CN1600683A - Method for preparing material of nano carbon tube - Google Patents
Method for preparing material of nano carbon tube Download PDFInfo
- Publication number
- CN1600683A CN1600683A CN 200410011179 CN200410011179A CN1600683A CN 1600683 A CN1600683 A CN 1600683A CN 200410011179 CN200410011179 CN 200410011179 CN 200410011179 A CN200410011179 A CN 200410011179A CN 1600683 A CN1600683 A CN 1600683A
- Authority
- CN
- China
- Prior art keywords
- preparation
- mixture
- modified montmorillonoid
- catalyzer
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
In the invention, polyolefin is used as carbon source material to be mixed with organic modified imvite and load metal catalytic agent as following weight composition ratio, polyolefin 75-97.5 percent, modified imvite 0-20 percent, load catalytic agent 0-5 percent, melting and mixing in banbury and Bitruder. Said mixed material is produced to carbon nanometre tube by method of gas flame heating burning. carbon source material is polyolefin or recovered polyolefin, the used load catalytic agent and modified imvite are easy to be prepared, the mixing device is common processing device of polymer material, the device to compose carbon nanometre tube material is ceramics crucible and common flame.
Description
Technical field
The present invention relates to a kind of method of synthesize nano carbon tube material, specifically, the present invention relates to utilize polyolefine-montmorillonite composite material under the supported catalyst effect, by the method for combustion method synthesizing carbon nanotubes.
Technical background
Know that from microcosmic, carbon nanotube is to constitute like this: a carbon atom combines with three adjacent carbon atoms, make to form the hexagon ring between the carbon atom,, then form cylindrical shape by planar development cellular, that multiple hexagon ring constitutes.The characteristics of carbon nanotube are that it typically has a diameter from several dusts to tens nanometers, and length-to-diameter ratio is tens to several thousand.Because carbon nanotube has excellent physical and mechanical performance and conductivity, is widely used.In recent years, people adopted the research of carbon nano-tube modification polymkeric substance more and more, and employed carbon nanotube and do not require that its structure is very perfect, but demand is big, and this just requires low and the carbon nanotube synthetic technology that output is big of preparation cost.
Usually, carbon nanotube adopts electric arc power generating method, laser evaporation method, electrochemical vapor deposition, catalysis synthesis process and the preparation of plasma synthesis method.The normally organic hydrocarbon small molecules of carbon source in these methods, as: methane, acetylene, ethene, CO or the like seldom have and adopt the carbon source material of organic polymer as made of carbon nanotubes; Simultaneously, all adopt protection of inert gas in the preparation process, and also more complicated of the equipment that is adopted.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of carbon nano-tube material.
The present invention adopts olefin polymer and modified montmorillonoid mixture as carbon source, and under the catalyst action, synthesizing carbon nanotubes in air is for the preparation carbon nanotube is explored new way.What is more important, along with polymer materials is widely used in industrial and agricultural production and the people's daily life, " white pollution " problem that waste or used plastics brought has produced serious threat to environment.Wherein, polyolefin polymers accounts for more than 50% of waste or used plastics.The present invention opens up a new way with the carbon source of polyolefins waste or used plastics as synthesizing carbon nanotubes for solving " white pollution ".
The purpose of carbon nano-tube material of the present invention preparation has been to overcome the shortcoming of raw material costliness in the above-mentioned prior art and institute's using appts complexity, and the problem of utilizing that in the existing technics of reclaim of plastic waste utilization it can not finally be solved waste or used plastics as the filler use, thereby a kind of carbon source material that utilizes cheap polyolefine and waste and old salvage material thereof as synthesizing carbon nanotubes is disclosed, under the synergy of ester/modified montmorillonite nano effect and catalyzer, the method for synthesizing carbon nanotubes.
The present invention mixes polyolefine with metal supported catalyst, organic modification montmonrillonite, above-mentioned mixing material is prepared carbon nanotube by the incendiary method.Its basic step and processing condition are:
A) prepare modified montmorillonoid by ion exchange reaction
The 1000mL temperature is in 80 ℃ of deionized waters with waiting mole concentrated hydrochloric acid with 1 mole of stearylamine acidifying, by volume 1: 1-2 joins and mixes in the montmorillonite dispersions, and mechanical stirring was mixed 30 minutes; Every 1500mL contains 20 gram polynites in this montmorillonite dispersions; Filtering precipitate, 80 ℃ washed with de-ionized water is pulverized throw out after air-dry, 60 ℃ of following vacuum-drying 24 hours, the micron order modified montmorillonoid.
B) adopt hydrogenation reduction method to prepare catalyzer
By weight 35-45 part nickel: (wherein the alumina weight ratio content is 10% to 55-65 part aluminium oxide-silicon oxide hybrid, the hybrid particle diameter is the 10-30 micron), the aqueous solution of nickelous nitrate and aluminium oxide-silicon oxide hybrid were stirred 0.5-1 hour down in 40-60 ℃, products therefrom was in 80-100 ℃ of oven dry 8-12 hour, calcined 2-4 hour down at 350-450 ℃ then, argon gas with hydrogen 5% is a reducing gas, flow velocity 25mL/min, 7.5 ℃/min of heat-up rate, temperature range is reduction 3-5 hour under 500-900 ℃ the condition; Stop heating, continue logical hydrogen simultaneously, treat that it is cooled to room temperature, obtain nickel particles and load on Ni type catalyzer on the micron-sized aluminium oxide-silicon oxide hybrid.
C) preparation of polyolefine-modified montmorillonoid-catalyst mixture
With polyolefine, modified montmorillonoid and catalyzer in Banbury mixer in 160-200 ℃, rotating speed 60-100 revolutions per second melting mixing 5-10 minute, polyolefin blend.Perhaps
Earlier with polyolefine and modified montmorillonoid pre-mixing at room temperature, from main charging opening this mixture is entered that melting mixing prepares masterbatch the forcing machine, from the 2nd charging opening catalyzer is added then and proceed melting mixing, each section of forcing machine temperature is in 160-200 ℃ of scope, the extruder screw rotating speed is 200-300 rev/min, gets polyene alkene mixture.
Ratio of components by weight wherein, polyolefine is 75-97.5%, and modified montmorillonoid is 0-20%, and catalyzer is 0-5%, and modified montmorillonoid and catalyzer are not 0% simultaneously.
Used polyolefine can be that polypropylene, polyethylene, ethylene-propylene copolymer are or/and polystyrene.
D) preparation of carbon nanotube and purification
The polyolefin blend of step c preparation is placed ceramic crucible and add a cover, being heated to the interior temperature of container is 550-650 ℃, be polymkeric substance the no flame generation to container top that takes fire heat-up time, is cooled to room temperature, obtains the black mixture of carbon nanotube and nickel catalyzator and polynite;
Hydrofluoric acid with 20-50% joins in the black mixture of step c preparation, stirs down and places 16-24 hour, separates obtaining black carbon powder; Additional proportion is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes 2-4 hour, separates the carbon nanotube that obtains purifying.
The carbon source material that adopts among the present invention is polyolefine or reclaims polyolefine, cheap, the source is abundant, supported catalyst that is adopted and modified montmorillonoid preparation are simple, employed mixing equipment is the common process equipment of polymer materials, and the equipment of employed synthesize nano carbon tube material is ceramic crucible and common flame.Comprehensive above-mentioned advantage, the cost that adopts method of the present invention to prepare carbon nano-tube material has advantage than other method, can solve the problem that technics of reclaim of plastic waste is utilized simultaneously.
Embodiment
Embodiment 1:
Prepare organic montmorillonoid by ion exchange reaction.At first, in 80 ℃ of deionized waters of 1000mL, with waiting mole concentrated hydrochloric acid with 1 mole of stearylamine acidifying, be injected into afterwards in the 1500mL montmorillonite dispersions, and continuing mechanically mixing 30 minutes, the white precipitate of acquisition filters, and with 80 ℃ of washed with de-ionized water 3 times, natural air drying then, and with pulverizer organic montmorillonoid is pulverized; At last, in 60 ℃ of vacuum drying ovens dry 24 hours.
Aluminium oxide-silicon oxide hybrid with 10 microns of particle diameters is a carrier, by weight 40 nickel: the ratio of 60 aluminium oxide-silicon oxide hybrids mixed the aqueous solution of nickelous nitrate and the hybrid of alumina silica 1 hour under 40 ℃.Products therefrom is put into retort furnace, 100 ℃ of oven dry 8 hours.400 ℃ of down calcinings 3 hours, the argon gas with hydrogen 5% is a reducing gas at last then, and flow velocity is 25mL/min, 7.5 ℃/min of heat-up rate, and temperature is to reduce 5 hours under 500 ℃ the condition.Stop to heat the back and continue logical hydrogen, treat that it is cooled to room temperature, obtain Ni type catalyzer.
By weight 90% polypropylene and 5% above-mentioned modified montmorillonoid, 5% above-mentioned supported catalyst are entered in the Banbury mixer simultaneously, under 200 ℃ and 100 rev/mins, carried out melting mixing 5 minutes, obtain polypropylene miser.
Get said mixture 1 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is 550 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 20% joins in the above-mentioned black mixture, and places 24 hours under magnetic agitation.Obtain black carbon powder after the centrifugation.Adding volume ratio then is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes after 4 hours, takes out and carries out centrifugation.Obtain carbon nanotube 0.13 gram of purifying this moment.
Embodiment 2
Prepare organic montmorillonoid by ion exchange reaction.At first, in 80 ℃ of deionized waters of 1000mL, with waiting mole concentrated hydrochloric acid with 1 mole of stearylamine acidifying, be injected into afterwards in the 1000mL montmorillonite dispersions, and continuing mechanically mixing 30 minutes, the white precipitate of acquisition filters, and with 80 ℃ of washed with de-ionized water 3 times, natural air drying then, and with pulverizer organic montmorillonoid is pulverized; At last, in 60 ℃ of vacuum drying ovens dry 24 hours.
Aluminium oxide-silicon oxide hybrid with 20 microns of particle diameters is a carrier, by weight 35 nickel: the ratio of 65 aluminium oxide-silicon oxide hybrids mixed the aqueous solution of nickelous nitrate and the hybrid of alumina silica 0.75 hour under 50 ℃.Products therefrom is put into retort furnace, 90 ℃ of oven dry 10 hours.350 ℃ of down calcinings 4 hours, the argon gas with hydrogen 5% is a reducing gas at last then, and flow velocity is 25mL/min, 7.5 ℃/min of heat-up rate, and temperature is to reduce 4 hours under 700 ℃ the condition.Stop heating then and continue logical hydrogen simultaneously, treat that it is cooled to room temperature, obtain Ni type catalyzer.
By weight 95% recovery polypropylene and 2.5% above-mentioned modified montmorillonoid, 2.5% above-mentioned supported catalyst are entered in the Banbury mixer simultaneously, under 200 ℃ and 60 rev/mins, carried out melting mixing 10 minutes, obtain polypropylene miser.
Get said mixture 3 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible, with vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is 600 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator.
Hydrofluoric acid with 30% joins in the above-mentioned black mixture, and places 24 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 2 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.18 gram of purifying this moment.
Embodiment 3
Prepare organic montmorillonoid by ion exchange reaction.At first, in 80 ℃ of deionized waters of 1000mL, with waiting mole concentrated hydrochloric acid with 1 mole of stearylamine acidifying, be injected into afterwards in the 2000mL montmorillonite dispersions, and continuing mechanically mixing 30 minutes, the white precipitate of acquisition filters, and with 80 ℃ of washed with de-ionized water 3 times, natural air drying then, and with pulverizer organic montmorillonoid is pulverized; At last, in 60 ℃ of vacuum drying ovens dry 24 hours.
Aluminium oxide-silicon oxide hybrid with 30 microns of particle diameters is a carrier, by weight 45 nickel: the ratio of 55 aluminium oxide-silicon oxide hybrids mixed the aqueous solution of nickelous nitrate and the hybrid of alumina silica 0.5 hour under 60 ℃.Products therefrom is put into retort furnace, 80 ℃ of oven dry 12 hours.450 ℃ of down calcinings 2 hours, the argon gas with hydrogen 5% is a reducing gas at last then, and flow velocity is 25mL/min, 7.5 ℃/min of heat-up rate, and temperature is to reduce 3 hours under 900 ℃ the condition.Stop heating then and continue logical hydrogen simultaneously, treat that it is cooled to room temperature.Obtain Ni type catalyzer.
By weight 5% above-mentioned supported catalyst and 80% recovery polypropylene and 15% above-mentioned modified montmorillonoid are added in the Banbury mixer simultaneously, under 200 ℃ and 80 rev/mins, carried out melting mixing 8 minutes, obtain polypropylene miser.
Get said mixture 2 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is 650 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 50% joins in the above-mentioned black mixture, and places 16 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 3 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.52 gram of purifying this moment.
Embodiment 4
By weight modified montmorillonoid in supported catalyst and 85% polystyrene in 5% example 2 and 10% example 1 is added in the Banbury mixer simultaneously, under 180 ℃ and 80 rev/mins, carried out melting mixing 8 minutes, obtain polystyrene blends.
Get said mixture 2 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is 600 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 40% joins in the above-mentioned black mixture, and places 16 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 4 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.21 gram of purifying this moment.
Embodiment 5
By weight modified montmorillonoid in 85% ethylene-propylene copolymer and 15% example 2 is added in the Banbury mixer simultaneously, under 170 ℃ and 70 rev/mins, carried out melting mixing 8 minutes, obtain the ethylene-propylene copolymer mixture.
Get said mixture 2 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is about about 600 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 20% joins in the above-mentioned black mixture, and places 24 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 3 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.08 gram of purifying this moment.
Embodiment 6
By weight modified montmorillonoid prepared in supported catalyst prepared in 5% example 2 and 75% polyethylene and 20% example 3 is added in the Banbury mixer simultaneously, under 160 ℃ and 80 rev/mins, carried out melting mixing 8 minutes, obtain polyethylene mixture.
Get said mixture 2 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is about about 650 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 30% joins in the above-mentioned black mixture, and places 20 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 3 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.31 gram of purifying this moment.
Embodiment 7
Adopt supported catalyst prepared in modified montmorillonoid prepared in the example 3 of weight ratio 10%, 5% example 2 and 85% polyethylene in twin screw extruder, to carry out two step melting mixing, screw speed is 200 rev/mins, and four sections temperature are respectively 160 ℃, 170 ℃, 170 ℃ and 170 ℃.In twin screw extruder, will contain polyethylene and modified montmorillonoid earlier and add, at the 2nd charging opening supported catalyst be added again at the 1st charging opening.
Get said mixture 1 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is about about 600 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 20% joins in the above-mentioned black mixture, and places 24 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 2 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.090 gram of purifying this moment.
Embodiment 8
Adopt supported catalyst prepared in modified montmorillonoid prepared in the example 1 of weight ratio 10%, 5% example 1 and 85% polypropylene in twin screw extruder, to carry out two step melting mixing, screw speed is 300 rev/mins, and four sections temperature are respectively 180 ℃, 190 ℃, 200 ℃ and 200 ℃.In twin screw extruder, will contain polypropylene and modified montmorillonoid earlier and add, at the 2nd charging opening supported catalyst be added again at the 1st charging opening.
Get said mixture 1 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is about about 650 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 30% joins in the above-mentioned black mixture, and places 20 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 3 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.42 gram of purifying this moment.
Embodiment 9
Adopt supported catalyst prepared in modified montmorillonoid prepared in the example 2 of weight ratio 10%, 5% example 3 and 85% polypropylene in twin screw extruder, to carry out two step melting mixing, screw speed is 250 rev/mins, and four sections temperature are respectively 180 ℃, 190 ℃, 200 ℃ and 200 ℃.In twin screw extruder, will contain polypropylene and modified montmorillonoid earlier and add, at the 2nd charging opening supported catalyst be added again at the 1st charging opening.
Get said mixture 1 gram and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With vapour lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.The interior temperature of crucible this moment is about about 650 ℃.Polymkeric substance behind the reignition, does not take off crucible, is put in shady and cool place and is cooled to room temperature.Obtain this moment is the black mixture of carbon nanotube and nickel catalyzator and polynite.
Hydrofluoric acid with 40% joins in the above-mentioned black mixture, and places 16 hours under magnetic agitation.Centrifugation then obtains black carbon powder.Add volume ratio then and be the mixture of 1: 1 vitriol oil and concentrated nitric acid, reflux after 4 hours, take out and carry out centrifugation.Obtain carbon nanotube 0.34 gram of purifying this moment.
Claims (5)
1. the preparation method of a carbon nano-tube material, its key step is:
A) prepare modified montmorillonoid by ion exchange reaction
With waiting mole concentrated hydrochloric acid with 1 mole of stearylamine acidifying, by volume 1: 1-2 joins and mixes in the montmorillonite dispersions, and continues mechanically mixing 30 minutes, and every 1500mL contains 20 gram polynites in this montmorillonite dispersions in 80 ℃ of following 1000mL deionized waters; Filtering precipitate, and with 60-80 ℃ of washed with de-ionized water is pulverized throw out after air-dry, 60 ℃ of following vacuum-drying 24 hours, modified montmorillonoid;
B) adopt hydrogenation reduction method to prepare catalyzer
By weight 35-45 part nickel: 55-65 part aluminium oxide-silicon oxide hybrid, wherein the alumina weight ratio content is 10%, the hybrid particle diameter is the 10-30 micron, the aqueous solution of nickelous nitrate and aluminium oxide-silicon oxide hybrid were stirred 0.5-1 hour down in 40-60 ℃, products therefrom was in 80-100 ℃ of oven dry 8-12 hour, calcined 2-4 hour down at 350-450 ℃ then, argon gas with hydrogen 5% is a reducing gas, flow velocity 25mL/min, 7.5 ℃/min of heat-up rate, temperature range is reduction 3-5 hour under 500-900 ℃ the condition; Stop heating, continue logical hydrogen simultaneously, treat that it is cooled to room temperature, obtain Ni type catalyzer;
C) preparation of polyolefine-modified montmorillonoid-catalyst mixture
With the catalyzer of the modified montmorillonoid of polyolefine, step a preparation and step b preparation in Banbury mixer in 160-200 ℃, rotating speed 60-100 revolutions per second melting mixing 5-10 minute, make polypropylene miser; Ratio of components by weight wherein, polyolefine is 75-97.5%, and modified montmorillonoid is 0-20%, and catalyzer is 0-5%, and modified montmorillonoid and catalyzer are not 0% simultaneously;
D) preparation of carbon nanotube and purification
The polyolefin blend of step c preparation is placed ceramic crucible and add a cover, being heated to the interior temperature of container is 550-650 ℃, be polymkeric substance the no flame generation to container top that takes fire heat-up time, is cooled to room temperature, obtains the black mixture of carbon nanotube and nickel catalyzator and polynite;
Hydrofluoric acid with 20-50% joins in the black mixture of step c preparation, stirs down and places 16-24 hour, separates obtaining black carbon powder; Additional proportion is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes 2-4 hour, separates the carbon nanotube that obtains purifying.
2. the preparation method of claim 1 is characterized in that, described modified montmorillonoid is a micron order.
3. the preparation method of claim 1 is characterized in that, described catalyzer is that nickel particles loads on the micron-sized aluminium oxide-silicon oxide hybrid.
4. the preparation method of claim 1, it is characterized in that, step c can also be earlier with polyolefine and modified montmorillonoid pre-mixing at room temperature, from main charging opening this mixture is entered that melting mixing prepares masterbatch the forcing machine, from the 2nd charging opening catalyzer is added then and proceed melting mixing, each section of forcing machine temperature is in 160-200 ℃ of scope, and the extruder screw rotating speed is 200-300 rev/min.
5. the preparation method of claim 1 is characterized in that, used polyolefine is polypropylene, polyethylene, ethylene-propylene copolymer or polystyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011179 CN1288076C (en) | 2004-10-26 | 2004-10-26 | Method for preparing material of nano carbon tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011179 CN1288076C (en) | 2004-10-26 | 2004-10-26 | Method for preparing material of nano carbon tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1600683A true CN1600683A (en) | 2005-03-30 |
| CN1288076C CN1288076C (en) | 2006-12-06 |
Family
ID=34662728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410011179 Expired - Fee Related CN1288076C (en) | 2004-10-26 | 2004-10-26 | Method for preparing material of nano carbon tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1288076C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Mechanically shearing process of preparing one-dimensional nanometer material |
| CN100431950C (en) * | 2005-06-03 | 2008-11-12 | 中国科学院长春应用化学研究所 | Method for synthesizing carbon nanotube and its compounds by polyolefin combustion with nickel oxide as catalyst |
| CN100434360C (en) * | 2005-12-09 | 2008-11-19 | 中国科学院理化技术研究所 | Method for preparing multi-wall carbon hano tube, chestnut-like carbon nano tube aggregator and carbon nano tube ball |
| CN100443401C (en) * | 2006-03-31 | 2008-12-17 | 中国科学院长春应用化学研究所 | Method of synthesizing nanometer carbon pipe by cracking polymer |
| CN100460358C (en) * | 2007-05-23 | 2009-02-11 | 上海应用技术学院 | Method of preparing high specific surface siloxicon ceramic nano-tube |
| CN100519408C (en) * | 2005-08-10 | 2009-07-29 | 中国科学院长春应用化学研究所 | Preparing hydrogen and Nano carbon tube through catalytic cracking polyolefine |
| CN1775671B (en) * | 2005-12-16 | 2010-05-05 | 中国科学院长春应用化学研究所 | Method for preparing carbon nano tube by nickel compound catalytic combustion of polyolefin |
| CN101792136A (en) * | 2010-04-12 | 2010-08-04 | 东北林业大学 | Method for synthesizing carbon nanotubes by using micro-molecular gas and polymer |
| WO2012174679A1 (en) * | 2011-06-23 | 2012-12-27 | 山东大展纳米材料有限公司 | Preparation method of nano carbon material by using clay catalytic material |
| CN102741161B (en) * | 2008-04-16 | 2014-06-25 | 日本瑞翁株式会社 | Equipment and method for producing orientated carbon nano-tube aggregates |
| CN107934938A (en) * | 2017-12-06 | 2018-04-20 | 武汉光谷环保科技股份有限公司 | The method that two-phase method catalytic pyrolysis waste plastic prepares carbon nanotubes |
| TWI810011B (en) * | 2022-08-05 | 2023-07-21 | 崑山科技大學 | Preparation and application of three-dimensional carbon nanotubes grown from soil clay and graphene oxide |
-
2004
- 2004-10-26 CN CN 200410011179 patent/CN1288076C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431950C (en) * | 2005-06-03 | 2008-11-12 | 中国科学院长春应用化学研究所 | Method for synthesizing carbon nanotube and its compounds by polyolefin combustion with nickel oxide as catalyst |
| CN100519408C (en) * | 2005-08-10 | 2009-07-29 | 中国科学院长春应用化学研究所 | Preparing hydrogen and Nano carbon tube through catalytic cracking polyolefine |
| CN100434360C (en) * | 2005-12-09 | 2008-11-19 | 中国科学院理化技术研究所 | Method for preparing multi-wall carbon hano tube, chestnut-like carbon nano tube aggregator and carbon nano tube ball |
| CN1775671B (en) * | 2005-12-16 | 2010-05-05 | 中国科学院长春应用化学研究所 | Method for preparing carbon nano tube by nickel compound catalytic combustion of polyolefin |
| CN100443401C (en) * | 2006-03-31 | 2008-12-17 | 中国科学院长春应用化学研究所 | Method of synthesizing nanometer carbon pipe by cracking polymer |
| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Mechanically shearing process of preparing one-dimensional nanometer material |
| CN100460358C (en) * | 2007-05-23 | 2009-02-11 | 上海应用技术学院 | Method of preparing high specific surface siloxicon ceramic nano-tube |
| CN102741161B (en) * | 2008-04-16 | 2014-06-25 | 日本瑞翁株式会社 | Equipment and method for producing orientated carbon nano-tube aggregates |
| CN101792136A (en) * | 2010-04-12 | 2010-08-04 | 东北林业大学 | Method for synthesizing carbon nanotubes by using micro-molecular gas and polymer |
| WO2012174679A1 (en) * | 2011-06-23 | 2012-12-27 | 山东大展纳米材料有限公司 | Preparation method of nano carbon material by using clay catalytic material |
| CN107934938A (en) * | 2017-12-06 | 2018-04-20 | 武汉光谷环保科技股份有限公司 | The method that two-phase method catalytic pyrolysis waste plastic prepares carbon nanotubes |
| TWI810011B (en) * | 2022-08-05 | 2023-07-21 | 崑山科技大學 | Preparation and application of three-dimensional carbon nanotubes grown from soil clay and graphene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1288076C (en) | 2006-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1288076C (en) | Method for preparing material of nano carbon tube | |
| Ma et al. | Metal-organic framework@ polyaniline nanoarchitecture for improved fire safety and mechanical performance of epoxy resin | |
| Yu et al. | Single-source-precursor synthesis of porous W-containing SiC-based nanocomposites as hydrogen evolution reaction electrocatalysts | |
| Zhang et al. | Enhanced photocatalytic performance for phenol degradation using ZnO modified with nano-biochar derived from cellulose nanocrystals | |
| Song et al. | Preparation of visible-light photocatalysts of Bi2O3/Bi embedded in porous carbon from Bi-based metal organic frameworks for highly efficient Rhodamine B removal from water | |
| CN1884188A (en) | Carbon nanotube/nano clay nano composite materials and method for preparing same | |
| CN109876841A (en) | A kind of method of 2- amino terephthalic acid (TPA) and amine compounds combined polymerization preparation graphite phase carbon nitride visible light catalyst | |
| CN110586183A (en) | Method for preparing TiO by using supercritical carbon dioxide2Method for preparing/COF catalytic material | |
| US7410629B2 (en) | Method of preparation for carbon nanotube material | |
| CN115057429A (en) | Method for co-production of nitrogen-doped lignin-based carbon nanotube and biochar | |
| Yu et al. | Facile synthesis of a BCN nanofiber and its ultrafast adsorption performance | |
| CN1182026C (en) | Process for preparing Fe-series catalyst used to synthesize nano carbon tubes | |
| CN113694914A (en) | Preparation method of MOF/graphene quantum dot nano composite photocatalyst | |
| CN1899956A (en) | Method for synthesizing single shape boron nitride nano tube | |
| CN1636868A (en) | Polyolefin burning process of synthesizing carbon nanotube | |
| CN1261222C (en) | Process for preparing Al2O3 aerogel carried catalyst and its application in preparing nano carbon tubes by catalytic cracking of methane | |
| CN1193931C (en) | Synthesis of double walled carbon nano-tubes | |
| CN1208385C (en) | Montmorillonite-TiCl4 catalyst and process for preparing polyolefin/montmorillonite composition | |
| CN1850583A (en) | Method for preparing hydrogen utilizing waste plastics | |
| CN1699154A (en) | Method for synthesizing carbon nanotube and its compounds by polyolefin combustion with nickel oxide as catalyst | |
| CN1872908A (en) | Method for preparing catalyst of montmorillonite-titanium tetrachloride, and composite material of polyethylene/montmorillonite | |
| CN1775671A (en) | Method for preparing carbon nano tube and its composite by nickel compound catalytic combustion of polyolefin | |
| CN1283358C (en) | Catalyst in use for preparing carbon fiber, preparation method and usage | |
| CN116081602B (en) | Method for preparing spiral carbon nano tube by using waste polyolefin | |
| CN111333906A (en) | Preparation method of solid acid catalyst and carbon nanofiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20131009 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20131009 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061206 Termination date: 20201026 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |