CN104477879A - Preparation method of starch-based carbon material - Google Patents
Preparation method of starch-based carbon material Download PDFInfo
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- CN104477879A CN104477879A CN201410730454.4A CN201410730454A CN104477879A CN 104477879 A CN104477879 A CN 104477879A CN 201410730454 A CN201410730454 A CN 201410730454A CN 104477879 A CN104477879 A CN 104477879A
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Abstract
The invention relates to a method for preparing a carbon material from starch. The method comprises the following steps: firstly, mixing starch, water and accessories according to certain proportions, gelatinizing and drying at 50-150 DEG C, so that crystallized starch is partially formed as amorphous starch, and carbonizing the amorphous starch in the atmosphere of inert gas at 180-450 DEG C so as to prepare the carbon material. The method disclosed by the invention is used for processing the starch without an organic solvent, so that melting and swelling of the starch when direct carbonization are avoided, and the method is conducive to preparation and forming; and the prepared carbon material is rich in oxygen-containing groups and aromatic hydrogen, is an excellent precursor for preparing functional carbon materials such as sulfonic acid and the carbon material is quite high in application value.
Description
Technical field
The present invention relates to a kind of method preparing carbon material, particularly relating to a kind of take starch as the preparation method of the starch base carbon material of carbon source.
Background technology
It is little that carbon material has density, the feature that stable chemical nature, thermostability are high, structural form is various, there is excellent physics, chemistry, electromagnetism is special can, at information, photoelectricity, life, the energy, sensor is multi-field presents wide application prospect and potential huge economic value, is the focus in 21st century new material research field.
Starch is as a kind of natural product, and abundance, kind is many, and output is large, is the high quality raw material preparing carbon material.Common starch is particulate state, has certain degree of crystallization, and in direct carbonization process, melting, trickling, expansion, such as 20 grams of starch carbonizations at 250 DEG C occur, and the foamed carbon material volume of formation can reach 500 milliliters.On the one hand, the characteristic that starch expands in carbonization process is conducive to forming porous carbon materials, and on the other hand, tens times of expansions cause carbon material intensity low, and the characteristic of trickling of expanding is unfavorable for commercialization volume production.For solving a difficult problem for the dilatational strain in carbonization process, recarbonize after starch conversion is made porous-starch by document (Vitaly Budarin, James H. Clark etc., Angew.Chem.Int.Ed. 2006,118,3866).But the method needs a large amount of organic solvent as ethanol, acetone etc., preparation process is complicated, and cost is higher, is difficult to the demand meeting commercialization volume production.And carbon material carbon content prepared by conventional high-temperature is high, oxy radical and fragrant hydrogen less, be difficult to grafting sulfonic acid, amino groups, method of modifying is single, mainly adopts the mode of oxidation to increase hydroxyl, carbonyl or carboxyl functional group.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, providing a kind of is raw material with starch, and the method for carbon material is prepared in carbonization at a lower temperature, solves the problem of melting expansion in starch carbonizing process, is conducive to mass-producing and utilizes.
Technical scheme of the present invention comprises the steps:
Pre-treatment step, by starch and water mixing, kneading becomes face embryo, compression moulding, and starch and quality ratio be, starch: water=65-85:15-35;
Maturation stage, gained face embryo steam heating at 60-150 DEG C of temperature, makes the abundant slaking in starch crystals district;
Dehydrating step, by the starch of abundant slaking drying and dehydrating at 50-120 DEG C of temperature;
Carburising step, will dewater aging starch under protection of inert gas, at 180-450 DEG C of temperature, keep 0.5-10 hour, obtain carbon material.
Described dehydrating step and carburising step can complete in two steps, also can complete continuously in a step.
In described pre-treatment step, starch material used is various plant roots and stems seeds processing gained starch, comprises purification starch or the undressed raw starch containing Mierocrystalline cellulose, protein.
Starch used comprises wheat starch, W-Gum, potato starch, sticky rice flour.
Described pre-treatment step comprises auxiliary material, and the mass ratio of starch, water and auxiliary material is, starch: water: auxiliary material=65-85:15-35:0-5.
Described auxiliary material is one or more in yeast, sodium bicarbonate, glycerine, polyoxyethylene glycol and lipid acid Tegin 55G.
Described carburising step, rare gas element is nitrogen, carbonic acid gas, argon gas or water vapour.
Advantageous effect of the present invention is as follows:
Take starch as carbon source, carbon material prepared by carbonization at a lower temperature contains abundant functional group, can prepare several functions carbon material by derivative reaction.The carbon material prepared under more traditional high temperature is compared, starch base carbon material carbonization temperature is usually below 500 DEG C, degree of carbonisation is lower, containing oxygen-containing functional group and fragrant hydrogen such as more hydroxyl, carboxyl, carbonyls, chemical modification can operating restraint wider, can sulfonation be carried out, chlorination, the multiple derivatization reaction such as amination.
The present invention simplifies preparation process, not with an organic solvent, with water and common starch for raw material, utilize pasted starch undefined structure, without the character of definite melting point, in carbonization process, temperature programming, forms vent when dehydration, is beneficial to gas and discharges, avoiding type to become, is a kind of carbon material preparation method with stronger practicality.
Embodiment
Embodiment 1
20 g wheat starches mix with 8.9 g water, make face embryo, and in 100 DEG C of steam, slaking 1 hour, is cooled to room temperature, slaking wheat starch are put into baking oven 120 DEG C of freeze-day with constant temperature to constant weight.Under nitrogen protection, by dried slaking wheat starch, be placed in retort furnace and carry out roasting, under nitrogen protection, be warmed up to 150 DEG C by room temperature with 10 DEG C/min, then, rise to 300 DEG C with the temperature rise rate of 2 DEG C/min, constant temperature 5 hours.Stop after naturally cooling to 100 DEG C for nitrogen, be cooled to room temperature, obtain black carbon material 12.4 g, without distortion, hardness is better.
Embodiment 2
20 g wheat starches, 8.9 g water and 0.2 g yeast mix, and make face embryo, and 30 DEG C of bottom fermentations 2 hours, then slaking 1 hour in 100 DEG C of steam, was cooled to room temperature, slaking wheat starch is put into baking oven 120 DEG C of freeze-day with constant temperature to constant weight.Under nitrogen protection, the slaking wheat starch sample of drying is placed in retort furnace and carries out roasting, be warmed up to 150 DEG C with 10 DEG C/min, then to rise in 300 DEG C of environment again constant temperature 5 hours with the temperature rise rate of 2 DEG C/min.Stop for nitrogen after being cooled to 100 DEG C, be cooled to room temperature and obtain aging starch carbon material 12.5 g without distortion, hardness is better.
Embodiment 3
20 g W-Gums mix with 15.6 g water and 0.2g sodium bicarbonate, make face embryo, and in 100 DEG C of steam, slaking 1 hour, is cooled to room temperature.Cooked corn starch is dried to constant weight under 120 DEG C of conditions.Then, under nitrogen protection, the cooked corn starch of drying is placed in retort furnace, is warmed up to 150 DEG C by room temperature with the speed of 20 DEG C/min, then to rise in 450 DEG C of environment again constant temperature 5 hours with the temperature rise rate of 2 DEG C/min.Stop after being cooled to 100 DEG C for nitrogen, be cooled to room temperature, obtain starch carbon material 22.7 g.
Embodiment 4
20 g wheat starches, 15.6 g water and 2 g glycerine mix, and make face embryo, and in 100 DEG C of steam, slaking 1 hour, is cooled to room temperature.Cooked corn starch is put into baking oven, at 120 DEG C, is dried to constant weight.Under nitrogen protection, the slaking wheat starch sample of drying is placed in retort furnace and carries out carbonization, be warmed up to 150 DEG C by room temperature with the speed of 20 DEG C/min, then rise to 300 DEG C with the temperature rise rate of 2 DEG C/min, constant temperature 5 hours.Stop for nitrogen after being cooled to 100 DEG C, be cooled to room temperature, obtain aging starch carbon material 22.5 g without distortion, hardness is better.
Embodiment 5
20 g wheat starches, 7 g water and 3 g lipid acid Tegin 55Gs mix, and make face embryo, in 150 DEG C of steam, slaking 1 hour, is cooled to room temperature, slaking wheat starch are put into baking oven 120 DEG C of freeze-day with constant temperature to constant weight.Under nitrogen protection, dry slaking wheat starch sample is placed in retort furnace and carries out roasting, to rise in 300 DEG C of environment constant temperature 5 hours by 150 DEG C with the temperature rise rate of 2 DEG C/min again.After completing insulation, stop for nitrogen after 100 DEG C, be cooled to room temperature and obtain aging starch carbon material 22.8 g without distortion, hardness is better.
Embodiment 6
20 g W-Gums mix with 12 g water and 3 g polyoxyethylene glycol, make face embryo, and in 100 DEG C of steam, slaking 1 hour, is cooled to room temperature.Cooked corn starch is put into baking oven 120 DEG C of freeze-day with constant temperature to constant weight.Under nitrogen protection in retort furnace, carbonization is carried out to the cooked corn starch sample of drying, to rise in 300 DEG C of environment again constant temperature 5 hours by 150 DEG C with the temperature rise rate of 2 DEG C/min.Complete and be incubated and stop for nitrogen after being cooled to 100 DEG C, be cooled to room temperature and obtain black carbon material 22.5 g without distortion, hardness is better.
Embodiment 7
20 g sweet potato starch mix with 15.6 g water, make face embryo, and in 120 DEG C of steam, slaking 1 hour, is cooled to room temperature.Slaking sweet potato starch is put into baking oven 100 DEG C of freeze-day with constant temperature to constant weight.Under nitrogen protection, in retort furnace, carbonization is carried out to the slaking sweet potato starch sample of drying, to rise in 250 DEG C of environment again constant temperature 5 hours by 150 DEG C with the temperature rise rate of 2 DEG C/min.Be cooled to room temperature and obtain aging starch carbon material 23 g without distortion, hardness is better.
Embodiment 8
Pre-treatment step, by wheat starch and water mixing, kneading becomes face embryo, compression moulding, and starch and quality ratio be, starch: water=65:35;
Maturation stage, gained face embryo steam heating at 60 DEG C of temperature, makes the abundant slaking in starch crystals district;
Dehydrating step, by the starch of abundant slaking drying and dehydrating at 50 DEG C of temperature;
Carburising step, will dewater aging starch under inert nitrogen gas protection, and keep 10 hours, obtain carbon material at 180 DEG C of temperature.
Embodiment 9
Pre-treatment step, by W-Gum and water mixing, kneading becomes face embryo, compression moulding, and starch and quality ratio be, starch: water=85:15;
Maturation stage, gained face embryo steam heating at 150 DEG C of temperature, makes the abundant slaking in starch crystals district;
Dehydrating step, by the starch of abundant slaking drying and dehydrating at 120 DEG C of temperature;
Carburising step, will dewater aging starch under protection of inert gas, keep 0.5 hour at 450 DEG C of temperature, obtain carbon material.
Embodiment 10
Pre-treatment step, by potato starch, water, glycerine, polyoxyethylene glycol mixing, kneading becomes face embryo, compression moulding, starch and
Water, glycerine, polyoxyethylene glycol mass ratio be, starch: water: glycerine: polyoxyethylene glycol=65:30:4:1; Other step is with embodiment 8.
Embodiment 11
Pre-treatment step, by glutinous rice starch, water, yeast, sodium bicarbonate, glycerine mixing, kneading becomes face embryo, compression moulding, and glutinous rice starch, water, yeast, sodium bicarbonate, qualities of glycerin ratio is, starch: water: yeast: sodium bicarbonate: glycerine=70:20:4:1:2:3; Other step is with embodiment 8.
Embodiment 11
Pre-treatment step, potato starch, water, yeast, sodium bicarbonate, glycerine, polyoxyethylene glycol and lipid acid Tegin 55G are mixed, kneading becomes face embryo, compression moulding, potato starch, water, yeast, sodium bicarbonate, glycerine, polyoxyethylene glycol and lipid acid Tegin 55G mass ratio be, potato starch: water: yeast: sodium bicarbonate: glycerine: polyoxyethylene glycol: lipid acid Tegin 55G=68:18:2:2:3:4:3; Other step is with embodiment 8.
Starch material used is various plant roots and stems seeds processing gained starch, comprises purification starch or the undressed raw starch containing Mierocrystalline cellulose, protein.Described auxiliary material is one or more in yeast, sodium bicarbonate, glycerine, polyoxyethylene glycol and lipid acid Tegin 55G.Above about specific descriptions of the present invention, be only not limited to the technical scheme described by the embodiment of the present invention for illustration of the present invention.Those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent replacement, to reach identical technique effect.Needs are used, all in protection scope of the present invention as long as meet.
Claims (7)
1. a preparation method for starch base carbon material, is characterized in that comprising the steps:
Pre-treatment step, by starch and water mixing, kneading becomes face embryo, compression moulding, and starch and quality ratio be, starch: water=65-85:15-35;
Maturation stage, gained face embryo steam heating at 60-150 DEG C of temperature, makes the abundant slaking in starch crystals district;
Dehydrating step, by the starch of abundant slaking drying and dehydrating at 50-120 DEG C of temperature;
Carburising step, will dewater aging starch under protection of inert gas, at 180-450 DEG C of temperature, keep 0.5-10 hour, obtain carbon material.
2. the preparation method of a kind of starch base carbon material according to claim 1, is characterized in that described dehydrating step and carburising step can complete in two steps, also can complete continuously in a step.
3. the preparation method of a kind of starch base carbon material according to claim 1, is characterized in that described pre-treatment step
In, starch material used is various plant roots and stems seeds processing gained starch, comprises purification starch or the undressed raw starch containing Mierocrystalline cellulose, protein.
4. the preparation method of a kind of starch base carbon material according to claim 3, is characterized in that starch used comprises wheat
Starch, W-Gum, potato starch, sticky rice flour.
5. the preparation method of a kind of starch base carbon material according to claim 1, is characterized in that described pre-treatment step
Comprise auxiliary material, the mass ratio of starch, water and auxiliary material is, starch: water: auxiliary material=65-85:15-35:0-5.
6. the preparation method of a kind of starch base carbon material according to claim 5, is characterized in that described auxiliary material is one or more in yeast, sodium bicarbonate, glycerine, polyoxyethylene glycol and lipid acid Tegin 55G.
7. the preparation method of a kind of starch base carbon material according to claim 1, is characterized in that described carburising step, and rare gas element is nitrogen, carbonic acid gas, argon gas or water vapour.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117593A (en) * | 2017-04-28 | 2017-09-01 | 华南理工大学 | A kind of starch glycosyl carbon material and its application in anisole sustained release |
| CN107385564A (en) * | 2017-08-28 | 2017-11-24 | 德阳力久云智知识产权运营有限公司 | A kind of preparation method of starch base carbon fibre |
| CN107651960A (en) * | 2017-10-27 | 2018-02-02 | 哈尔滨工业大学 | A kind of method that foamed carbon material is made based on amylofermentation principle |
| CN108002363A (en) * | 2017-12-08 | 2018-05-08 | 湖南大学 | A kind of preparation method of porous nano carbon |
| CN113044836A (en) * | 2021-02-03 | 2021-06-29 | 成都理工大学 | Preparation method of porous activated carbon and oil-water separation application thereof |
| CN115367748A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | High-specific-surface-area formed carbon material and preparation method thereof |
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| CN101181986A (en) * | 2007-11-16 | 2008-05-21 | 广西师范大学 | Micron porous carbon microsphere and preparation method thereof |
| CN103708440A (en) * | 2014-01-07 | 2014-04-09 | 上海交通大学 | Method for preparing light sub-micron carbon microspheres by using biomass carbon source material |
| CN104118861A (en) * | 2014-07-14 | 2014-10-29 | 天津工业大学 | Preparation method of multilevel porous carbon with ultrahigh specific surface area |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101181986A (en) * | 2007-11-16 | 2008-05-21 | 广西师范大学 | Micron porous carbon microsphere and preparation method thereof |
| CN103708440A (en) * | 2014-01-07 | 2014-04-09 | 上海交通大学 | Method for preparing light sub-micron carbon microspheres by using biomass carbon source material |
| CN104118861A (en) * | 2014-07-14 | 2014-10-29 | 天津工业大学 | Preparation method of multilevel porous carbon with ultrahigh specific surface area |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117593A (en) * | 2017-04-28 | 2017-09-01 | 华南理工大学 | A kind of starch glycosyl carbon material and its application in anisole sustained release |
| CN107385564A (en) * | 2017-08-28 | 2017-11-24 | 德阳力久云智知识产权运营有限公司 | A kind of preparation method of starch base carbon fibre |
| CN107651960A (en) * | 2017-10-27 | 2018-02-02 | 哈尔滨工业大学 | A kind of method that foamed carbon material is made based on amylofermentation principle |
| CN108002363A (en) * | 2017-12-08 | 2018-05-08 | 湖南大学 | A kind of preparation method of porous nano carbon |
| CN108002363B (en) * | 2017-12-08 | 2020-12-04 | 湖南大学 | Preparation method of porous nano carbon |
| CN113044836A (en) * | 2021-02-03 | 2021-06-29 | 成都理工大学 | Preparation method of porous activated carbon and oil-water separation application thereof |
| CN115367748A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | High-specific-surface-area formed carbon material and preparation method thereof |
| CN115367748B (en) * | 2021-05-20 | 2024-02-02 | 中国石油化工股份有限公司 | High specific surface area formed carbon material and preparation method thereof |
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