect: the method that a kind of carbon nano-tube catalyst self-circulation provided by the invention utilizes, avoid the loss of active phase and carrier in purge process, reduce or remit the discharging of waste liquid containing catalyst elements and the latency environment pollution brought thereof, provide a kind of method of green preparation in macroscopic quantity carbon nanotube.
Accompanying drawing explanation
The schematic flow sheet of Fig. 1 carbon nano-tube catalyst self-circulation Application way.
Fig. 2 carbon nano-tube catalyst self-circulation Application way prepares the high-resolution-ration transmission electric-lens photo (TEM) of carbon nanotube-sample.
Fig. 3 carbon nano-tube catalyst self-circulation Application way prepares the Raman spectrogram of carbon nanotube-sample.
Fig. 4 carbon nano-tube catalyst self-circulation Application way prepares the adsorption/desorption curve of carbon nanotube-sample.
Fig. 5 carbon nano-tube catalyst self-circulation Application way prepares the pore distribution figure of carbon nanotube-sample.
Embodiment
Below by accompanying drawing and specific embodiment, the present invention is further illustrated:
Embodiment 1
Adopt Fe as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 20kg and be placed in stirring tank, add the sulphuric acid soln of 600L massfraction 10%, under agitation process 12 hours, temperature of reaction maintains 80 DEG C.Adopt filtering separation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 1kg disodium EDTA with the iron ion in complex solution, add the sal volatile 400L of 2mol/L, the pH of mixing solutions is adjusted to 8.5, liquid phase coprecipitation reaction is carried out, 2 hours reaction times under room temperature condition.Adopt centrifugation to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 30% wherein, then adds active phase Fe, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, carries out the growth of carbon nanotube.Accompanying drawing 2 provides the high-resolution-ration transmission electric-lens photo (TEM) that the method prepares carbon nanotube-sample, and accompanying drawing 3 provides its Raman spectrogram, and 4,5, accompanying drawing is adsorption/desorption curve and the pore distribution figure of sample respectively.Characterization result shows, and the method for the carbon nano-tube catalyst recycle that this patent provides can prepare the good carbon nanotube of quality.
Embodiment 2
Adopt Co as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 2kg and be placed in stirring tank, add the sulphuric acid soln of 30L massfraction 20%, under agitation process 2 hours, temperature of reaction maintains 90 DEG C.Adopt filtering separation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, vacuum high-temperature, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 0.2kg disodium EDTA with the metal ion in complex solution, add the sodium hydroxide solution 8L of 10mol/L, the pH of mixing solutions is adjusted to 8.5, liquid phase coprecipitation reaction is carried out, 6 hours reaction times under room temperature condition.Adopt filter type to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 10% wherein, then adds active phase Co, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare few-wall carbon nanotube by carbon nano-tube catalyst self-circulation.
Embodiment 3
Adopt Ni as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 200kg and be placed in stirring tank, add the salpeter solution of 1000L massfraction 40%, under agitation process 24 hours, temperature of reaction maintains 50 DEG C.Adopt centrifugation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 2kg disodium EDTA with the metal ion in complex solution, add sodium carbonate solid, the pH of mixing solutions is adjusted to 8.5, liquid phase coprecipitation reaction is carried out, 6 hours reaction times under room temperature condition.Adopt centrifugation to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device slurry bed system, adds the solid holdup of water to 20% wherein, then adds active phase Ni, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare double-walled carbon nano-tube by carbon nano-tube catalyst self-circulation.
Embodiment 4
Adopt Co, Mo as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 20kg and be placed in stirring tank, add the hydrochloric acid soln of 600L massfraction 10%, under agitation process 24 hours, temperature of reaction maintains 30 DEG C.Adopt centrifugation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 1kg disodium EDTA with the metal ion in complex solution, add potassium hydroxide solid, the pH of mixing solutions is adjusted to 9, liquid phase coprecipitation reaction is carried out, 24 hours reaction times under room temperature condition.Adopt centrifugation to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 10% wherein, then adds active phase CoMo, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare Single Walled Carbon Nanotube by carbon nano-tube catalyst self-circulation.
Embodiment 5
Adopt Fe, W as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 20kg and be placed in stirring tank, add the acetum of 300L massfraction 20%, under agitation process 12 hours, temperature of reaction maintains 40 DEG C.Adopt centrifugation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 0.5kg disodium EDTA with the metal ion in complex solution, add volatile salt, sodium carbonate solid, the pH of mixing solutions is adjusted to 9, liquid phase coprecipitation reaction is carried out, 12 hours reaction times under room temperature condition.Adopt centrifugation to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 2% wherein, then adds active phase FeW, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare few-wall carbon nanotube by carbon nano-tube catalyst self-circulation.
Embodiment 6
Adopt Fe, Mo as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 20g and be placed in stirring tank, add the formic acid solution of 300mL massfraction 20%, under agitation process 1 hour, temperature of reaction maintains 40 DEG C.Adopt filtering separation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 2g disodium EDTA with the metal ion in complex solution, add sodium carbonate solid, the pH of mixing solutions is adjusted to 11, liquid phase coprecipitation reaction is carried out, 12 hours reaction times under room temperature condition.Adopt filter type to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 2% wherein, then adds active phase FeMo, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare Single Walled Carbon Nanotube by carbon nano-tube catalyst self-circulation.
Embodiment 7
Adopt Fe as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 100kg and be placed in stirring tank, add the sulphuric acid soln of 300L massfraction 20%, under agitation process 12 hours, temperature of reaction maintains 90 DEG C.Adopt centrifugation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 2kg disodium EDTA with the metal ion in complex solution, add sodium carbonate solid, the pH of mixing solutions is adjusted to 9, liquid phase coprecipitation reaction is carried out, 12 hours reaction times under room temperature condition.Adopt centrifugation to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 15% wherein, then adds active phase Fe, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare Single Walled Carbon Nanotube by carbon nano-tube catalyst self-circulation.
Embodiment 8
Adopt Fe, Co as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 10kg and be placed in stirring tank, add the hydrochloric acid soln of 300L massfraction 5%, under agitation process 24 hours, temperature of reaction maintains 20 DEG C.Adopt centrifugation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 1.5kg disodium EDTA with the metal ion in complex solution, add sodium carbonate solid, the pH of mixing solutions is adjusted to 10, liquid phase coprecipitation reaction is carried out, 6 hours reaction times under room temperature condition.Adopt centrifugation to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 15% wherein, then adds active phase FeCo, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare Single Walled Carbon Nanotube by carbon nano-tube catalyst self-circulation.
Embodiment 9
Adopt Co as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 100g and be placed in stirring tank, add the salpeter solution of 1L massfraction 40%, under agitation process 4 hours, temperature of reaction maintains 50 DEG C.Adopt filtering separation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, high-temperature vacuum purification process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 5g disodium EDTA with the metal ion in complex solution, add sodium carbonate solid, the pH of mixing solutions is adjusted to 7, liquid phase coprecipitation reaction is carried out, 6 hours reaction times under room temperature condition.Adopt filtration to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 1% wherein, then adds active phase Co, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare single, double wall carbon nano tube by carbon nano-tube catalyst self-circulation.
Embodiment 10
Adopt Fe as catalyst activity component, magnesium oxide as support of the catalyst, the carbon nanotube prepared by chemical Vapor deposition process.Get 100kg and be placed in stirring tank, add the sulphuric acid soln of 500L massfraction 20%, under agitation process 24 hours, temperature of reaction maintains 80 DEG C.Adopt filtering separation, collect solid and liquid respectively.Solid obtains carbon nanotube product through rinse repeatedly, drying, high-temperature vacuum purification process, and encapsulation is preserved.Liquid transfer is in catalyst recovery devices stirring tank, wherein add 1kg disodium EDTA with the metal ion in complex solution, add sodium carbonate solid, the pH of mixing solutions is adjusted to 8.7, liquid phase coprecipitation reaction is carried out, 18 hours reaction times under room temperature condition.Adopt filtration to carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse.Solid Conveying and Melting separation obtained, in catalyst cupport device stirring tank, adds the solid holdup of water to 20% wherein, then adds active phase Fe, prepare appropriate carbon nanotube growth catalysts.Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst.Carbon nano-tube catalyst for subsequent use returns chemical vapor deposition processes, is utilized prepare Single Walled Carbon Nanotube by carbon nano-tube catalyst self-circulation.
Claims (7)
1. a method for carbon nano-tube catalyst self-circulation utilization, it is characterized in that, the method comprises the following steps:
1) using transition metal as catalyst activity component, magnesium oxide, as support of the catalyst, passes through chemical vapor deposition for carbon nanotubes;
2) above-mentioned carbon nano tube products is transported to purifying plant, adds acid and react;
3) carry out solid-liquor separation, collect solid and liquid; Solid obtains carbon nanotube product through rinse repeatedly, drying, weak oxide process or vacuum high-temperature process, and encapsulation is preserved; Liquid transfer is to catalyst recovery devices;
4) in the liquid of catalyst separating gained, disodium EDTA is added with the metal ion in complex solution, add basic cpd and the pH of mixing solutions is adjusted to 7-10, carry out liquid phase coprecipitation reaction, reaction times 1-24 hour, obtain the mixture containing solid phase precipitation;
5) carry out solid-liquor separation, repeatedly collect separating obtained solid after rinse;
6) Solid Conveying and Melting separation obtained, to catalyst cupport device, adds the solid holdup of water to 1%-40% wherein, then adds catalyst activity component, prepare appropriate carbon nanotube growth catalysts; Post catalyst reaction carries out solid-liquor separation, drying, calcining are for subsequent use as carbon nano-tube catalyst;
7) carbon nano-tube catalyst for subsequent use is returned step 1), carry out the growth of carbon nanotube.
2. method according to claim 1, is characterized in that, described transition metal is more than one in Fe, Co, Ni, Mo, W.
3. method according to claim 1, is characterized in that, step 2) described in acid be more than one in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid, formic acid.
4. method according to claim 1, is characterized in that, step 2) in temperature of reaction be 0-100 DEG C, the reaction times is 0.1-24 hour.
5. method according to claim 1, is characterized in that, step 4) described in basic cpd be more than one in volatile salt, sodium carbonate, bicarbonate of ammonia, sodium bicarbonate, ammoniacal liquor, potassium hydroxide, salt of wormwood.
6. in accordance with the method for claim 1, it is characterized in that, described catalyst recovery devices be stirring tank, slurry bed system, bubbling bed more than one.
7. in accordance with the method for claim 1, it is characterized in that, described catalyst cupport device is more than one in stirring tank, water heating kettle, slurry bed system.
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| CN111943171A (en) * | 2020-08-21 | 2020-11-17 | 温州大学 | Controllable preparation method of high-density single-walled carbon nanotube horizontal array |
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