CN107857247A - A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion - Google Patents
A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion Download PDFInfo
- Publication number
- CN107857247A CN107857247A CN201711222949.6A CN201711222949A CN107857247A CN 107857247 A CN107857247 A CN 107857247A CN 201711222949 A CN201711222949 A CN 201711222949A CN 107857247 A CN107857247 A CN 107857247A
- Authority
- CN
- China
- Prior art keywords
- magnetic metal
- carbon onion
- metal carbon
- embedded
- prepares
- 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.)
- Pending
Links
Abstract
The method that a kind of catalystic pyrolysis of the present invention prepares embedded magnetic metal carbon onion, belongs to technical field of nano-composite material preparation technology.Using magnetic metal or metal-oxide powder as catalyst, the paraffin gas such as natural gas, coal bed gas, biogas are unstripped gas, catalytic cracking reaction device is passed through under 600 ~ 1000 DEG C and 1 ~ 8bar of pressure and carries out catalytic cracking reaction, the embedded magnetic metal carbon onion prepared is with remaining catalyst after weak acid scrubbing, it is placed in again in nitration mixture and stirs 24h, high-graphitized embedded magnetic metal carbon onion is made.Shell carbon-coating can protect core inner magnetic metal not to be corroded, and can be widely used for the fields such as electro-catalysis, electrochemistry, wave-absorbing and camouflage.The embedded magnetic metal carbon onion cost of the inventive method preparation is low, energy consumption is low, yield is high, high income, and reaction condition is gentle, it is small that environment and synthesis personnel are endangered, can mass production.The present invention is used for the preparation for embedding magnetic metal carbon onion.
Description
Technical field
The present invention relates to a kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion, one kind is in particular, provided
Low cost, batch grow the preparation method of the regulatable embedded magnetic metal carbon onion of core metal, belong to carbon onion technology neck
Domain.
Background technology
Emerging member of the carbon onion as fullerene family, be a kind of zero dimension carbon nanomaterial, due to its good electronics,
Mechanical performance, chemical stability, heat endurance, biocompatibility, it is being widely used in electronics, chemical industry, is inhaling ripple, biology
Deng field.Wherein, solid or hollow carbon onion has wide answer in ultracapacitor, catalyst load, medicament slow release etc.
Use prospect.And embedded magnetic metal carbon onion is protected wherein active due to the excellent physicochemical properties of graphitization shell
Magnetic metal, in electromagnetism, optical Quality Research and Magnetic resonance imaging, electro-catalysis, magnetic suspension sealing fluid, wave-absorbing and camouflage
There is important application Deng field.
By the development of 25 years, scientific research personnel devised a variety of method synthesis carbon onions, as chemical vapor deposition, electric arc are put
The methods of electricity, laser evaporation, carbonium ion injection, pyrolysis.But most of synthetic method is required for the special installation of costliness, with
And very high energy consumption, and it is unfavorable for industrialized mass production." prepared by chemical gas-phase method for first technology CN1598046A one kind
Onion-like fullerene " method and CN1931717A one kind " preparation side of the onion like fulvene compounding material of uniform particle sizes
The technique that CVD prepares carbon onion is provided in method ", but by CVD temperature limiting, reacts the low-activation energy of offer so that being closed
Carbon-coating degree of graphitization into carbon onion is low, and above two method does not provide and can be used for mass production carbon onion
Technological parameter.
To sum up, magnetic metal carbon onion cost height, high energy consumption embedded in the presence of preparation in the prior art, yield poorly, can not criticize
Quantify many engineering problems such as production, the low, severe reaction conditions of degree of graphitization, therefore, it is necessary to make improvements.
The content of the invention
In the presence of overcoming the shortcomings of prior art, the present invention provides a kind of zero-emission, mass prepares graphitization
On the one hand carbon onion crude product obtained by CVD is further placed in by the method for the high embedded magnetic metal carbon onion of degree, this method
Stirred in concentrated acid so that the degree of graphitization of carbon onion carbon-coating is significantly increased, and on the other hand realizes carbon onion by adjusting parameter
Mass production, and methane gas used can be again introduced into cracking reactor by EGR so that whole reaction is except production
Without other greenhouses and pernicious gas outside raw hydrogen.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion, is carried out in the steps below：
S1：Catalyst is placed in catalytic cracking reaction device, and is passed through air in nitrogen discharge catalytic cracking reaction device；It is described to urge
Agent is magnetic metal or magnetic metal oxide；
S2：Using paraffin gas as unstripped gas, it is passed through catalytic cracking reaction device and carries out catalytic cracking reaction；
S3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature under nitrogen protection, collects product and remaining catalysis
Agent, it is placed in diluted acid and stirs, obtains embedded metal carbon onion crude product；
S4：Embedded metal carbon onion crude product is placed in nitration mixture and stirred, it is clear to stand, then clear again with distilled water diluting, standing
It is clear, vacuum filtration, obtain embedded magnetic metal carbon onion.
In S1, the magnetic metal is iron, nickel or the two mixture.
Further, the magnetic metal is carried on stainless steel, and the magnetic metal particle loaded is 10-100
nm。
In S1, the magnetic metal oxide is iron oxide, nickel oxide or the two mixture.
Further, the magnetic metal oxide is placed in magnetic boat, and the magnetic metal oxide particle loaded is
10-100 nm。
In S2, paraffin gas is passed through under 600 ~ 1000 DEG C and 1 ~ 8 bar of pressure with 200-500 sccm flow velocity
Catalytic cracking reaction device, reaction time 2-8h.
Further, the paraffin gas is at least one of natural gas, coal bed gas, biogas and methane.
In S3, the diluted acid is 1 mol/L HCl, HNO3Or H2SO4, stirring at normal temperature 10h.
In S4, the nitration mixture is the mixture of the concentrated sulfuric acid and concentrated nitric acid, volume ratio 1:3.
Further, the embedded metal carbon onion crude product is placed in nitration mixture and stood after stirring 24h.
Compared with prior art, the advantageous effect of present invention is that：
1）Reaction raw materials of the present invention are paraffin gas and magnetic metal or magnetic metal oxide, thus raw material into
This is cheap, and reaction principle is simple and easy, very low to equipment requirement；
2）Implementation steps of the present invention are simply controllable, and reaction condition is relatively mild, and raw material availability is high, and product quality is stable, particle diameter
Uniformly, product prepares yield and is up to 90.2%；
3）The present invention greatly improved the utilization rate of natural gas, coal bed gas or biogas and effectively control greenhouse gases CO2's
Discharge, compared to these gases direct burning utilize, the present invention except can produce high added value carbon onion nano material and
Hydrogen, while zero-discharge technology is also achieved, it is very friendly to environment；
4）The present invention originates in the progress volume production experiment of thing filling mixture ratio by adjusting, and revises experiment parameter, realizes embedded magnetic gold
Prepared by the mass for belonging to carbon onion, each independent experiment synthesis quality of mass production experiment can reach three hectograms
Rank, semi-industrial volume production being realized, application demand of the prepared product in fields such as electrode material, wave-absorbing and camouflage materials is high,
Prospect is considerable.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any reasonable combination.
Embodiment 1：
Step 1：Catalyst is placed in catalytic cracking reaction device, catalyst is magnetic metal or magnetic metal oxide, is passed through
Air in nitrogen discharge catalytic cracking reaction device；
Step 2：Using paraffin gas as unstripped gas, under 600 ~ 1000 DEG C and 1 ~ 8 bar of pressure, with 200-500 sccm
Flow velocity be passed through catalytic cracking reaction device carry out catalytic cracking reaction, reaction time 2-8h；
Step 3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature and collects product and remaining under nitrogen protection
Catalyst；Stirring at normal temperature 10h in diluted acid is subsequently placed in, obtains embedded metal carbon onion crude product；
Step 4：Embedded metal carbon onion crude product is placed in nitration mixture after stirring 24h and stood clearly, it is then dilute with a large amount of distilled water
Release, stand clear rear vacuum filtration again, obtain embedded magnetic metal carbon onion.
Embodiment 2：The present embodiment is as different from Example 1：The catalyst is nano-nickel powder.Other parameters are with implementing
Example 1 is identical.
Embodiment 3：The present embodiment is as different from Example 1：The catalyst is nano nickel iron mixture.Other parameters
It is same as Example 1.
Embodiment 4：The present embodiment is as different from Example 1：The catalyst is alpha-iron oxide nano-powder, cracking temperature
For 800 ~ 1000 DEG C.Other parameters are same as Example 1.
Embodiment 5：The present embodiment is as different from Example 1：The catalyst is nano-nickel oxide powder, cracking temperature
For 800 ~ 1000 DEG C.Other parameters are same as Example 1.
Embodiment 6：The present embodiment is as different from Example 1：The catalyst is that nano-sized iron oxide and nickel oxide mix
Powder, cracking temperature are 800 ~ 1000 DEG C.Other parameters are same as Example 1.
With following verification experimental verification beneficial effects of the present invention：
Experiment 1：
The method that this experiment catalystic pyrolysis prepares embedded ferrous metal carbon onion is carried out according to the following steps：
Step 1：The stainless (steel) wire of 0.5g load Nanoscale Irons is placed in catalytic cracking reaction device, is passed through nitrogen discharge catalytic pyrolysis
Air in reactor；
Step 2：Using paraffin gas as unstripped gas, under 600 DEG C and 1 bar of pressure, it is passed through with 200 sccm flow velocity
Catalytic cracking reaction device carries out catalytic cracking reaction, reaction time 4h；
Step 3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature and collects product and remaining under nitrogen protection
Catalyst；Stirring at normal temperature 10h in diluted acid is subsequently placed in, obtains embedded iron carbon onion crude product；
Step 4：Embedded iron carbon onion crude product is placed in nitration mixture after stirring 24h and stood clearly, it is then dilute with a large amount of distilled water
Release, stand clear rear vacuum filtration again, obtain 30-100 nm embedded iron carbon onion, conversion ratio 87.4%.
Experiment 2：
The method that this experiment catalystic pyrolysis prepares embedded nickel metal carbon onion is carried out according to the following steps：
Step 1：The stainless (steel) wire of 0.5g load nano nickels is placed in catalytic cracking reaction device, is passed through nitrogen discharge catalytic pyrolysis
Air in reactor；
Step 2：Using paraffin gas as unstripped gas, under 800 DEG C and 2 bar of pressure, it is passed through with 300 sccm flow velocity
Catalytic cracking reaction device carries out catalytic cracking reaction, reaction time 4h；
Step 3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature and collects product and remaining under nitrogen protection
Catalyst；Stirring at normal temperature 10h in diluted acid is subsequently placed in, obtains embedded nickel carbon onion crude product；
Step 4：Embedded nickel carbon onion crude product is placed in nitration mixture after stirring 24h and stood clearly, it is then dilute with a large amount of distilled water
Release, stand clear rear vacuum filtration again, obtain 20-80 nm embedded nickel carbon onion, conversion ratio 85.7%.
Experiment 3：
The method that this experiment catalystic pyrolysis prepares embedded iron nickel metal carbon onion is carried out according to the following steps：
Step 1：The stainless (steel) wire of 0.5g load Nanoscale Iron nickel is placed in catalytic cracking reaction device, nitrogen discharge catalysis is passed through and splits
Solve air in reactor；
Step 2：Using paraffin gas as unstripped gas, under 700 DEG C and 4 bar of pressure, it is passed through with 400 sccm flow velocity
Catalytic cracking reaction device carries out catalytic cracking reaction, reaction time 8h；
Step 3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature and collects product and remaining under nitrogen protection
Catalyst；Stirring at normal temperature 10h in diluted acid is subsequently placed in, obtains embedded iron nickel carbon onion crude product；
Step 4：Embedded iron nickel carbon onion crude product is placed in nitration mixture after stirring 24h and stood clearly, it is then dilute with a large amount of distilled water
Release, stand clear rear vacuum filtration again, obtain 30-100 nm embedded iron nickel carbon onion, conversion ratio 90.2%.
Experiment 4：
The method that this experiment catalystic pyrolysis mass prepares embedded iron nickel metal carbon onion is carried out according to the following steps：
Step 1：The stainless (steel) wire of 50g load Nanoscale Iron nickel is placed in catalytic cracking reaction device, is passed through nitrogen discharge catalytic pyrolysis
Air in reactor；
Step 2：Using paraffin gas as unstripped gas, under 830 DEG C and 8 bar of pressure, it is passed through with 500 sccm flow velocity
Catalytic cracking reaction device carries out catalytic cracking reaction, reaction time 8h；
Step 3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature and collects product and remaining under nitrogen protection
Catalyst；Stirring at normal temperature 10h in diluted acid is subsequently placed in, obtains embedded iron nickel carbon onion crude product；
Step 4：Embedded iron nickel carbon onion crude product is placed in nitration mixture after stirring 24h and stood clearly, it is then dilute with a large amount of distilled water
Release, stand clear rear vacuum filtration again, obtain 300g embedded iron nickel carbon onion, conversion ratio 89.4%.
Only presently preferred embodiments of the present invention is explained in detail above, but the present invention is not limited to above-described embodiment,
In those of ordinary skill in the art's possessed knowledge, it can also be made on the premise of present inventive concept is not departed from each
Kind change, various change should be included in the scope of the protection.
Claims (10)
1. a kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion, it is characterised in that：Carry out in the steps below：
S1：Catalyst is placed in catalytic cracking reaction device, and is passed through air in nitrogen discharge catalytic cracking reaction device；It is described to urge
Agent is magnetic metal or magnetic metal oxide；
S2：Using paraffin gas as unstripped gas, it is passed through catalytic cracking reaction device and carries out catalytic cracking reaction；
S3：After the completion of cracking reaction, catalytic cracking reaction device is cooled to room temperature under nitrogen protection, collects product and remaining catalysis
Agent, it is placed in diluted acid and stirs, obtains embedded metal carbon onion crude product；
S4：Embedded metal carbon onion crude product is placed in nitration mixture and stirred, it is clear to stand, then clear again with distilled water diluting, standing
It is clear, vacuum filtration, obtain embedded magnetic metal carbon onion.
2. the method that a kind of catalystic pyrolysis according to claim 1 prepares embedded magnetic metal carbon onion, its feature exist
In：In S1, the magnetic metal is iron, nickel or the two mixture.
3. a kind of catalystic pyrolysis according to claim 1 or 2 prepares the method for embedded magnetic metal carbon onion, its feature
It is：The magnetic metal is carried on stainless steel, and the magnetic metal particle loaded is 10-100 nm.
4. the method that a kind of catalystic pyrolysis according to claim 1 prepares embedded magnetic metal carbon onion, its feature exist
In：In S1, the magnetic metal oxide is iron oxide, nickel oxide or the two mixture.
5. a kind of catalystic pyrolysis according to claim 1 or 4 prepares the method for embedded magnetic metal carbon onion, its feature
It is：The magnetic metal oxide is placed in magnetic boat, and the magnetic metal oxide particle loaded is 10-100 nm.
6. the method that a kind of catalystic pyrolysis according to claim 1 prepares embedded magnetic metal carbon onion, its feature exist
In：In S2, paraffin gas is passed through catalysis under 600 ~ 1000 DEG C and 1 ~ 8 bar of pressure, with 200-500 sccm flow velocity and split
Solve reactor, reaction time 2-8h.
7. a kind of catalystic pyrolysis according to claim 1 or 6 prepares the method for embedded magnetic metal carbon onion, its feature
It is：The paraffin gas is at least one of natural gas, coal bed gas, biogas and methane.
8. the method that a kind of catalystic pyrolysis according to claim 1 prepares embedded magnetic metal carbon onion, its feature exist
In：In S3, the diluted acid is 1 mol/L HCl, HNO3Or H2SO4, stirring at normal temperature 10h.
9. the method that a kind of catalystic pyrolysis according to claim 1 prepares embedded magnetic metal carbon onion, its feature exist
In：In S4, the nitration mixture is the mixture of the concentrated sulfuric acid and concentrated nitric acid, volume ratio 1:3.
10. the method that a kind of catalystic pyrolysis according to claim 1 or 9 prepares embedded magnetic metal carbon onion, it is special
Sign is：The embedded metal carbon onion crude product is placed in nitration mixture and stood after stirring 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711222949.6A CN107857247A (en) | 2017-11-29 | 2017-11-29 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711222949.6A CN107857247A (en) | 2017-11-29 | 2017-11-29 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107857247A true CN107857247A (en) | 2018-03-30 |
Family
ID=61704339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711222949.6A Pending CN107857247A (en) | 2017-11-29 | 2017-11-29 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107857247A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109147986A (en) * | 2018-09-13 | 2019-01-04 | 慈溪市万金电子元件有限公司 | A kind of carbon onion conductive material of embedded metal and preparation method thereof |
| CN111115617A (en) * | 2019-12-24 | 2020-05-08 | 谢春艳 | Large-scale preparation method of high-purity hollow carbon nano-onion |
| CN110944500B (en) * | 2019-12-07 | 2021-04-02 | 太原理工大学 | Application of core-shell magnetic nano onion carbon-based composite material as wave-absorbing material |
| CN112758915A (en) * | 2020-12-30 | 2021-05-07 | 温州大学 | Preparation method of highly-graphitized mesoporous-rich nano-carbon onion |
| CN113394027A (en) * | 2020-03-12 | 2021-09-14 | 天津理工大学 | Carbon nano onion film-based supercapacitor used in field of alternating current line filtering |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058169A (en) * | 2010-08-02 | 2013-04-24 | 无锡诚信碳材料科技有限公司 | Preparation method for carbon nanomaterials with high graphitization degree |
-
2017
- 2017-11-29 CN CN201711222949.6A patent/CN107857247A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058169A (en) * | 2010-08-02 | 2013-04-24 | 无锡诚信碳材料科技有限公司 | Preparation method for carbon nanomaterials with high graphitization degree |
Non-Patent Citations (2)
| Title |
|---|
| 常东军: "水溶性内包铁洋葱状富勒烯优化制备及结构表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 张敏: "化学气相沉积法制备CNOs 及其磁选纯化研究", 《人工晶体学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109147986A (en) * | 2018-09-13 | 2019-01-04 | 慈溪市万金电子元件有限公司 | A kind of carbon onion conductive material of embedded metal and preparation method thereof |
| CN110944500B (en) * | 2019-12-07 | 2021-04-02 | 太原理工大学 | Application of core-shell magnetic nano onion carbon-based composite material as wave-absorbing material |
| CN111115617A (en) * | 2019-12-24 | 2020-05-08 | 谢春艳 | Large-scale preparation method of high-purity hollow carbon nano-onion |
| CN113394027A (en) * | 2020-03-12 | 2021-09-14 | 天津理工大学 | Carbon nano onion film-based supercapacitor used in field of alternating current line filtering |
| CN113394027B (en) * | 2020-03-12 | 2022-03-15 | 天津理工大学 | Carbon nano onion film-based supercapacitor used in field of alternating current line filtering |
| CN112758915A (en) * | 2020-12-30 | 2021-05-07 | 温州大学 | Preparation method of highly-graphitized mesoporous-rich nano-carbon onion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107857247A (en) | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion | |
| CN111170309B (en) | Preparation method of ultra-long few-wall carbon nanotube array | |
| CN101905881B (en) | Preparation method of nano-carbon material with high graphitization degree | |
| CN103754878B (en) | The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ | |
| CN111167495B (en) | Catalyst Ni for ammonia borane hydrogen production 2-x Fe x @ CN-G and preparation method thereof | |
| CN109759117A (en) | A method of nitrogen-doped carbon coating metal nano granule composite material is prepared using carbon fiber | |
| CN113135562B (en) | Method and device for preparing carbon nano tube and hydrogen | |
| CN110272036B (en) | Preparation method of magnetic substance doped multi-walled carbon nanotube and multi-walled carbon nanotube prepared by same | |
| CN101856614B (en) | Chemical vaporous deposition method for preparing carbon nano-onions by using Ni-Fe alloy as catalyst | |
| CN107032326A (en) | A kind of method that solid catalysis prepares spiral carbon nano pipe | |
| CN106379885B (en) | A kind of high efficiency preparation method of carbon nanotube or graphene | |
| CN102963938A (en) | Spinel ferrite/CNx nanocomposite and preparation method thereof | |
| CN105060271A (en) | Carbon nano-tube purification method | |
| CN104520231A (en) | Method for preparing sulfur-containing carbon material and sulfur-containing carbon material prepared therewith | |
| Quevedo et al. | Growth of nitrogen-doped carbon nanotubes using Ni/La2Zr2O7 as catalyst: Electrochemical and magnetic studies | |
| CN105293468A (en) | Method for efficiently preparing sulphur-doped hollow carbon spheres | |
| CN109616626B (en) | Low-temperature macro preparation method of carbon-coated ferroferric oxide nanocrystal | |
| CN109573982A (en) | A kind of three-dimensional structure carbon material | |
| CN111943722A (en) | Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof | |
| Yang et al. | Experimental and simulation research on the preparation of carbon nano-materials by chemical vapor deposition | |
| Bamoharram et al. | Synthesis of carbon nanotubes via catalytic chemical vapor deposition method and their modification with Preyssler anion,[NaP5W30O110] 14 | |
| CN108423653A (en) | A kind of preparation method of the carbon nanotube with electromagnetic wave shielding function | |
| CN110252304A (en) | Fe-series catalyst and its preparation method and application and carbon nanotube and preparation method thereof | |
| CN1113990C (en) | High elastic screw carbon fibre and its preparing method | |
| CN108516535B (en) | Method for preparing carbon nano tube in large scale |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180330 |