CN1775671A - Method for preparing carbon nano tube and its composite by nickel compound catalytic combustion of polyolefin - Google Patents
Method for preparing carbon nano tube and its composite by nickel compound catalytic combustion of polyolefin Download PDFInfo
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- CN1775671A CN1775671A CN 200510119084 CN200510119084A CN1775671A CN 1775671 A CN1775671 A CN 1775671A CN 200510119084 CN200510119084 CN 200510119084 CN 200510119084 A CN200510119084 A CN 200510119084A CN 1775671 A CN1775671 A CN 1775671A
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Abstract
The invention belongs to the technical field of synthetic carbon nano tube material and its complex. The invention provides a method for preparing carbon nano tube and the carbon nano tube-montmorillonite complex by nickel compound catalyzing polyolefin burning, characterized in that the catalyst comprises nickel hydroxide, basic nickel carbonate, nickel carbonate, nickel oxalate and nickel formate and need not be high temperature resolved into nickel oxides, even reduced into monomeric substances and can be directly used; the polyolefins are polypropylene, polyethylene, copolymer of ethylene and propylene (EPM), terpolymer of ethylene, propylene and di- or polyene (EPDM) and polystyrene, or their mixture in arbitrary ratio and their recovered materials. The invention largely simplifies the preparing process; and the cost of catalyst can be reduced by about 50%.
Description
Technical field
The invention belongs to the technical field of a kind of synthesize nano carbon tube material and mixture thereof, be specifically related to the method that the nickel compound catalytic combustion of polyolefin prepares carbon nanotube and mixture thereof.
Background technology
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.Meanwhile, the mixture of carbon nanotube/polynite also causes people's attention gradually, and this class material has a potential application prospect in catalysis, separation and with polymkeric substance is compound.
On the 2641-2646 page or leaf of rolling up in 2002 the 40th of " carbon " (" Carbon ") magazine, reported the method for montmorillonite load iron catalyst catalyzing acetylene synthesizing carbon nanotubes/montmorillonite composite.In this method catalyzed reaction time longer, with respect to catalyst content, the carbon productive rate is lower.Having reported a kind of in the Chinese patent application 200510016849.97 is carbon source material with the polyolefine, in the presence of organic modification montmonrillonite, nickel oxide catalyzer, prepares the method for carbon nano-tube material by combustion method.Nickel oxide is wherein mainly obtained by the oxyhydroxide or the nickel salt pyrolytic decomposition of nickel.So far, Shang Weijian directly adopt the oxyhydroxide of nickel and nickel salt catalytic combustion of polyolefin obtain carbon nanotube and with the report of montmorillonite composite.
Summary of the invention
In order to overcome catalyst preparation process complexity in the above-mentioned prior art, the shortcoming that cost is high, the present invention discloses and a kind ofly utilizes cheap nickel compound as catalyzer, catalytic combustion of polyolefin prepare carbon nanotube and with the method for modified montmorillonoid mixture.
The purpose of this invention is to provide class nickel compound catalyst burning polyolefin prepared carbon nanotube and with the method for modified montmorillonoid mixture
The step of method of the present invention and condition are:
A) preparation of polyolefine-modified montmorillonoid-nickel compound catalyst mixture
Ratio of components adds melting mixing in the Banbury mixer with 50-95% polyolefine, 4.5-40% modified montmorillonoid and 0.5-45% nickel compound by weight, makes polyolefine-modified montmorillonoid-nickel compound catalyst mixture; Perhaps press said ratio with polyolefine and modified montmorillonoid pre-mixing at room temperature, from main charging opening melting mixing this mixture adding forcing machine is prepared masterbatch, from the 2nd charging opening nickel compound is added then, proceed melting mixing and get polyolefine-modified montmorillonoid-nickel compound catalyst mixture.
Used polyolefine can be polypropylene, polyethylene, binary second third glue, ethylene-propylene diene copolymer, polystyrene, or the mixture of its any ratio and their reclaimed materials; Used modified montmorillonoid is the organic ammonium modified montmorillonoid; Used nickel compound is nickel hydroxide, basic nickel carbonate, nickelous carbonate, nickelous oxalate, nickel formate, or it is arbitrarily than mixture.
B) preparation of carbon nanotube/montmorillonite composite
Polyolefine-modified montmorillonoid-nickel compound catalyst mixture with the step a) preparation, place and be heated to 600-950 ℃ ceramic crucible and add a cover, continue to be heated to the no flame in container top and produce, be cooled to room temperature, obtain the black composite of carbon nanotube/polynite.
C) preparation of carbon nanotube and purification
With mass concentration is that the hydrofluoric acid of 10-30% joins in carbon nanotube/polynite black composite that step b) makes, and places 25-30 hour, separates obtaining black carbon powder; Adding volume ratio is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxed 2-4 hour, after the separation, with washed with de-ionized water to pH=7, the carbon nanotube that obtains purifying.
Advantage of the present invention: the nickel compound source is very wide among the present invention, and the oxyhydroxide of nickel and the cost that the nickel salt pyrolytic decomposition obtains the oxide compound of nickel have been saved, price advantage is obvious, for example replaces nickel protoxide with basic nickel carbonate, and the cost of catalyzer can lower about 50%.
Embodiment
Embodiment 1
Melting mixing obtains polypropylene miser in the Banbury mixer by weight 50% polypropylene, 40% modified montmorillonoid, 10% nickel hydroxide are added simultaneously.
Get said mixture 1 gram and be put in 15 milliliters of crucibles of 600 ℃ that heat with combustion gas lamp flame envelope, and cover crucible, continue to be heated to the no flame in container top and produce, take off crucible, be put in shady and cool place and be cooled to room temperature.Obtain carbon nanotube/montmorillonite composite 0.69 gram this moment.
With mass concentration is that 10% hydrofluoric acid joins in the above-mentioned black composite, places 30 hours.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, cleaning.Obtain carbon nanotube 0.27 gram of purifying this moment.
Embodiment 2
By weight 35% recovery polypropylene, 60% ethylene-propylene diene copolymer, 4.5% modified montmorillonoid, 0.5% basic nickel carbonate are added in the Banbury mixer simultaneously, melting mixing obtains polyolefin blend.
Get said mixture 4 grams and be put in 30 milliliters of crucibles of 950 ℃ that heat with combustion gas lamp flame envelope, and cover crucible, continue to be heated to the no flame in container top and produce, take off crucible, be put in shady and cool place and be cooled to room temperature.Obtain carbon nanotube/montmorillonite composite 1.4 grams this moment.
With mass concentration is that 30% hydrofluoric acid joins in the above-mentioned black composite, places 25 hours.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 2 hours, takes out and carries out centrifugation, cleaning.Obtain carbon nanotube 1.2 grams of purifying this moment.
Embodiment 3
By weight with 55% polyethylene, 20% binary second, third glue, the pre-mixing at room temperature of 15% modified montmorillonoid, from main charging opening melting mixing this mixture adding forcing machine is prepared masterbatch, from the 2nd charging opening 5% nickelous carbonate, 5% nickelous oxalate are added then, proceed melting mixing and get polyolefin blend.
Get said mixture 3 grams and be put in 30 milliliters of crucibles of 850 ℃ that heat with combustion gas lamp flame envelope, and cover crucible, continue to be heated to the no flame in container top and produce, take off crucible, be put in shady and cool place and be cooled to room temperature.Obtain carbon nanotube/montmorillonite composite 1.3 grams this moment.
With mass concentration is that 25% hydrofluoric acid joins in the above-mentioned black composite, places 27 hours.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 3 hours, takes out and carries out centrifugation, cleaning.Obtain carbon nanotube 1.1 grams of purifying this moment.
Embodiment 4
By weight 45% polystyrene, 10% modified montmorillonoid, 45% nickel formate are added in the Banbury mixer simultaneously, melting mixing obtains polystyrene blends.
Get said mixture 3 grams and be put in 30 milliliters of crucibles of 750 ℃ that heat with combustion gas lamp flame envelope, and cover crucible, continue to be heated to the no flame in container top and produce, take off crucible, be put in shady and cool place and be cooled to room temperature.Obtain carbon nanotube/montmorillonite composite 0.8 gram this moment.
With mass concentration is that 15% hydrofluoric acid joins in the above-mentioned black composite, places 28 hours.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 3 hours, takes out and carries out centrifugation, cleaning.Obtain carbon nanotube 0.2 gram of purifying this moment.
Claims (4)
1. the nickel compound catalytic combustion of polyolefin prepares the method for carbon nanotube and mixture thereof, it is characterized in that its step and condition are:
A) preparation of polyolefine-modified montmorillonoid-nickel compound catalyst mixture
Ratio of components by weight, with 50-95% polyolefine, 4.5-40% modified montmorillonoid and 0.5-45% nickel compound catalyzer, melting mixing makes polyolefine-modified montmorillonoid-nickel compound catalyst mixture;
B) preparation of carbon nanotube/montmorillonite composite
Polyolefine-modified montmorillonoid-nickel catalyzator the mixture of step a) preparation placed be heated to 600-950 ℃ ceramic crucible and add a cover, continue to be heated to the no flame generation in container top, be cooled to room temperature, obtain the black composite of carbon nanotube/polynite;
C) preparation of carbon nanotube
With mass concentration is that the hydrofluoric acid of 10-30% joins in the black composite of carbon nanotube/polynite that step b) makes, and places 25-30 hour, separates obtaining black carbon powder; Adding volume ratio is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxed 2-4 hour, after the separation, with washed with de-ionized water to pH=7, the carbon nanotube that obtains purifying.
2. nickel compound catalytic combustion of polyolefin as claimed in claim 1 prepares the method for carbon nanotube and mixture thereof, it is characterized in that used modified montmorillonoid is the organic ammonium modified montmorillonoid.
3. nickel compound catalytic combustion of polyolefin as claimed in claim 1 prepares the method for carbon nanotube and mixture thereof, it is characterized in that used nickel catalyzator is nickel hydroxide, basic nickel carbonate, nickelous carbonate, nickelous oxalate, nickel formate, or the mixture of its any ratio.
4. nickel compound catalytic combustion of polyolefin as claimed in claim 1 prepares the method for carbon nanotube and mixture thereof, it is characterized in that used polyolefine is polypropylene, polyethylene, binary second third glue, ethylene-propylene diene copolymer, polystyrene, or the mixture of its any ratio and their reclaimed materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200510119084 CN1775671B (en) | 2005-12-16 | 2005-12-16 | Method for preparing carbon nano tube by nickel compound catalytic combustion of polyolefin |
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| CN 200510119084 CN1775671B (en) | 2005-12-16 | 2005-12-16 | Method for preparing carbon nano tube by nickel compound catalytic combustion of polyolefin |
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| CN1775671A true CN1775671A (en) | 2006-05-24 |
| CN1775671B CN1775671B (en) | 2010-05-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556537C (en) * | 2008-01-03 | 2009-11-04 | 厦门大学 | The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation |
| CN101898760A (en) * | 2010-07-23 | 2010-12-01 | 东北林业大学 | Method for catalyzing polymer with multi-metallic catalyst to compound carbon nano-tube in situ |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140448C (en) * | 2000-03-07 | 2004-03-03 | 天津大学 | Process of nickel catalytic cracking methane preparing carbon nanometer tube |
| CN1288076C (en) * | 2004-10-26 | 2006-12-06 | 中国科学院长春应用化学研究所 | Method for preparing material of nano carbon tube |
| CN1323029C (en) * | 2004-12-10 | 2007-06-27 | 中国科学院长春应用化学研究所 | Polyolefin burning process of synthesizing carbon nanotube |
| 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 |
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2005
- 2005-12-16 CN CN 200510119084 patent/CN1775671B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556537C (en) * | 2008-01-03 | 2009-11-04 | 厦门大学 | The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation |
| CN101898760A (en) * | 2010-07-23 | 2010-12-01 | 东北林业大学 | Method for catalyzing polymer with multi-metallic catalyst to compound carbon nano-tube in situ |
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| CN1775671B (en) | 2010-05-05 |
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Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20131008 |
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