CN106219517B - It is a kind of using lignin as magnetic carbon nanometer micro ball of carbon source and preparation method thereof - Google Patents
It is a kind of using lignin as magnetic carbon nanometer micro ball of carbon source and preparation method thereof Download PDFInfo
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- CN106219517B CN106219517B CN201610652178.3A CN201610652178A CN106219517B CN 106219517 B CN106219517 B CN 106219517B CN 201610652178 A CN201610652178 A CN 201610652178A CN 106219517 B CN106219517 B CN 106219517B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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Abstract
The invention belongs to nanocomposite technical fields, disclose a kind of using lignin as magnetic carbon nanometer micro ball of carbon source and preparation method thereof.The preparation method is that：Lignin and ferric acetyl acetonade are dissolved in N, in N dimethylformamides, the lignin electrostatic solution containing ferric acetyl acetonade is obtained, the lignin nanoparticle containing ferric acetyl acetonade is then obtained by electrostatic；Gained lignin nanoparticle is pre-oxidized at a temperature of 250~280 DEG C, then carries out carbonization treatment at a temperature of 400~900 DEG C, is obtained described using lignin as the magnetic carbon nanometer micro ball of carbon source.The preparation method raw material of the present invention are easy to get, and energy conservation and environmental protection, products therefrom microscopic appearance, dispersion performance and magnetic property are good, there is preferable application prospect in the fields such as information, the energy, detection and biology.
Description
Technical field
The invention belongs to nanocomposite technical fields, and in particular to a kind of using lignin as the magnetic carbon nanometer of carbon source
Microballoon and preparation method thereof.
Background technology
In recent years, how abundant, renewable and environmentally friendly biomass resource effectively and is fully used, alleviates the severe energy
With environmental problem, the extensive concern of various circles of society has been obtained.
One of the resource that lignin is most widely present as nature is that plant kingdom's content is only second to the second largest of cellulose
The polyphenol polymer of unformed shape.It is a kind of renewable, green, environmentally friendly natural macromolecular material.Commercial wood element conduct
The byproduct of paper industry, is present in black liquid, is seldom further processed and is utilized, and the waste of resource is caused,
Environmental problem even can be brought.Lignin molecule have abundant carbon content, thus can be further processed be prepared as carbon material into
It exercises and uses.Cause the attention of various countries researcher using the lignin that nature is widely present as carbon source, 1975, material scholar
Johnson proposes to prepare carbon fibre material by carbon source of lignin first.The carbon material that people use at present is generally petrochemical industry base
Carbon material, its own has that non-renewable, the feature of environmental protection is poor and of high cost.Magnetic material is in machinery, electronics, optics, magnetic
It learns, chemistry and biology field has a wide range of applications.Currently, rarely having both at home and abroad to using simple lignin as carbon source system
Research in terms of standby magnetism carbon nanometer micro ball, the problem of being primarily present are that lignin prepares Nano carbon balls and is difficult to keep its microcosmic shape
Looks cause it to be restricted in further using.
Invention content
In order to solve the disadvantage that the above prior art and shortcoming, the primary purpose of the present invention is that providing one kind with wood
Quality is the preparation method of the magnetic carbon nanometer micro ball of carbon source.
Another object of the present invention is to provide it is a kind of by the above method be prepared using lignin as the magnetic of carbon source
Property carbon nanometer micro ball.
The object of the invention is achieved through the following technical solutions：
It is a kind of using lignin as the preparation method of the magnetic carbon nanometer micro ball of carbon source, including following preparation process：
(1) lignin and ferric acetyl acetonade are dissolved in n,N-Dimethylformamide, obtain the wood containing ferric acetyl acetonade
Quality electrostatic solution；
(2) the lignin electrostatic solution containing ferric acetyl acetonade obtained by step (1) is transferred in the equipment of electrostatic,
The lignin nanoparticle containing ferric acetyl acetonade is obtained by electrostatic；
(3) the lignin nanoparticle containing ferric acetyl acetonade is pre-oxidized at a temperature of 250~280 DEG C；
(4) the lignin nanoparticle containing ferric acetyl acetonade of pre-oxidation is carbonized at a temperature of 400~900 DEG C
Processing obtains described using lignin as the magnetic carbon nanometer micro ball of carbon source.
Preferably, in the lignin electrostatic solution containing ferric acetyl acetonade described in step (1), the quality point of lignin
Number is 20%~50%, and the content of ferric acetyl acetonade is the 5%~30% of lignin quality.
Preferably, the condition of electrostatic described in step (2) is：Electrostatic pressure is 10~30kv, receive distance for 10~
The fltting speed of 20cm, electrostatic solution are 1~3ml/h.
Preferably, preoxidation process described in step (3) carries out in air atmosphere, and preoxidation time is 2~6h, heating
Rate is 0.2~1 DEG C/min.
Preferably, carbonization treatment process described in step (4) carries out under nitrogen or argon gas atmosphere, the time of carbonization treatment
For 0.5~2h, heating rate is 0.5~2 DEG C/min.
It is a kind of using lignin as the magnetic carbon nanometer micro ball of carbon source, be prepared by the above method.
The present invention preparation method and obtained product has the following advantages that and advantageous effect：
(1) it is with inexpensive, renewable, degradable that the be able to lignin of the present invention, which is the magnetic carbon nanometer micro ball of carbon source,
Commercial wood element is as carbon source, compared with previous carbon nanomaterial, there are raw material to be easy to get, fully consider that energy saving and environmental protection is former
Then, this has great importance for the sustainable development of resource and environment；
(2) the be able to lignin of the present invention is that the microscopic appearance of the magnetic carbon nanometer micro ball of carbon source is good, while having good
Good dispersion performance, can be improved the performance of lignin carbon material；
(3) the be able to lignin of the present invention, which is the magnetic carbon nanometer micro ball of carbon source, has good magnetic property, in information, energy
There is preferable application prospect in the fields such as source, detection and biology；
(4) present invention is simple as the preparation method of the magnetic carbon nanometer micro ball of carbon source using lignin, and manufacturing cost is cheap, tool
There is good actual application value.
Description of the drawings
Fig. 1 is the preparation of the embodiment of the present invention 1 using lignin as the microscopic appearance figure of the magnetic carbon nanometer micro ball of carbon source
((a) 5000 ×, (b) 10000 ×).
Fig. 2 is the preparation of the embodiment of the present invention 4 using lignin as the hysteresis loop figure of the magnetic carbon nanometer micro ball of carbon source.
Fig. 3 is the preparation of the embodiment of the present invention 5 using lignin as the hysteresis loop figure of the magnetic carbon nanometer micro ball of carbon source.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) commercial wood element and ferric acetyl acetonade are weighed, the use of n,N-Dimethylformamide is solvent, is configured to lignin
(wherein acetylacetone,2,4-pentanedione iron content is lignin to the lignin electrostatic solution containing ferric acetyl acetonade that mass fraction is 35%
10%, w/w)；
(2) the lignin electrostatic solution containing ferric acetyl acetonade of step (1) is transferred in the equipment of electrostatic, quiet
Voltage is 25kv, and it is 15cm to receive distance, and the fltting speed of electrostatic solution obtains to carry out electrostatic under conditions of 3ml/h
Lignin nanoparticle containing ferric acetyl acetonade；
(3) it is pre- using 250 DEG C among by gained, the lignin nanoparticle containing ferric acetyl acetonade is positioned over tube furnace
Oxidizing temperature pre-oxidizes the lignin nanoparticle, pre-oxidation carry out in air, heating rate be 0.2 DEG C/
Min, preoxidation time 3h；
(4) the lignin nanoparticle containing ferric acetyl acetonade of above-mentioned pre-oxidation is subjected to carbonization treatment, carburizing temperature
It it is 400 DEG C, carbonization carries out in nitrogen, and heating rate is 2 DEG C/min, and carbonization time 0.5h is finally obtained with lignin
For the magnetic carbon nanometer micro ball of carbon source.
Obtained in the present embodiment using lignin as the scanning electron microscope (SEM) photograph of the magnetic carbon nanometer micro ball of carbon source as shown in Figure 1,
As seen from Figure 1：Good spherical morphology is presented by the magnetic carbon nanometer micro ball of carbon source of lignin, while being had preferably
Dispersion performance.
Embodiment 2
(1) commercial wood element and ferric acetyl acetonade are weighed, the use of n,N-Dimethylformamide is solvent, is configured to lignin
(wherein acetylacetone,2,4-pentanedione iron content is lignin to the lignin electrostatic solution containing ferric acetyl acetonade that mass fraction is 45%
30%, w/w)；
(2) the lignin electrostatic solution containing ferric acetyl acetonade of step (1) is transferred in the equipment of electrostatic, quiet
Voltage is 15kv, and it is 15cm to receive distance, and the fltting speed of electrostatic solution obtains to carry out electrostatic under conditions of 3ml/h
Lignin nanoparticle containing ferric acetyl acetonade；
(3) it is pre- using 280 DEG C among by gained, the lignin nanoparticle containing ferric acetyl acetonade is positioned over tube furnace
Oxidizing temperature pre-oxidizes the lignin nanoparticle, pre-oxidation carry out in air, heating rate be 0.5 DEG C/
Min, preoxidation time 6h；
(4) the lignin nanoparticle containing ferric acetyl acetonade of above-mentioned pre-oxidation is subjected to carbonization treatment, carburizing temperature
It it is 400 DEG C, carbonization carries out in nitrogen, and heating rate is 1 DEG C/min, and carbonization time 2h finally obtains favorable dispersibility
Using lignin as the magnetic carbon nanometer micro ball of carbon source.
Embodiment 3
(1) commercial wood element and ferric acetyl acetonade are weighed, the use of n,N-Dimethylformamide is solvent, is configured to lignin
(wherein acetylacetone,2,4-pentanedione iron content is lignin to the lignin electrostatic solution containing ferric acetyl acetonade that mass fraction is 35%
20%, w/w)；
(2) the lignin electrostatic solution containing ferric acetyl acetonade of step (1) is transferred in the equipment of electrostatic, quiet
Voltage is 15kv, and it is 10cm to receive distance, and the fltting speed of electrostatic solution obtains to carry out electrostatic under conditions of 2ml/h
Lignin nanoparticle containing ferric acetyl acetonade；
(3) it is pre- using 280 DEG C among by gained, the lignin nanoparticle containing ferric acetyl acetonade is positioned over tube furnace
Oxidizing temperature pre-oxidizes the lignin nanoparticle, pre-oxidation carry out in air, heating rate be 0.2 DEG C/
Min, preoxidation time 2h；
(4) the lignin nanoparticle containing ferric acetyl acetonade of above-mentioned pre-oxidation is subjected to carbonization treatment, carburizing temperature
It it is 600 DEG C, carbonization carries out in argon gas, and heating rate is 0.5 DEG C/min, carbonization time 1h, and it is good to finally obtain dispersibility
It is good using lignin as the magnetic carbon nanometer micro ball of carbon source.
Embodiment 4
(1) commercial wood element and ferric acetyl acetonade are weighed, the use of n,N-Dimethylformamide is solvent, is configured to lignin
(wherein acetylacetone,2,4-pentanedione iron content is lignin to the lignin electrostatic solution containing ferric acetyl acetonade that mass fraction is 35%
5%, w/w)；
(2) the lignin electrostatic solution containing ferric acetyl acetonade of step (1) is transferred in the equipment of electrostatic, quiet
Voltage is 15kv, and it is 10cm to receive distance, and the fltting speed of electrostatic solution obtains to carry out electrostatic under conditions of 2ml/h
Lignin nanoparticle containing ferric acetyl acetonade；
(3) it is pre- using 280 DEG C among by gained, the lignin nanoparticle containing ferric acetyl acetonade is positioned over tube furnace
Oxidizing temperature pre-oxidizes the lignin nanoparticle, pre-oxidation carry out in air, heating rate be 0.2 DEG C/
Min, preoxidation time 2h；
(4) the lignin nanoparticle containing ferric acetyl acetonade of above-mentioned pre-oxidation is subjected to carbonization treatment, carburizing temperature
It it is 800 DEG C, carbonization carries out in nitrogen, and heating rate is 2 DEG C/min, and carbonization time 2h finally obtains favorable dispersibility
Using lignin as the magnetic carbon nanometer micro ball of carbon source.
The be able to lignin of the present embodiment is that the hysteresis loop figure of the magnetic carbon nanometer micro ball of carbon source is as shown in Figure 2.
Embodiment 5
(1) commercial wood element and ferric acetyl acetonade are weighed, the use of n,N-Dimethylformamide is solvent, is configured to lignin
(wherein acetylacetone,2,4-pentanedione iron content is lignin to the lignin electrostatic solution containing ferric acetyl acetonade that mass fraction is 35%
30%, w/w)；
(2) the lignin electrostatic solution containing ferric acetyl acetonade of step (1) is transferred in the equipment of electrostatic, quiet
Voltage is 15kv, and it is 10cm to receive distance, and the fltting speed of electrostatic solution obtains to carry out electrostatic under conditions of 2ml/h
Lignin nanoparticle containing ferric acetyl acetonade；
(3) it is pre- using 280 DEG C among by gained, the lignin nanoparticle containing ferric acetyl acetonade is positioned over tube furnace
Oxidizing temperature pre-oxidizes the lignin nanoparticle, pre-oxidation carry out in air, heating rate be 0.2 DEG C/
Min, preoxidation time 2h；
(4) the lignin nanoparticle containing ferric acetyl acetonade of above-mentioned pre-oxidation is subjected to carbonization treatment, carburizing temperature
It it is 900 DEG C, carbonization carries out in nitrogen, and heating rate is 1 DEG C/min, carbonization time 0.5h, and it is good to finally obtain dispersibility
It is good using lignin as the magnetic carbon nanometer micro ball of carbon source.
The be able to lignin of the present embodiment is that the hysteresis loop figure of the magnetic carbon nanometer micro ball of carbon source is as shown in Figure 3.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (5)
1. a kind of using lignin as the preparation method of the magnetic carbon nanometer micro ball of carbon source, it is characterised in that including preparing step as follows
Suddenly：
(1) lignin and ferric acetyl acetonade are dissolved in n,N-Dimethylformamide, obtain the lignin containing ferric acetyl acetonade
Electrostatic solution；
(2) the lignin electrostatic solution containing ferric acetyl acetonade obtained by step (1) is transferred in the equipment of electrostatic, is passed through
Electrostatic obtains the lignin nanoparticle containing ferric acetyl acetonade；
(3) the lignin nanoparticle containing ferric acetyl acetonade is pre-oxidized at a temperature of 250~280 DEG C；
(4) the lignin nanoparticle containing ferric acetyl acetonade of pre-oxidation is carried out at a temperature of 400~900 DEG C at carbonization
Reason obtains described using lignin as the magnetic carbon nanometer micro ball of carbon source；
In lignin electrostatic solution containing ferric acetyl acetonade described in step (1), the mass fraction of lignin is 20%~
50%, the content of ferric acetyl acetonade is the 5%~30% of lignin quality.
2. according to claim 1 a kind of using lignin as the preparation method of the magnetic carbon nanometer micro ball of carbon source, feature
It is that the condition of electrostatic described in step (2) is：Electrostatic pressure is 10~30kv, and it is 10~20cm to receive distance, and electrostatic is molten
The fltting speed of liquid is 1~3ml/h.
3. according to claim 1 a kind of using lignin as the preparation method of the magnetic carbon nanometer micro ball of carbon source, feature
It is：Preoxidation process carries out in air atmosphere described in step (3), and preoxidation time is 2~6h, heating rate 0.2
~1 DEG C/min.
4. according to claim 1 a kind of using lignin as the preparation method of the magnetic carbon nanometer micro ball of carbon source, feature
It is：Carbonization treatment process carries out under nitrogen or argon gas atmosphere described in step (4), and the time of carbonization treatment is 0.5~2h,
Heating rate is 0.5~2 DEG C/min.
5. a kind of using lignin as the magnetic carbon nanometer micro ball of carbon source, it is characterised in that：Pass through any one of Claims 1 to 4 institute
The method stated is prepared.
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| CN107221641B (en) * | 2017-06-26 | 2019-12-03 | 浙江工业大学 | A kind of lignin is the MoS of carbon source2The preparation method of@C combination electrode material |
| CN107349905A (en) * | 2017-08-30 | 2017-11-17 | 华南理工大学 | The method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater |
| CN107758640B (en) * | 2017-10-27 | 2019-08-13 | 华中科技大学 | A kind of preparation method and product of the hollow carbon of erythrocyte shape |
| CN109012590B (en) * | 2018-08-24 | 2020-04-07 | 华南理工大学 | Lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof |
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| CN102634872A (en) * | 2011-02-11 | 2012-08-15 | 李翠花 | Preparation method of nanometer carbon fiber material containing iron oxide |
| CN105819426A (en) * | 2016-04-06 | 2016-08-03 | 华南理工大学 | Alkali lignin carbon nanometer microsphere as well as preparation method and application thereof |
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| US20140271443A1 (en) * | 2013-03-15 | 2014-09-18 | University Of Tennessee Research Foundation | High Glass Transition Lignins and Lignin Derivatives for the Manufacture of Carbon and Graphite Fibers |
| US9540244B2 (en) * | 2013-06-05 | 2017-01-10 | Mississippi State University | Methods for synthesizing graphene from a lignin source |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102634872A (en) * | 2011-02-11 | 2012-08-15 | 李翠花 | Preparation method of nanometer carbon fiber material containing iron oxide |
| CN105819426A (en) * | 2016-04-06 | 2016-08-03 | 华南理工大学 | Alkali lignin carbon nanometer microsphere as well as preparation method and application thereof |
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