CN109694053A - A kind of low cost nano carbon material preparation method for material - Google Patents
A kind of low cost nano carbon material preparation method for material Download PDFInfo
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- CN109694053A CN109694053A CN201711003567.4A CN201711003567A CN109694053A CN 109694053 A CN109694053 A CN 109694053A CN 201711003567 A CN201711003567 A CN 201711003567A CN 109694053 A CN109694053 A CN 109694053A
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- carbon
- catalyst
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- carbon material
- gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention discloses a kind of inexpensive nano carbon material preparation method for material, using paraffin gas as unstripped gas, different catalyst is added at 600~800 DEG C of temperature and the pressure of 1~8bar, the unstrpped gas for having aromatic hydrocarbon will be closed and be passed through catalytic cracking reaction device progress catalytic cracking reaction, the nano-carbon material of different-shape is prepared, the present invention utilizes methane splitting mechanism on a catalyst are as follows: CH4Following cracking reaction: CH can occur under certain condition4→C+2H2Methane catalytic decomposition, low energy consumption, by changing reaction condition, the especially structure and type of catalyst, this reaction can produce nano-carbon material, such as the carbon nanotube of superior structural, carbon nano-fiber and carbon nano-particle, catalyst carrier, hydrogen storage material and reinforcing material can be widely applied to, while can be with zero-emission hydrogen.
Description
Technical field
The present invention relates to a kind of preparation methods of high graphitization carbon material, in particular, provide a kind of inexpensive, mass
Gas-phase decomposition aromatic hydrocarbon produces a kind of high carbon nanotubes, nano carbon microsphere, the nano-onions carbon etc. of degree of graphitization of morphology controllable
The preparation method of nano-carbon material.
Background technique
High-graphitized carbon material, such as carbon ball, carbon nanotubes, carbon fiber, onion carbon, due to its good electronics,
Mechanical performance, chemical inertness, biocompatibility are being widely used in the fields such as engineering, electronics, chemical industry, biology.Its
In, graphited onion carbon, electrochemical capacitance, catalyst load, in terms of have broad application prospects.And carbon wraps up
Magnetic metal ion (catalyst) due to the excellent physicochemical properties of graphitization shell, protect wherein active magnetism gold
Belong to, is had important application in the fields such as electromagnetism, optical Quality Research and Magnetic resonance imaging, magnetic suspension sealing fluid.
So far, scientists explore a variety of methods for preparing graphitized carbon material, such as chemical vapor deposition
(CVD), the methods of arc discharge, laser evaporation, solvent pyrolysis.But most of method requires expensive special installation, with
And a large amount of energy input, and it is unfavorable for industrialized mass production.One-dimensional nanoreticular carbon materials are prepared using catalytic pyrolysis method, generally
Using fragrant appropriate hydrocarbon gas as carbon source, hydrogen, argon gas or nitrogen are as carrier gas and carrier gas.The effect master of carrier gas and carrier gas
If entrainment carbon source enters reaction, C/Hratio in reaction process is adjusted.It is one-dimensional in order to obtain better quality in actual application
Nano-carbon material, the key of process are high activity to be developed (methane has high conversion per pass), high stability and high selection
The catalyst of property.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides prepared by a kind of zero-emission, mass, degree of graphitization is high to be received
Rice carbon materials preparation method for material.
In order to achieve the above object, the manufacturing process that the invention patent uses are as follows:
Using paraffin gas as unstripped gas different catalyst is added 600 in a kind of low cost nano carbon material preparation method for material
At~800 DEG C of temperature and the pressure of 1~8bar, the unstrpped gas containing aromatic hydrocarbon is passed through catalytic cracking reaction device and is catalyzed
Cracking reaction prepares the nano-carbon material of different-shape.
The catalyst is the Mo of different Mo, Ni (Fe, Co) and Mg contentxThe catalysis of-Ni (Fe, Co) y-MgOz solid solution
Agent, the zeolite structured catalyst of Ni/Y- type, La2NiO4Catalyst, Ni/MCM-41 catalyst, Fe-Cr alloy catalyst and
LaNi0.9Co0.1O3Catalyst.
The catalyst is the Mo of different Mo, Ni (Fe, Co) and Mg contentx- Ni (Fe, Co)y-MgOzSolid solution is then urged
Obtained graphitized carbon material is single-walled carbon nanotube (SWCNT) after changing cracking.
The catalyst is La2NiO4, then obtained carbon material is multi-walled carbon nanotube (MWCNT) after catalytic pyrolysis,
Resultant multi-wall carbon nanotube internal diameter is 15nm or so, and parietal layer 40 once controlled.
It is passed through benzene (volume fraction 100ppm) simultaneously in the unstripped gas, catalyst Ni/MCM-41, catalytic pyrolysis
Obtained carbon material is micron order disk carbon (MCD) of the diameter in 500 rans afterwards.
The catalyst is Fe-Cr alloy catalyst, and obtained carbon material is nano-onions carbon after catalytic pyrolysis
(CNO), and the nano-onions carbon carbon-coating is at 50 layers or so, and diameter is in 100nm or so.
The catalyst is LaNi0.9Co0.1O3, obtained carbon material is micron grade carbon fiber after catalytic pyrolysis.
The present invention utilizes methane splitting mechanism on a catalyst are as follows: CH4It can occur to crack as follows under certain condition anti-
It answers: CH4→C+2H2Methane catalytic decomposition, low energy consumption, by changing the structure and type of reaction condition, especially catalyst, this
One reaction can produce nano-carbon material, such as the carbon nanotube of superior structural, carbon nano-fiber and carbon nano-particle, can answer extensively
For catalyst carrier, hydrogen storage material and reinforcing material, while can be with zero-emission hydrogen.
Specific embodiment
The present invention is using paraffin gas such as natural gas, coal bed gas, biogas as unstripped gas, in the presence of a catalyst, 600~
At 800 DEG C of temperature and the pressure of 1~8bar, unstrpped gas is passed through reactor progress catalytic cracking reaction and prepares nano carbon material
Material, when selected catalyst is respectively the Mo of different Mo, Ni (Fe, Co) and Mg contentx- Ni (Fe, Co)y-MgOzSolid solution catalysis
Agent, the zeolite structured catalyst of Ni/Y- type, La2NiO4Catalyst, Ni/MCM-41 catalyst, Fe-Cr alloy catalyst and
LaNi0.9Co0.1O3When catalyst, cracking stock gas preparation carbon material mutually should be the high single-wall carbon nanotubes of degree of graphitization,
Nano carbon microsphere, nano-onions carbon, micron carbon disk, micron carbon fiber etc..
Below with reference to implementation column, the invention will be further described, but not limited to this.
Embodiment 1:
With the Mo of different Mo, Ni (Fe, Co) and Mg contentx- Ni (Fe, Co)y-MgOzSolid solution is catalyst, cracking temperature
It is 800 DEG C, gained carbon material is single-walled carbon nanotube (SWCNT) after catalytic pyrolysis under normal pressure；With Mo0.1Fe0.05Mg0.85Ox、
Mo0.105Co0.045Mg0.85OxAnd Mo0.2Ni0.1Mg0.7OxSoild oxide is catalyst, then obtained carbon materials after catalytic pyrolysis
Material is thin wall carbon nano-tube (TWCNT), caliber sequence are as follows: TWCNTFe< TWCNTCo< TWCNTNi, and TWCNTFeAnd TWCNTCo
To be closed thin wall carbon nano-tube, TWCNTNiFor port open formula carbon nanotube；With La2NiO4For catalyst, institute after catalytic pyrolysis
Obtained carbon material is multi-walled carbon nanotube (MWCNT), and resultant multi-wall carbon nanotube internal diameter is 15nm or so, 40 Zeng Zuo of parietal layer
It is right.
Embodiment 2:
Benzene (volume fraction 100ppm) is passed through using Ni/MCM-41 as catalyst simultaneously in unstripped gas, institute after catalytic pyrolysis
Obtained carbon material is micron order disk carbon (MCD) of the diameter in 500 rans；Using Fe-Cr alloy as catalyst, catalysis is split
Obtained carbon material is nano-onions carbon (CNO) after solution, and at 800 DEG C, which is 90% or so, is turned close to theoretical
Rate (92.9%), and produced nano-onions carbon, at 50 layers or so, diameter is in 100nm or so；With LaNi0.9Co0.1O3For catalysis
Agent, obtained carbon material is micron grade carbon fiber after catalytic pyrolysis.
Claims (1)
1. a kind of low cost nano carbon material preparation method for material, using paraffin gas as unstripped gas, be added different catalyst 600~
At 800 DEG C of temperature and the pressure of 1~8bar, the unstrpped gas containing aromatic hydrocarbon is passed through catalytic cracking reaction device and be catalyzed and is split
Solution reaction, prepares the nano-carbon material of different-shape；It is characterized by: benzene is passed through in the unstripped gas simultaneously, volume point
Counting is 100ppm, catalyst Ni/MCM-41, the micron order circle that obtained carbon material is 500 nanometers of diameter after catalytic pyrolysis
Disk carbon MCD.
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| CN201711003567.4A CN109694053A (en) | 2017-10-24 | 2017-10-24 | A kind of low cost nano carbon material preparation method for material |
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| CN201711003567.4A CN109694053A (en) | 2017-10-24 | 2017-10-24 | A kind of low cost nano carbon material preparation method for material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043376A (en) * | 2022-06-01 | 2022-09-13 | 苏州道顺电子有限公司 | Method for preparing hydrogen and byproduct carbon material by catalytic cracking of methane |
-
2017
- 2017-10-24 CN CN201711003567.4A patent/CN109694053A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043376A (en) * | 2022-06-01 | 2022-09-13 | 苏州道顺电子有限公司 | Method for preparing hydrogen and byproduct carbon material by catalytic cracking of methane |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190430 |
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| WD01 | Invention patent application deemed withdrawn after publication |