CN101181987A - Method for preparing starch-based carbon microsphere - Google Patents
Method for preparing starch-based carbon microsphere Download PDFInfo
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- CN101181987A CN101181987A CNA2007101502518A CN200710150251A CN101181987A CN 101181987 A CN101181987 A CN 101181987A CN A2007101502518 A CNA2007101502518 A CN A2007101502518A CN 200710150251 A CN200710150251 A CN 200710150251A CN 101181987 A CN101181987 A CN 101181987A
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Abstract
The invention discloses a method used for preparing starch-based carbon microsphere, which pertains to the preparation technique of carbon microsphere. The procedure of the method comprises that cereal starch, tuber starch, bean starch and fruit starch of bananas and plantain are used as raw materials with a particle diameter of 2 to 120 micron; the raw materials are put into a heating furnace, heated to 62 to 300 DEG C at a certain heating rate in oxidizing atmosphere (for example, air, oxygen, ozone, etc.) and go through oxidation treatment under constant temperature for 2 to 72 hours. The starch after oxidation is put into a carbonization furnace, heated to 600 DEG C to 3000 DEG C at a certain heating rate under the protection of inert gas, treated for 0.5 to 48 hours at a constant temperature and then cooled to indoor temperature, and the starch-based carbon microsphere which keep original starch particle shape is obtained. The invention has the advantages of reproducible raw materials, wide source, low price, simple preparation process and low production cost, and being easy for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of starch-based carbon microsphere, belong to the technology of preparing of carbon microspheres.
Background technology
The carbon microspheres material is new variety of the later stage seventies 20th century being developed a kind of high-grade raw material of wood-charcoal material successfully by flourishing countries of industry such as Japan, the U.S., Germany and the Soviet Union.It can be divided three classes by the raw material difference: coal-based, polymer-based and asphaltic base carbon microspheres.The preparation method of carbon microspheres mainly contains at present: thermal polycondensation process, emulsion method, direct pyrolysis method, suspension method, arc discharge method, template, chemical Vapor deposition process etc.Emulsion method is to be raw material with mesophase pitch etc., and heated and stirred forms emulsion in the high-temperature silicon oil through pulverizing, pouring into, again by means such as cooling, centrifugation, sedimentation, filtration, drying and carbonizations, obtains the asphaltic base carbon microspheres.Song Huaihe etc. have elaborated other preparation methods in " a kind of preparation method of polymer based carbon balls " in (ZL200510000055.3).
Wang Qing etc. " pyrolyzed hard carbon material and its production and use " (ZL01807830.3) in, hard carbon precursor (as: Mierocrystalline cellulose, starch etc.) and solvent are mixed with the homodisperse system are placed on liquid-phase dehydration in the pressurized vessel, obtain the hard carbon microspheres material of pyrolysis through washing, filtration, drying, charing.
Above-mentioned technology generally exists complex process, to problems such as equipment requirements strictnesses, and used starting material are Nonrenewable resources (as: oil, pitch etc.) and the serious organic compound of environmental pollution, can not satisfy the requirement of " green chemical industry ".
Summary of the invention
The object of the present invention is to provide a kind of preparation method of starch-based carbon microsphere.This method has the advantages that raw material sources are extensive, preparation process is simple, production cost is low.
The present invention is realized that by following technical proposals a kind of preparation method of starch-based carbon microsphere is characterized in that comprising following process:
(1) be that the fruit kind of starch of cereal kind of starch, potato starch, legume starch and the banana of 2-120 μ m and bajiao banana etc. is a raw material with the particle diameter; Raw material is added in the process furnace, in the atmosphere of air, oxygen, ozone, sulfurous gas, nitrogen peroxide or sulphur trioxide, is that 0.5-50 ℃/min is heated to 60-300 ℃ with the temperature rise rate, carries out oxide treatment in constant temperature 2-72 hour.
(2) starch of step (1) through peroxidation is added in the charring furnace; under the protection of nitrogen or helium, rise to 600 ℃-3000 ℃, constant temperature thermal treatment 0.5-48 hour with the temperature rise rate of 0.5-50 ℃/min; rate of temperature fall with 1-50 ℃/min is cooled to room temperature afterwards, makes starch-based carbon microsphere.
The present invention has following advantage: the preparation raw material sources are extensive, and starch is the common form of green plants accumulation energy and storage carbohydrate, is a kind of recyclability resource, limited resources such as final alternative day by day withered thirsty oil, Sweet natural gas.The farm crop that are used for Starch Production at present mainly contain corn, cassava, potato, wheat etc.China is agriculture production big country, so starch resource is very abundant and cheap.Production technique of the present invention is simple, saves time, and is laborsaving, easily realizes mass preparation; And the starch of different varieties exists difference in granular size and vpg connection, so can select for use different sorts starch to prepare the microballoon raw material of wood-charcoal material of different shape as requested.
Description of drawings
The stereoscan photograph of the W-Gum raw material that Fig. 1-be embodiment of the invention 1 is adopted.
The stereoscan photograph of the starch-based carbon microsphere that Fig. 2-be embodiment of the invention 1 makes.
Embodiment
Embodiment 1
In process furnace, in air atmosphere, add 13.5g W-Gum (spherical in shape or polygon), with the temperature rise rate of 0.5 ℃/min process furnace is risen to 120 ℃ after, constant temperature oxide treatment 48h; Then the starch after oxide treatment is added in the charring furnace, at N
2Protection down; nitrogen flow is 25ml/min; temperature rise rate with 2 ℃/min is heated to 600 ℃ with charring furnace; behind the constant temperature 2h; speed with 0.2 ℃/min is cooled to room temperature with charring furnace again; obtain the starch-based carbon microsphere that median size is 15 μ m, the yield of carbon microspheres is 21.0%, and the specific surface area of measuring carbon microspheres with the BET method is 350.3m
2/ g; True density is 1.591g/cm
3
In process furnace, in air atmosphere, add the 14.0g W-Gum, with the temperature rise rate of 5 ℃/min process furnace is risen to 180 ℃ after, constant temperature oxide treatment 20h; Then the starch after oxide treatment is added in the charring furnace, at N
2Protection down; nitrogen flow is 50ml/min; temperature rise rate with 5 ℃/min is heated to 1000 ℃ with charring furnace; behind the constant temperature 1.5h; speed with 1 ℃/min is cooled to room temperature with charring furnace again; obtain the starch-based carbon microsphere that median size is 12 μ m, the yield of carbon microspheres is 16.5%, and the specific surface area of measuring carbon microspheres with the BET method is 110.8m
2/ g; True density is 1.617g/cm
3
In process furnace, in air atmosphere, add 20.0g W-Gum (spherical in shape or polygon), with the temperature rise rate of 20 ℃/min process furnace is risen to 260 ℃ after, constant temperature oxide treatment 12h; Then the starch after oxide treatment is added in the charring furnace, at N
2Protection down; nitrogen flow is 40ml/min; temperature rise rate with 10 ℃/min is heated to 2600 ℃ with charring furnace; behind the constant temperature 1h; speed with 20 ℃/min is cooled to room temperature with charring furnace again; obtain the starch-based carbon microsphere that median size is 10 μ m, the yield of carbon microspheres is 13.4%, and true density is 1.497g/cm
3
Operational condition is with embodiment 1, and difference is: starch material is green starch (a spherical in shape or elliposoidal).The starch-based carbon microsphere average size of products that makes is 15 μ m, and yield is 22.7%, and true density is 1.885g/cm
3
Embodiment 5
Operational condition is with embodiment 1, and difference is: starch material is yam starch (spherical in shape or avette).The starch-based carbon microsphere average size of products that makes is 25 μ m, and yield is 20.9%, and true density is 1.875g/cm
3
Claims (1)
1. the preparation method of a starch-based carbon microsphere is characterized in that comprising following process:
(1) be that cereal kind of starch, potato starch, legume starch and the banana of 2-120 μ m and the fruit kind of starch of bajiao banana are raw material with the particle diameter; Raw material is added in the process furnace, in the atmosphere of air, oxygen, ozone, sulfurous gas, nitrogen peroxide or sulphur trioxide, is that 0.5-50 ℃/min is heated to 60-300 ℃ with the temperature rise rate, carries out oxide treatment in constant temperature 2-72 hour;
(2) will add through the starch of step (1) oxidation in the charring furnace; under the protection of nitrogen or helium, rise to 600 ℃-3000 ℃, constant temperature thermal treatment 0.5-48 hour with the temperature rise rate of 0.5-50 ℃/min; rate of temperature fall with 1-50 ℃/min is cooled to room temperature afterwards, makes starch-based carbon microsphere.
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| CNA2007101502518A CN101181987A (en) | 2007-11-21 | 2007-11-21 | Method for preparing starch-based carbon microsphere |
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| CNA2007101502518A CN101181987A (en) | 2007-11-21 | 2007-11-21 | Method for preparing starch-based carbon microsphere |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580637A (en) * | 2012-02-24 | 2012-07-18 | 大连理工大学 | Simple preparation method of graded-hole micronscale magnetic carbon microspheres |
| CN103647082A (en) * | 2013-12-24 | 2014-03-19 | 中国船舶重工集团公司第七一二研究所 | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material |
| CN104817065A (en) * | 2015-04-02 | 2015-08-05 | 安徽农业大学 | Preparation method of cellular starch-based porous carbon material |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| 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 |
| CN110386601A (en) * | 2019-06-24 | 2019-10-29 | 鞍钢股份有限公司 | Method for removing quinoline insoluble particles on surface of carbon microsphere |
| CN115175653A (en) * | 2020-03-05 | 2022-10-11 | 因特科股份有限公司 | Cosmetic composition containing optimized starch and cosmetic application thereof |
| CN116062731A (en) * | 2023-02-07 | 2023-05-05 | 湖北万润新能源科技股份有限公司 | Method for preparing hard carbon |
| WO2023173772A1 (en) * | 2022-03-15 | 2023-09-21 | 广东邦普循环科技有限公司 | Preparation method for and use of hard carbon negative electrode material |
-
2007
- 2007-11-21 CN CNA2007101502518A patent/CN101181987A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580637A (en) * | 2012-02-24 | 2012-07-18 | 大连理工大学 | Simple preparation method of graded-hole micronscale magnetic carbon microspheres |
| CN103647082A (en) * | 2013-12-24 | 2014-03-19 | 中国船舶重工集团公司第七一二研究所 | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material |
| CN103647082B (en) * | 2013-12-24 | 2016-05-04 | 中国船舶重工集团公司第七一二研究所 | The preparation method of the hard carbon microsphere cathode material of a kind of lithium rechargeable battery |
| CN104817065A (en) * | 2015-04-02 | 2015-08-05 | 安徽农业大学 | Preparation method of cellular starch-based porous carbon material |
| 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 |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN110386601A (en) * | 2019-06-24 | 2019-10-29 | 鞍钢股份有限公司 | Method for removing quinoline insoluble particles on surface of carbon microsphere |
| CN110386601B (en) * | 2019-06-24 | 2022-09-16 | 鞍钢股份有限公司 | Method for removing quinoline insoluble particles on surface of carbon microsphere |
| CN115175653A (en) * | 2020-03-05 | 2022-10-11 | 因特科股份有限公司 | Cosmetic composition containing optimized starch and cosmetic application thereof |
| CN115175653B (en) * | 2020-03-05 | 2024-09-10 | 因特科股份有限公司 | Cosmetic composition containing optimized starch and cosmetic application thereof |
| WO2023173772A1 (en) * | 2022-03-15 | 2023-09-21 | 广东邦普循环科技有限公司 | Preparation method for and use of hard carbon negative electrode material |
| CN116062731A (en) * | 2023-02-07 | 2023-05-05 | 湖北万润新能源科技股份有限公司 | Method for preparing hard carbon |
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