CN103058169A - Preparation method for carbon nanomaterials with high graphitization degree - Google Patents
Preparation method for carbon nanomaterials with high graphitization degree Download PDFInfo
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Abstract
The invention discloses a preparation method for carbon nanomaterials with high graphitization degree. The preparation method comprises the steps as follows: taking paraffin gases such as natural gas, coal bed gas, methane, acetylene and the like as raw material gases; adding different catalysts; and filling the raw material gases with hydrocarbon compounds into a catalytic cracking reactor for catalytic cracking reaction under the pressure of 1-8 bar at the temperature of 600-800 DEG C so as to prepare the carbon nanomaterials with different morphologies. The methane catalytic cracking mechanism is that CH4 can have the following cracking reaction under a certain condition: CH4->C+2H2; the energy consumption for the methane catalytic cracking reaction is low; the carbon nanomaterials such as carbon nanotubes, carbon nanofibers and carbon nanoparticles excellent in structure can be produced by changing the reaction conditions, especially the structures and the categories of the catalysts, and can be widely applied to catalyst carriers, hydrogen storage materials and enhanced materials; and meanwhile, hydrogen gas can be generated with zero discharge.
Description
The present invention is that the patent No. is: 201010250457.X, patent name is: the nano carbon material preparation method for material that a kind of degree of graphitization is high, the date of application is: 2010 08 month 02 day divides an application.
Technical field:
The present invention relates to a kind of highly-graphitized carbon material preparation method, the preparation method of the nano-carbon materials such as the high CNT (carbon nano-tube) of the controlled degree of graphitization of a kind of low cost, a kind of pattern of mass gas-phase decomposition production of hydrocarbons, nano carbon microsphere, nano-onions carbon particularly is provided.
Technical background:
High-graphitized carbon material, such as carbon ball, CNT (carbon nano-tube), carbon fiber, onion carbon etc., owing to its good electronics, mechanical property, unreactiveness, biocompatibility is being widely used in the fields such as engineering, electronics, chemical industry, biology.Wherein, graphited onion carbon has broad application prospects at aspects such as electrochemical capacitance, catalyst cupport, medicament slow releases.And the magnetic metal ion (catalyzer) of carbon parcel is because the physicochemical property of greying shell excellence; protected wherein active magneticmetal, in fields such as the research of electromagnetism, optical property and Magnetic resonance imaging, magnetic suspension sealing liquids important application has been arranged.
Up to now, scientists has been explored the multiple method for preparing graphitized carbon material, such as methods such as chemical vapour deposition (CVD), arc-over, laser evaporation, solvent pyrolysis.But most of method all needs expensive specific installation, and the input of a large amount of energy, and is unfavorable for industrialized mass production.Adopt catalytic pyrolysis method to prepare One-dimensional nanoreticular carbon materials, generally adopt hydrocarbon gas as carbon source, hydrogen, argon gas or nitrogen are as carrier gas and carrier gas.The effect of carrier gas and carrier gas mainly is to carry carbon source secretly to enter reaction ratio of carbon-hydrogen in the conditioned reaction process.In the application of reality, in order to obtain the better quality One-dimensional nanoreticular carbon materials, the key of process is to develop the catalyzer of high reactivity (methane has high per pass conversion), high stability and highly selective.
Summary of the invention:
The present invention is directed to the deficiencies in the prior art, provide a kind of zero release, mass to prepare the high nano carbon material preparation method for material of degree of graphitization.
For realizing above purpose, the making processes that patent of the present invention adopts is:
The nano carbon material preparation method for material that a kind of degree of graphitization is high, take paraffin gass such as Sweet natural gas, coal-seam gas, biogas, acetylene as unstripped gas, add different catalyzer under the pressure of 600~800 ℃ of temperature and 1~8bar, the unstripped gas that will contain hydrocarbon polymer passes into the catalytic cracking reaction device and carries out catalytic cracking reaction, prepares the nano-carbon material of different-shape.
Described catalyzer is the Mo of different Mo, Ni (Fe, Co) and Mg content
x-Ni (Fe, Co) y-MgOz solid solution catalyst, the zeolite structured catalyzer of Ni/Y-type, La
2NiO
4Catalyzer, Ni/MCM-41 catalyzer, Fe-Cr alloy catalyst and LaNi
0.9Co
0.1O
3Catalyzer.
Described catalyzer is the Mo of different Mo, Ni (Fe, Co) and Mg content
x-Ni (Fe, Co)
y-MgO
zSosoloid, then resulting graphitized carbon material is Single Walled Carbon Nanotube (SWCNT) behind the catalytic pyrolysis.
Described catalyzer is La
2NiO
4, then resulting carbon material is multi-walled carbon nano-tubes (MWCNT) behind the catalytic pyrolysis, gained multi-wall carbon nano-tube bore is about 15nm, parietal layer 40 once about.
Pass into simultaneously benzene (volume fraction is 100ppm) in the described unstripped gas, catalyzer is Ni/MCM-41, and resulting carbon material is the micron order disk carbon (MCD) of diameter about 500 nanometers behind the catalytic pyrolysis.
Described catalyzer is the Fe-Cr alloy catalyst, and resulting carbon material is nano-onions carbon (CNO) behind the catalytic pyrolysis, and this nano-onions carbon carbon-coating is about 50 layers, and diameter is about 100nm.
Described catalyzer is LaNi
0.9Co
0.1O
3, resulting carbon material is the micron order carbon fiber behind the catalytic pyrolysis.
The present invention utilizes methane splitting mechanism on catalyzer to be: CH
4Following scission reaction: CH can occur under certain condition
4→ C+2H
2Methane catalytic decomposition, energy consumption is low, by changing reaction conditions, especially the structure of catalyzer and kind, this reaction can be produced nano-carbon material, carbon nanotube, carbon nanofiber and carbon nano-particle such as superior structural can be widely used in support of the catalyst, hydrogen storage material and strongthener, simultaneously can the zero release hydrogen.
Embodiment:
The present invention is take paraffin gass such as Sweet natural gas, coal-seam gas, biogas as unstripped gas, in the presence of catalyzer, under the pressure of 600~800 ℃ of temperature and 1~8bar, unstripped gas is passed into reactor carries out catalytic cracking reaction and prepares nano-carbon material, be respectively the Mo of different Mo, Ni (Fe, Co) and Mg content when selected catalyzer
x-Ni (Fe, Co)
y-MgO
zSolid solution catalyst, the zeolite structured catalyzer of Ni/Y-type, La
2NiO
4Catalyzer, Ni/MCM-41 catalyzer, Fe-Cr alloy catalyst and LaNi
0.9Co
0.1O
3During catalyzer, the carbon material of cracking stock gas preparation should be the high Single Walled Carbon Nanotube of degree of graphitization, nano carbon microsphere, nano-onions carbon, micron carbon dish, micron carbon fiber etc. mutually.
The invention will be further described below in conjunction with implementation column, but be not limited to this.
Embodiment 1:
Mo with different Mo, Ni (Fe, Co) and Mg content
x-Ni (Fe, Co)
y-MgO
zSosoloid is catalyzer, and cracking temperature is 800 ℃, under the normal pressure behind the catalytic pyrolysis gained carbon material be Single Walled Carbon Nanotube (SWCNT); With Mo
0.1Fe
0.05Mg
0.85O
x, Mo
0.105Co
0.045Mg
0.85O
xAnd Mo
0.2Ni
0.1Mg
0.7O
xSoild oxide is catalyzer, and then resulting carbon material is thin wall carbon nano-tube (TWCNT) behind the catalytic pyrolysis, and caliber sequentially is: TWCNT
Fe<TWCNT
Co<TWCNT
Ni, and TWCNT
FeAnd TWCNT
CoBe closed thin wall carbon nano-tube, TWCNT
NiBe port open formula carbon nanotube; With La
2NiO
4Be catalyzer, resulting carbon material is multi-walled carbon nano-tubes (MWCNT) behind the catalytic pyrolysis, and gained multi-wall carbon nano-tube bore is about 15nm, parietal layer 40 once about.
Embodiment 2:
Pass into simultaneously benzene (volume fraction is 100ppm) in the unstripped gas take Ni/MCM-41 as catalyzer, resulting carbon material is the micron order disk carbon (MCD) of diameter about 500 nanometers behind the catalytic pyrolysis; Take the Fe-Cr alloy as catalyzer, resulting carbon material is nano-onions carbon (CNO) behind the catalytic pyrolysis, under 800 ℃, this reaction conversion ratio is about 90%, near theoretical yield (92.9%), and the nano-onions carbon that produces about 50 layers, diameter is about 100nm; With LaNi
0.9Co
0.1O
3Be catalyzer, resulting carbon material is the micron order carbon fiber behind the catalytic pyrolysis.
Claims (1)
1. nano carbon material preparation method for material that degree of graphitization is high, with Sweet natural gas, coal-seam gas, biogas, acetylene, paraffin gas is unstripped gas, add different catalyzer under the pressure of 600~800 ℃ of temperature and 1~8bar, the unstripped gas that will contain hydrocarbon polymer passes into the catalytic cracking reaction device and carries out catalytic cracking reaction, prepare the nano-carbon material of different-shape, it is characterized in that: described catalyzer is LaNi
0.9Co
0.1O
3, resulting carbon material is the micron order carbon fiber behind the catalytic pyrolysis.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103449402A (en) * | 2013-08-23 | 2013-12-18 | 吉林大学 | Hydrogenated carbon nanosphere as well as preparation method and application thereof |
CN106058218A (en) * | 2016-08-12 | 2016-10-26 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube composite nickel-cobalt-magnesium-titanium quaternary positive electrode material |
WO2017031529A1 (en) * | 2015-08-26 | 2017-03-02 | Hazer Group Ltd | A process of controlling the morphology of graphite |
CN107857247A (en) * | 2017-11-29 | 2018-03-30 | 山西中兴环能科技股份有限公司 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
Citations (1)
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CN1495127A (en) * | 1999-06-02 | 2004-05-12 | ����˹���ѧ���»� | Method and catalyst for producing carbon nano tube |
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2010
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Patent Citations (1)
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CN1495127A (en) * | 1999-06-02 | 2004-05-12 | ����˹���ѧ���»� | Method and catalyst for producing carbon nano tube |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103449402A (en) * | 2013-08-23 | 2013-12-18 | 吉林大学 | Hydrogenated carbon nanosphere as well as preparation method and application thereof |
CN103449402B (en) * | 2013-08-23 | 2015-10-14 | 吉林大学 | A kind of hydrogenated carbon nanometer ball and its production and use |
WO2017031529A1 (en) * | 2015-08-26 | 2017-03-02 | Hazer Group Ltd | A process of controlling the morphology of graphite |
CN108348901A (en) * | 2015-08-26 | 2018-07-31 | 哈泽尔集团公司 | A method of control graphite form |
JP2018528921A (en) * | 2015-08-26 | 2018-10-04 | ヘイザー グループ リミテッド | Process for controlling the morphology of graphite |
AU2016312962B2 (en) * | 2015-08-26 | 2019-03-07 | Hazer Group Ltd | A process of controlling the morphology of graphite |
AU2016312962B9 (en) * | 2015-08-26 | 2019-04-04 | Hazer Group Ltd | A process of controlling the morphology of graphite |
US11691126B2 (en) | 2015-08-26 | 2023-07-04 | Hazer Group Ltd. | Process of controlling the morphology of graphite |
CN106058218A (en) * | 2016-08-12 | 2016-10-26 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube composite nickel-cobalt-magnesium-titanium quaternary positive electrode material |
CN106058218B (en) * | 2016-08-12 | 2019-04-19 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube composite nickel-cobalt-magnesium-titanium quaternary positive electrode material |
CN107857247A (en) * | 2017-11-29 | 2018-03-30 | 山西中兴环能科技股份有限公司 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
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