CN105439116B - A kind of method that carbon nano-tube catalyst self-loopa utilizes - Google Patents
A kind of method that carbon nano-tube catalyst self-loopa utilizes Download PDFInfo
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- CN105439116B CN105439116B CN201410397879.8A CN201410397879A CN105439116B CN 105439116 B CN105439116 B CN 105439116B CN 201410397879 A CN201410397879 A CN 201410397879A CN 105439116 B CN105439116 B CN 105439116B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses the method that a kind of carbon nano-tube catalyst self-loopa for belonging to new material preparing technical field utilizes.The inventive method uses carries out carbon nano tube growth containing the catalyst of transition metal and magnesium oxide carrier, passes through chemical purification acquisition solid phase carbon nanotube product and the liquid containing catalytic component；Catalyst circulation, regeneration are carried out using disodium EDTA and alkaline matter, the carbon nano-tube catalyst for obtaining self-loopa is used for the green circulatory growth of CNT.Catalyst self-loopa regeneration method provided by the invention, avoid the discharging of waste liquid during Purification of Carbon Nanotubes containing catalyst elements and its latency environment brought pollution, there is provided a kind of green magnanimity prepares the new method of CNT.
Description
Technical field
The invention belongs to new material preparing technical field, and in particular to what a kind of carbon nano-tube catalyst self-loopa utilized
Method.
Background technology
The high speed development of nanometer science and technology be only we preferably the knowledge of natural environment opens the new visual field, while
Multi-functional, the diversified nano material that future society sustainable development needed badly is brought for us.CNT is exactly it
In one of most important advanced material.Its excellent intrinsic performance makes it in many fields all there is being widely applied prospect,
Such as nesa coating, nano-complex filler, can energy storage electrode material.More preferably broadly to realize these
It is a premise to be prepared using possible, controllable CNT magnanimity.
In general, compared to arc discharge method and laser ablation method, chemical vapour deposition technique is acknowledged as most probable
Realize a kind of growing method of CNT magnanimity production.In chemical vapor deposition processes, often using transition metal as
The conduct such as catalyst activity component, aluminum oxide, magnesia catalyst carrier (such as WO200294713A, CN1327943A,
CN101049927A、CN 1884058A、CN 1948144A、CN 101348249A、CN101665249、CN101665248、
WO2003002456-A, US2006039849-A1, ChemSusChem 2011,4,864-889；Small 2013,9,1237-
1265).But the CNT of actual use often proposes higher requirement to its purity, catalyst residue content.So
This just needs using purifying, i.e., CNT to be further purified by the methods of acid treatment, selective oxidation, vacuum high-temperature processing
(such as CN1436722, CN03150121.4, US531504P, CN202898036-U, CN102442661-A,
CN201310298689.6 etc.).Solution containing catalyst elements can be produced by purifying, if directly discharge not only results in
The waste of material, and environmental pollution can be caused.It is if the method for catalyst self-loopa can be developed, i.e., further by post-processing
Catalyst is regenerated, it is possible to achieve the recycling of catalyst, and then improve the efficiency and economy of CNT production process.
Therefore, the very corn of a subject is：Develop a kind of simple and easy, optionally reclaim the magnesium ion in solution
Method, to realize recycling for material, while make technique more energy-conserving and environment-protective.
The content of the invention
The purpose of the present invention is useless containing catalyst elements caused by the purge process for overcoming producing Nano carbon tubes continuously
The problems such as material waste caused by liquid and latency environment pollute, the method utilized by catalyst self-loopa, realizes CNT
It is prepared by green, efficient magnanimity.
To reach above-mentioned purpose, technology contents of the invention are：
A kind of method that carbon nano-tube catalyst self-loopa utilizes, this method comprise the following steps：
1) using transition metal as catalyst activity component, magnesia passes through chemical vapor deposition as catalyst carrier
Method prepares CNT；
2) above-mentioned carbon nano tube products are transported to purifying plant, add acid and reacted；
3) solid-liquor separation is carried out, collects solid and liquid；Solid is high through rinse repeatedly, drying, weak oxide processing or vacuum
Temperature processing obtains carbon nanotube product, and encapsulation preserves；Liquid is transported to catalyst recovery devices；
4) into the separating obtained liquid of catalyst add disodium EDTA with the metal in complex solution from
Son, add alkali compounds and the pH of mixed solution is adjusted to 7-10, carry out liquid phase coprecipitation reaction, hour in reaction time 1-24,
Obtain the mixture containing solid phase precipitation；
5) solid-liquor separation is carried out, collects separating obtained solid after rinse repeatedly；
6) by isolated Solid Conveying and Melting to catalyst load device, water to consolidating for 1%-40% is added thereto and is contained
Rate, catalyst activity component is then added, appropriate carbon nanotube growth catalysts are prepared；Post catalyst reaction carries out liquid and divided admittedly
From, dry, calcining as carbon nano-tube catalyst it is standby；
7) by standby carbon nano-tube catalyst return to step 1), carry out the growth of CNT.
The transition metal is one or more of Fe, Co, Ni, Mo, W.
Acid described in step 2) is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid, formic acid.
In step 2) reaction temperature be 0-100 DEG C, the reaction time be 0.1-24 hours.
Alkali compounds described in step 4) is ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate, ammoniacal liquor, hydroxide
One or more of potassium, potassium carbonate.
The catalyst recovery devices be stirred tank, slurry bed system, bubbling bed more than one.
The catalyst load device is one or more of stirred tank, water heating kettle, slurry bed system.
The present invention compared with prior art, has the following advantages that and high-lighting effect：A kind of CNT provided by the invention
The method that catalyst self-loopa utilizes, the loss of catalyst activity phase and carrier in purge process is avoided, reduced or remitted containing catalysis
The discharging of waste liquid of agent element and its latency environment pollution brought, there is provided a kind of method that green magnanimity prepares CNT.
Brief description of the drawings
The schematic flow sheet of Fig. 1 carbon nano-tube catalyst self-loopa Application ways.
The high-resolution-ration transmission electric-lens that carbon nanotube-sample is prepared in Fig. 2 carbon nano-tube catalyst self-loopa Application ways shine
Piece (TEM).
The Raman spectrograms of carbon nanotube-sample are prepared in Fig. 3 carbon nano-tube catalyst self-loopa Application ways.
The adsorption/desorption curve of carbon nanotube-sample is prepared in Fig. 4 carbon nano-tube catalyst self-loopa Application ways.
The pore size distribution figure of carbon nanotube-sample is prepared in Fig. 5 carbon nano-tube catalyst self-loopa Application ways.
Embodiment
Below by accompanying drawing and specific embodiment, the present invention is further illustrated：
Embodiment 1
Prepared using Fe as catalyst activity component, magnesia as catalyst carrier by chemical vapour deposition technique
CNT.Take 20kg to be placed in stirred tank, add the sulfuric acid solution of 600L mass fractions 10%, it is small to handle 12 under agitation
When, reaction temperature maintains 80 DEG C.Using being separated by filtration, solid and liquid are collected respectively.Solid is through rinse repeatedly, drying, weak
Oxidation processes obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
1kg disodium EDTAs are added 2mol/L sal volatile 400L, will mixed molten with the iron ion in complex solution
The pH of liquid is adjusted to 8.5, and liquid phase coprecipitation reaction, 2 hours reaction time are carried out under room temperature condition.Liquid is carried out using centrifugation
Gu separation, collects separating obtained solid repeatedly after rinse.Isolated Solid Conveying and Melting to catalyst load device is stirred
In kettle, the solid holdup of water to 30% is added thereto, then adds catalyst activity phase Fe, carbon nano tube growth is prepared and urges
Agent.Post catalyst reaction progress solid-liquor separation, drying, calcining are standby as carbon nano-tube catalyst.Standby CNT is urged
Agent returns to chemical vapor deposition processes, carries out the growth of CNT.Accompanying drawing 2 provides this method and CNT sample is prepared
The high-resolution-ration transmission electric-lens photo (TEM) of product, accompanying drawing 3 provide its Raman spectrogram, and 4,5, accompanying drawing is that the absorption of sample takes off respectively
Attached curve and pore size distribution figure.Characterization result shows that the method that the carbon nano-tube catalyst that this patent provides recycles can be prepared
The preferable CNT of mass.
Embodiment 2
Prepared using Co as catalyst activity component, magnesia as catalyst carrier by chemical vapour deposition technique
CNT.Take 2kg to be placed in stirred tank, add the sulfuric acid solution of 30L mass fractions 20%, handle 2 hours under agitation,
Reaction temperature maintains 90 DEG C.Using being separated by filtration, solid and liquid are collected respectively.Solid is high through rinse repeatedly, drying, vacuum
Temperature obtains carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding 0.2kg second
Edetate disodium salt adds 10mol/L sodium hydroxide solution 8L, by mixed solution with the metal ion in complex solution
PH be adjusted to 8.5, under room temperature condition carry out liquid phase coprecipitation reaction, 6 hours reaction time.Liquid is carried out using filter type to consolidate
Separation, collects separating obtained solid repeatedly after rinse.By isolated Solid Conveying and Melting to catalyst load device stirred tank
In, the solid holdup of water to 10% is added thereto, then adds catalyst activity phase Co, and carbon nano tube growth catalysis is prepared
Agent.Post catalyst reaction progress solid-liquor separation, drying, calcining are standby as carbon nano-tube catalyst.Standby carbon nanometer pipe catalytic
Agent returns to chemical vapor deposition processes, is utilized by carbon nano-tube catalyst self-loopa and prepares few-wall carbon nanotube.
Embodiment 3
Prepared using Ni as catalyst activity component, magnesia as catalyst carrier by chemical vapour deposition technique
CNT.Take 200kg to be placed in stirred tank, add the salpeter solution of 1000L mass fractions 40%, handle 24 under agitation
Hour, reaction temperature maintains 50 DEG C.Using centrifugation, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
Weak oxide handles to obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
2kg disodium EDTAs are added sodium carbonate solid, the pH of mixed solution are adjusted to the metal ion in complex solution
8.5, liquid phase coprecipitation reaction, 6 hours reaction time are carried out under room temperature condition.Solid-liquor separation is carried out using centrifugation, instead
Separating obtained solid is collected after multiple rinse.By isolated Solid Conveying and Melting into catalyst load device slurry bed system, Xiang Qi
The middle solid holdup for adding water to 20%, then adds catalyst activity phase Ni, appropriate carbon nanotube growth catalysts is prepared.Reaction
Rear catalyst progress solid-liquor separation, drying, calcining are standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returnization
Vapor deposition processes are learned, is utilized by carbon nano-tube catalyst self-loopa and prepares double-walled carbon nano-tube.
Embodiment 4
Using Co, Mo as catalyst activity component, magnesia is as catalyst carrier, by chemical vapour deposition technique system
Standby CNT.Take 20kg to be placed in stirred tank, add the hydrochloric acid solution of 600L mass fractions 10%, handle 24 under agitation
Hour, reaction temperature maintains 30 DEG C.Using centrifugation, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
Weak oxide handles to obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
1kg disodium EDTAs are added potassium hydroxide solid, the pH of mixed solution are adjusted with the metal ion in complex solution
To 9, liquid phase coprecipitation reaction, 24 hours reaction time are carried out under room temperature condition.Solid-liquor separation is carried out using centrifugation, instead
Separating obtained solid is collected after multiple rinse.By isolated Solid Conveying and Melting into catalyst load device stirred tank, Xiang Qi
The middle solid holdup for adding water to 10%, then adds catalyst activity phase CoMo, appropriate carbon nanotube growth catalysts is prepared.Instead
Answer rear catalyst progress solid-liquor separation, drying, calcining standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returns
Chemical vapor deposition processes, utilized by carbon nano-tube catalyst self-loopa and prepare single-walled carbon nanotube.
Embodiment 5
Using Fe, W as catalyst activity component, magnesia is as catalyst carrier, by chemical vapour deposition technique system
Standby CNT.Take 20kg to be placed in stirred tank, add the acetum of 300L mass fractions 20%, handle 12 under agitation
Hour, reaction temperature maintains 40 DEG C.Using centrifugation, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
Weak oxide handles to obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
0.5kg disodium EDTAs are added ammonium carbonate, sodium carbonate solid, will mixed molten with the metal ion in complex solution
The pH of liquid is adjusted to 9, and liquid phase coprecipitation reaction, 12 hours reaction time are carried out under room temperature condition.Liquid is carried out using centrifugation
Gu separation, collects separating obtained solid repeatedly after rinse.Isolated Solid Conveying and Melting to catalyst load device is stirred
In kettle, the solid holdup of water to 2% is added thereto, then adds catalyst activity phase FeW, carbon nano tube growth is prepared and urges
Agent.Post catalyst reaction progress solid-liquor separation, drying, calcining are standby as carbon nano-tube catalyst.Standby CNT is urged
Agent returns to chemical vapor deposition processes, is utilized by carbon nano-tube catalyst self-loopa and prepares few-wall carbon nanotube.
Embodiment 6
Using Fe, Mo as catalyst activity component, magnesia is as catalyst carrier, by chemical vapour deposition technique system
Standby CNT.Take 20g to be placed in stirred tank, add the formic acid solution of 300mL mass fractions 20%, handle 1 under agitation
Hour, reaction temperature maintains 40 DEG C.Using being separated by filtration, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
Weak oxide handles to obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
2g disodium EDTAs are added sodium carbonate solid, the pH of mixed solution are adjusted to the metal ion in complex solution
11, liquid phase coprecipitation reaction, 12 hours reaction time are carried out under room temperature condition.Solid-liquor separation is carried out using filter type, instead
Separating obtained solid is collected after multiple rinse.By isolated Solid Conveying and Melting into catalyst load device stirred tank, Xiang Qi
The middle solid holdup for adding water to 2%, then adds catalyst activity phase FeMo, appropriate carbon nanotube growth catalysts is prepared.Instead
Answer rear catalyst progress solid-liquor separation, drying, calcining standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returns
Chemical vapor deposition processes, utilized by carbon nano-tube catalyst self-loopa and prepare single-walled carbon nanotube.
Embodiment 7
Prepared using Fe as catalyst activity component, magnesia as catalyst carrier by chemical vapour deposition technique
CNT.Take 100kg to be placed in stirred tank, add the sulfuric acid solution of 300L mass fractions 20%, handle 12 under agitation
Hour, reaction temperature maintains 90 DEG C.Using centrifugation, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
Weak oxide handles to obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
2kg disodium EDTAs are added sodium carbonate solid, the pH of mixed solution are adjusted to the metal ion in complex solution
9, liquid phase coprecipitation reaction, 12 hours reaction time are carried out under room temperature condition.Solid-liquor separation is carried out using centrifugation, repeatedly
Separating obtained solid is collected after rinse.By isolated Solid Conveying and Melting into catalyst load device stirred tank, thereto
The solid holdup of water to 15% is added, catalyst activity phase Fe is then added, appropriate carbon nanotube growth catalysts is prepared.After reaction
Catalyst progress solid-liquor separation, drying, calcining are standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returns to chemistry
Vapor deposition processes, utilized by carbon nano-tube catalyst self-loopa and prepare single-walled carbon nanotube.
Embodiment 8
Using Fe, Co as catalyst activity component, magnesia is as catalyst carrier, by chemical vapour deposition technique system
Standby CNT.Take 10kg to be placed in stirred tank, add the hydrochloric acid solution of 300L mass fractions 5%, handle 24 under agitation
Hour, reaction temperature maintains 20 DEG C.Using centrifugation, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
Weak oxide handles to obtain carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
1.5kg disodium EDTAs are added sodium carbonate solid, the pH of mixed solution are adjusted with the metal ion in complex solution
To 10, liquid phase coprecipitation reaction, 6 hours reaction time are carried out under room temperature condition.Solid-liquor separation is carried out using centrifugation, instead
Separating obtained solid is collected after multiple rinse.By isolated Solid Conveying and Melting into catalyst load device stirred tank, Xiang Qi
The middle solid holdup for adding water to 15%, then adds catalyst activity phase FeCo, appropriate carbon nanotube growth catalysts is prepared.Instead
Answer rear catalyst progress solid-liquor separation, drying, calcining standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returns
Chemical vapor deposition processes, utilized by carbon nano-tube catalyst self-loopa and prepare single-walled carbon nanotube.
Embodiment 9
Prepared using Co as catalyst activity component, magnesia as catalyst carrier by chemical vapour deposition technique
CNT.Take 100g to be placed in stirred tank, add the salpeter solution of 1L mass fractions 40%, handle 4 hours under agitation,
Reaction temperature maintains 50 DEG C.Using being separated by filtration, solid and liquid are collected respectively.Solid is true through rinse repeatedly, drying, high temperature
Empty purification process obtains carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, wherein adding
5g disodium EDTAs are added sodium carbonate solid, the pH of mixed solution are adjusted to the metal ion in complex solution
7, liquid phase coprecipitation reaction, 6 hours reaction time are carried out under room temperature condition.Solid-liquor separation, repeatedly rinse are carried out using filtering
Separating obtained solid is collected afterwards.By isolated Solid Conveying and Melting into catalyst load device stirred tank, add thereto
The solid holdup of water to 1%, catalyst activity phase Co is then added, appropriate carbon nanotube growth catalysts are prepared.It is catalyzed after reaction
Agent progress solid-liquor separation, drying, calcining are standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returns to chemical gaseous phase
Deposition process, utilized by carbon nano-tube catalyst self-loopa and prepare single, double wall carbon nano tube.
Embodiment 10
Prepared using Fe as catalyst activity component, magnesia as catalyst carrier by chemical vapour deposition technique
CNT.Take 100kg to be placed in stirred tank, add the sulfuric acid solution of 500L mass fractions 20%, handle 24 under agitation
Hour, reaction temperature maintains 80 DEG C.Using being separated by filtration, solid and liquid are collected respectively.Solid through rinse repeatedly, drying,
High-temperature vacuum purification process obtains carbon nanotube product, and encapsulation preserves.Liquid is transported in catalyst recovery devices stirred tank, its
Middle addition 1kg disodium EDTAs add sodium carbonate solid, by mixed solution with the metal ion in complex solution
PH is adjusted to 8.7, and liquid phase coprecipitation reaction, 18 hours reaction time are carried out under room temperature condition.Solid-liquor separation is carried out using filtering,
Separating obtained solid is collected after rinse repeatedly.By isolated Solid Conveying and Melting into catalyst load device stirred tank, to
The solid holdup of water to 20% is wherein added, catalyst activity phase Fe is then added, appropriate carbon nanotube growth catalysts is prepared.Instead
Answer rear catalyst progress solid-liquor separation, drying, calcining standby as carbon nano-tube catalyst.Standby carbon nano-tube catalyst returns
Chemical vapor deposition processes, utilized by carbon nano-tube catalyst self-loopa and prepare single-walled carbon nanotube.
Claims (1)
1. a kind of method that carbon nano-tube catalyst self-loopa utilizes, it is characterised in that this method comprises the following steps：
1) using transition metal as catalyst activity component, magnesia is as catalyst carrier, by chemical vapour deposition technique system
Standby CNT；
2) above-mentioned carbon nano tube products are transported to purifying plant, add acid and reacted；
3) solid-liquor separation is carried out, collects solid and liquid；Solid through rinse repeatedly, drying, weak oxide processing or vacuum high-temperature at
Reason obtains carbon nanotube product, and encapsulation preserves；Liquid is transported to catalyst recovery devices；
4) disodium EDTA is added into the separating obtained liquid of catalyst with the metal ion in complex solution, is added
Enter alkali compounds and the pH of mixed solution is adjusted to 7-10, carry out liquid phase coprecipitation reaction, hour in reaction time 1-24, contained
There is the mixture of solid phase precipitation；
5) solid-liquor separation is carried out, collects separating obtained solid after rinse repeatedly；
6) by isolated Solid Conveying and Melting to catalyst load device, water is added thereto to 1%-40% solid holdup, so
After add catalyst activity component, appropriate carbon nanotube growth catalysts are prepared；Post catalyst reaction carries out solid-liquor separation, done
Dry, calcining is used as carbon nano-tube catalyst standby；
7) by standby carbon nano-tube catalyst return to step 1), carry out the growth of CNT；
The transition metal is one or more of Fe, Co, Ni, Mo, W；
Acid described in step 2) is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid, formic acid；
In step 2) reaction temperature be 0-100 DEG C, the reaction time be 0.1-24 hours；
Alkali compounds described in step 4) is ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium acid carbonate, ammoniacal liquor, potassium hydroxide,
One or more of potassium carbonate；
The catalyst recovery devices be stirred tank, slurry bed system, bubbling bed more than one；
The catalyst load device is one or more of stirred tank, water heating kettle, slurry bed system.
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| CN111943171B (en) * | 2020-08-21 | 2022-03-04 | 温州大学 | Controllable preparation method of high-density single-walled carbon nanotube horizontal array |
| CN115228483B (en) * | 2022-07-12 | 2023-11-14 | 远景动力技术(江苏)有限公司 | Catalyst for synthesizing carbon nano tube and application thereof |
| CN115532268A (en) * | 2022-09-24 | 2022-12-30 | 山东碳峰新材料科技有限公司 | Preparation and application of iron-based carbon nanotube catalyst |
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