CN102580637A - Simple preparation method of graded-hole micronscale magnetic carbon microspheres - Google Patents
Simple preparation method of graded-hole micronscale magnetic carbon microspheres Download PDFInfo
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- CN102580637A CN102580637A CN2012100449613A CN201210044961A CN102580637A CN 102580637 A CN102580637 A CN 102580637A CN 2012100449613 A CN2012100449613 A CN 2012100449613A CN 201210044961 A CN201210044961 A CN 201210044961A CN 102580637 A CN102580637 A CN 102580637A
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Abstract
The invention discloses a simple preparation method of graded-hole micronscale magnetic carbon microspheres, belonging to the technical field of the carbon material. The simple preparation method of graded-hole micronscale magnetic carbon microspheres comprises the following two steps of: 1) dissolving a metal salt and sodium hydroxide in a 30-70mL of ethylene glycol solution according to a certain ratio, reacting in an oil bath at 170-190 DEG C for 3-6hours under the protection of the inert atmosphere to prepare metal/metal oxide nanoparticles, adding 5-10g of porous starch, performing suction filtering and drying to obtain a metal/metal oxide porous starch complex; and 2) placing the complex in a drying cabinet to perform pre-oxidation at 170-190 DEG C for 24-48hours, and carbonizing in the hydrogen atmosphere at 700-1000 DEG C for 4-8hours to obtain the graded-hole micronscale magnetic carbon microspheres. The raw material used by the method is cheap and available commercial porous starch, and the obtained magnetic carbon material is characterized by irregular circular particles and has potential application prospects in fields such as biological materials, catalysis and separation.
Description
Technical field
The present invention relates to the method for a kind of easy manufacture classification hole micron order magnetic carbon microspheres, belong to the carbon material technical field.
Background technology
Characteristics such as the raw material of wood-charcoal material is heat-resisting owing to high heat conduction, the height of its excellence, good chemical inertia, high conductivity make it be widely used in many national economy fields such as the energy, chemical industry, environmental protection, electronics, Aero-Space.And, the research and the application of these traditional raw material of wood-charcoal material and carbon product are very limited as a large amount of exploitations of the fossil resource (as: coal, oil, pitch etc.) of raw material of wood-charcoal material and carbon product main source and the environmental problem that is on the rise.The reproducible resource of therefore, seeking cheapness, cleaning has enjoyed the extensive concern of Chinese scholars as the raw material of preparation raw material of wood-charcoal material.
Starch is a kind of wide material sources, cheap renewable natural carbon source, adopts certain physical method, chemical method and enzyme modifying technology, can carry out modulation to molecular structure, the physicochemical properties of starch.But be that the raw material of wood-charcoal material of various new constructions of carbon source is successfully synthetic with the starch of cheap and easy to get and physicochemical properties modulation in recent years.The Clark of York University etc. are carbon source with starch; The character of utilizing starch to be easy to expand has been synthesized the adjustable mesopore charcoal catalysis material in aperture, their work show after the sulfonation starch base mesopore raw material of wood-charcoal material be a kind ofly reuse, eco-friendly acid esters catalysts; Doctors Shen Wenzhong of China Petroleum Univ. (East-China) etc. are that carbon source has been synthesized multiple dimensioned mesopore raw material of wood-charcoal material (aperture is 3.8-4.2nm, 6-10nm and 11-15nm) with the water soluble starch.Wang Chengyang etc. are in " preparation method of starch base the carbosphere " (patent No.: 200710150251), be carbon source with starch, adopt pre-oxidation-charing two-step method to prepare the starch base carbosphere of elliposoidal; Professor Li Qingyu of Guangxi Normal University also is that carbon source has been synthesized various starch-based carbon materials such as active carbon, porous carbon ball etc. with starch; And the chemical property of starch-based carbon material tested; In addition; They are in " preparation method of the micron porous carbon microsphere " (patent No.: 200710050549); With the starch after the modification (porous-starch) is carbon source, and solubility stannate, pink salt or silicate are the protective agent of spherical porous starch, adopts charring to prepare micrometer level porous carbosphere.But, be carbon source with the porous-starch, by simple and effective preoxidation technique, preparation has the method for the classification pore structure micron order magnetic carbon microspheres of magnetic separation function concurrently and does not appear in the newspapers both at home and abroad.The present invention adopts simple pre-oxidation and the charing two-step method making classification hole micron order magnetic carbon microspheres of having got everything ready.
Summary of the invention
The present invention provides the method for a kind of easy manufacture classification hole micron order magnetic carbon microspheres; This method adopts simple pre-oxidation and the charing two-step method making classification hole micron order magnetic carbon microspheres of having got everything ready; Preparation technology is simple, low-cost, is the magnetic porous carbon microspheres with high added value that the presoma preparation has specific morphology and function with the porous-starch.
The technical scheme that the present invention adopts: the method for a kind of easy manufacture classification hole micron order magnetic carbon microspheres comprises the following steps:
(1) with the slaine of certain proportioning and dissolution of sodium hydroxide in 30～70mL ethylene glycol solution; Under the inert atmosphere protection; In 170～190 ℃ of oil baths, react after 3～6h makes the metal/metal oxide nano particle; To wherein adding 5～10g porous-starch, suction filtration is also dry, obtains metal or metal oxide/porous-starch complex;
(2) metal or metal oxide/porous-starch complex are placed drying box; At 170～190 ℃ of pre-oxidation 24～48h; And then with this complex under hydrogen atmosphere, be warming up to 700～1000 ℃ with 2～10 ℃/min, charing 4～8h; Naturally cool to room temperature, obtain classification hole micron order magnetic carbon microspheres.
Described porous-starch comprises porous cornstarch, porous farina or porous tapioca.
Described slaine is selected from ferric nitrate, cobalt nitrate or nickel nitrate, or the acetate of metal.
The proportioning of described slaine and NaOH is 1: 3 or metering in 1: 2 in molar ratio.
The invention has the beneficial effects as follows: the method for this easy manufacture classification hole micron order magnetic carbon microspheres comprises following two steps: 1, with in slaine and the dissolution of sodium hydroxide ethylene glycol solution; Under the inert atmosphere protection; After heating makes the metal/metal oxide nano particle in oil bath; To wherein adding porous-starch, suction filtration is also dry, obtains metal or metal oxide/porous-starch complex; 2, place drying box in pre-oxidation on metal or metal oxide/porous-starch complex, and then, naturally cool to room temperature, obtain classification hole micron order magnetic carbon microspheres the charing under hydrogen atmosphere of this complex.This method is raw materials used to be commercialization porous-starch cheap and easy to get, and the preparation process is not high to equipment requirements, and parameter is controlled easily; Processing ease; Be easy to amplify, the magnetic raw material of wood-charcoal material of gained has the irregular cycle particle characteristic, and its classification pore passage structure comes from three aspects: the macropore of micro-meter scale is derived from porous-starch itself; Micropore and mesopore then are derived from and contain the hole that forms in the carbon matrix precursor carbonization process, and this material has potential application prospect in fields such as biomaterial, catalysis, separation.
Description of drawings
Fig. 1 is the stereoscan photograph of classification of the present invention hole micron order magnetic carbon microspheres.
The practical implementation method
Through embodiment the present invention is further specified below.
Embodiment one
Take by weighing 0.5g ferric nitrate and 0.2g dissolution of sodium hydroxide in 30mL ethylene glycol, sonicated is fully dissolved it, then mixed liquor is made iron/ferrous oxide nano particle in 180 ℃ of heating 3h, during constantly feed nitrogen as protection gas; Take by weighing 5g porous cornstarch and be added in iron/ferrous oxide nano particle, back suction filtration and the dry complex that obtains iron/ferrous oxide nano particle and porous cornstarch stir; And then this complex placed 180 ℃ of air dry oven pre-oxidation 24h, at last in the tubular type retort under hydrogen atmosphere charing 4h, wherein, heating rate is 5 ℃/min, carbonization temperature is 900 ℃, has finally made classification hole micron order magnetic carbon microspheres.
Embodiment two
Take by weighing 1g cobalt nitrate and 0.4g dissolution of sodium hydroxide in 60mL ethylene glycol, magnetic agitation is fully dissolved it, then mixed liquor is made iron/cobalt oxide nano particle in 180 ℃ of heating 4h, during constantly feed argon gas as protection gas; Take by weighing 10g porous cornstarch and be added in iron/cobalt oxide nano particle, back suction filtration and the dry complex that obtains iron/ferrous oxide nano particle and porous cornstarch stir; And then this complex placed 180 ℃ of air dry oven pre-oxidation 30h, at last in the tubular type retort under hydrogen atmosphere charing 7h, wherein, heating rate is 10 ℃/min, carbonization temperature is 700 ℃, has finally made classification hole micron order magnetic carbon microspheres.
Embodiment three
Take by weighing 0.5g nickel nitrate and 0.2g dissolution of sodium hydroxide in 40mL ethylene glycol, sonicated is fully dissolved it, then mixed liquor is made nickel/nickel oxide nano particle in 170 ℃ of heating 5h, during constantly feed nitrogen as protection gas; Take by weighing 6g porous farina and be added in nickel/nickel oxide nano particle, back suction filtration and the dry complex that obtains nickel/nickel oxide nano particle and porous cornstarch stir; And then this complex placed 170 ℃ of air dry oven pre-oxidation 36h, at last in the tubular type retort under hydrogen atmosphere charing 6h, wherein, heating rate is 2 ℃/min, carbonization temperature is 800 ℃, has finally made classification hole micron order magnetic carbon microspheres.
Embodiment four
Take by weighing 0.5g ferric acetate and 0.2g dissolution of sodium hydroxide in 50mL ethylene glycol, sonicated is fully dissolved it, then mixed liquor is made iron/ferrous oxide nano particle in 190 ℃ of heating 3h, during constantly feed argon gas as protection gas; Take by weighing 8g porous cornstarch and be added in iron/ferrous oxide nano particle, back suction filtration and the dry complex that obtains iron/ferrous oxide nano particle and porous cornstarch stir; And then this complex placed 180 ℃ of air dry oven pre-oxidation 48h, at last in the tubular type retort under hydrogen atmosphere charing 8h, wherein, heating rate is 6 ℃/min, carbonization temperature is 900 ℃, has finally made classification hole micron order magnetic carbon microspheres.
Embodiment five
Take by weighing 1g nickel acetate and 0.4g dissolution of sodium hydroxide in 70mL ethylene glycol, sonicated is fully dissolved it, then mixed liquor is made iron/nickel oxide nano particle in 170 ℃ of heating 6h, during constantly feed nitrogen as protection gas; Take by weighing 10g porous tapioca and be added in iron/nickel oxide nano particle, back suction filtration and the dry complex that obtains iron/ferrous oxide nano particle and cassava cornstarch stir; And then this complex placed 190 ℃ of air dry oven pre-oxidation 32h, at last in the tubular type retort under hydrogen atmosphere charing 5h, wherein, heating rate is 8 ℃/min, carbonization temperature is 1000 ℃, has finally made classification hole micron order magnetic carbon microspheres.
Embodiment six
Take by weighing 1g cobalt acetate and 0.4g dissolution of sodium hydroxide in 70mL ethylene glycol, sonicated is fully dissolved it, then mixed liquor is made iron/cobalt oxide nano particle in 170 ℃ of heating 6h, during constantly feed nitrogen as protection gas; Take by weighing 10g porous tapioca and be added in iron/cobalt oxide nano particle, back suction filtration and the dry complex that obtains iron/ferrous oxide nano particle and cassava cornstarch stir; And then this complex placed 190 ℃ of air dry oven pre-oxidation 28h, at last in the tubular type retort under hydrogen atmosphere charing 5h, wherein, heating rate is 4 ℃/min, carbonization temperature is 1000 ℃, has finally made classification hole micron order magnetic carbon microspheres.
Claims (4)
1. the method for an easy manufacture classification hole micron order magnetic carbon microspheres, it is characterized in that: this method comprises the following steps:
(1) with the slaine of certain proportioning and dissolution of sodium hydroxide in 30～70mL ethylene glycol solution; Under the inert atmosphere protection; In 170～190 ℃ of oil baths, react after 3～6h makes the metal/metal oxide nano particle; To wherein adding 5～10g porous-starch, suction filtration is also dry, obtains metal or metal oxide/porous-starch complex;
(2) metal or metal oxide/porous-starch complex are placed drying box; At 170～190 ℃ of pre-oxidation 24～48h; And then with this complex under hydrogen atmosphere, be warming up to 700～1000 ℃ with 2～10 ℃/min, charing 4～8h; Naturally cool to room temperature, obtain classification hole micron order magnetic carbon microspheres.
2. the method for easy manufacture classification according to claim 1 hole micron order magnetic carbon microspheres, it is characterized in that: described porous-starch comprises porous cornstarch, porous farina or porous tapioca.
3. the method for easy manufacture classification according to claim 1 hole micron order magnetic carbon microspheres, it is characterized in that: described slaine is selected from ferric nitrate, cobalt nitrate or nickel nitrate, or the acetate of metal.
4. the method for easy manufacture classification according to claim 1 hole micron order magnetic carbon microspheres is characterized in that: the proportioning of described slaine and NaOH is 1: 3 or metering in 1: 2 in molar ratio.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103041758A (en) * | 2013-01-17 | 2013-04-17 | 复旦大学 | Magnetic hollow multihole carbon ball with core-shell structure and preparation method of magnetic hollow multihole carbon ball |
| CN106299265A (en) * | 2015-06-08 | 2017-01-04 | 北京化工大学 | A kind of preparation method of high-performance starch based carbon microsphere/metal-oxide negative material |
| CN106925217A (en) * | 2017-04-08 | 2017-07-07 | 桂林理工大学 | A kind of preparation method of the magnetic porous carbon of peach gum base |
| CN111019820A (en) * | 2019-12-10 | 2020-04-17 | 沈阳农业大学 | Bioreactor and method for preparing pectin oligosaccharide and natural food preservative thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041758A (en) * | 2013-01-17 | 2013-04-17 | 复旦大学 | Magnetic hollow multihole carbon ball with core-shell structure and preparation method of magnetic hollow multihole carbon ball |
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| CN106299265A (en) * | 2015-06-08 | 2017-01-04 | 北京化工大学 | A kind of preparation method of high-performance starch based carbon microsphere/metal-oxide negative material |
| CN106925217A (en) * | 2017-04-08 | 2017-07-07 | 桂林理工大学 | A kind of preparation method of the magnetic porous carbon of peach gum base |
| CN111019820A (en) * | 2019-12-10 | 2020-04-17 | 沈阳农业大学 | Bioreactor and method for preparing pectin oligosaccharide and natural food preservative thereof |
| CN111019820B (en) * | 2019-12-10 | 2022-11-25 | 沈阳农业大学 | Bioreactor and method for preparing pectin oligosaccharide and natural food preservative thereof |
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Application publication date: 20120718 |