CN104326470A - Method for preparing high specific surface area micron-scale spherical activated carbon from carboxymethyl cellulose - Google Patents
Method for preparing high specific surface area micron-scale spherical activated carbon from carboxymethyl cellulose Download PDFInfo
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- CN104326470A CN104326470A CN201410612515.7A CN201410612515A CN104326470A CN 104326470 A CN104326470 A CN 104326470A CN 201410612515 A CN201410612515 A CN 201410612515A CN 104326470 A CN104326470 A CN 104326470A
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Abstract
The invention discloses a method for preparing high specific surface area micron-scale spherical activated carbon from carboxymethyl cellulose. The method is characterized by comprising the following steps: by taking carboxymethyl cellulose as a raw material, performing ultrasonic oscillation on carboxymethyl cellulose solutions of different concentrations, transferring into a sealed high-pressure reaction kettle that polytetrafluoroethylene is lined inside, and performing hydrothermal carbonization reaction while controlling the temperature and the time; and naturally cooling the reaction system to be the room temperature, and washing with distilled water and absolute ethyl alcohol, thereby obtaining precursor carbon spheres; putting a certain amount of the precursor carbon spheres into a tubular furnace, gradually heating in the presence of N2 while controlling the heating velocity, the activation temperature and the activation time, introducing N2 after the activation is completed, and naturally cooling to be the room temperature, thereby obtaining the micron-scale spherical activated carbon, wherein the specific surface area of the prepared micron-scale spherical activated carbon can be about 1000m<2>/g, and the average aperture of the prepared micron-scale spherical activated carbon is within 2-4nm. The method has the main characteristics that the carboxymethyl cellulose biomass material is low in price and rich in resource, the operation of hydrothermal carbonization equipment is simple, the process is green and environment-friendly, and the morphology, the particle size and the dispersity of a product can be controlled by conditioning and controlling the reaction conditions.
Description
Art:
The present invention relates to field prepared by Carbon Materials, particularly relate to the method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose.
Background technology:
Carbon microspheres material has the feature such as regular globosity, good tap density and high-specific surface area, excellent electrical and thermal conductivity performance because of it, is widely used in the fields such as the preparation of support of the catalyst, electrode materials, template and matrix material.The different novel charcoal materials preparing pattern, Various Functions of reaction raw materials and preparation technology.Compared with traditional industrial chemicals, biomass-based Carbon Materials is subject to the extensive concern of investigator because of its feature such as environmental protection, wide material sources.
Japanese Patent 50-018879 and 55-113608 describes a kind of preparation method of ball shape active carbon, by the media such as asphalt series stock dispersion Yu Shui, prepares spherical particle, then spherical particle is carried out carbonization-activation to prepare ball shape active carbon.Ball shape active carbon hardness prepared by this method is higher, and sphere sizes is less and evenly, but its raw material choose tradition industrial chemicals, and in source, economic and aspect of performance has certain limitation.
US Patent No. 5206207, US5324703 etc. adopt wood material to prepare specific surface area up to 2500m through phosphoric acid activation at 480 DEG C
2the granulated active carbon of about/g, although its absorption property reached is comparatively strong, its preparation technology's cycle is longer, and energy consumption is comparatively large, and the irregular Application Areas limiting it of the pattern obtaining granulated active carbon.
The preparation method of publication number a kind of ball shape active carbon that has been the Introduction To Cn Patent of CNNIO2259853A, the method with powdered carbon and pitch powder for raw material, mix by a certain percentage, use bowl granulator to prepare charcoal ball, then the charcoal ball of preparation is carried out activation in Slapple activating furnace and obtain ball shape active carbon.Ball shape active carbon particle diameter prepared by this method is at about 1 ~ 10mm, and particle diameter is larger and uneven, and morphology control is undesirable.
The preparation method of publication number a kind of mesopore spherical activated carbon that has been the Introduction To Cn Patent of CN101177265A; the method with styrene diethylene benzene copoly mer bead for presoma; after liquor zinci chloridi dipping, polymer globules is dry; then activate under nitrogen protection; use dilute hydrochloric acid and distilled water to be removed by chlorion, obtain mesopore spherical activated carbon.Ball shape active carbon prepared by this method, mesoporous can reach 74% ~ 85%, good application prospect is had in fields such as liquid phase adsorption, catalysis, biomedicines, but the method take zinc chloride as activator, easily cause the pollution of product, and the reusing of activator is poor, preparation technology expends higher.
Publication number a kind of preparation method with the ball shape active carbon of high-specific surface area that has been the Introduction To Cn Patent of CN101062770A; raw material is various sphere material; as petroleum pitch ball, coal pitch spheres, styrene resin ball, phenolic resin balls etc.; raw material is carbonized process under protection of inert gas; by KOH solution, carbide is activated, after cooling and washing, obtain the ball shape active carbon of high-specific surface area.Though this method can obtain the ball shape active carbon of high specific surface area, but adopt alkali activation relatively more serious to equipment corrosion, and other elements that easily adulterate.
In sum, prepare the method for ball shape active carbon at present, most with traditional chemical materials for presoma, although the Carbon Materials specific surface area prepared is large, cost is higher, and chemical activation processes intensity is large, corrosive equipment and cause environmental pollution.
Summary of the invention:
The object of the present invention is to provide the method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose.And the pattern of ball shape active carbon and size tunable, process is simple, and cheaper starting materials is easy to get.
In order to achieve the above object, the technical solution used in the present invention comprises: the method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose, it is characterized in that: take carboxymethyl cellulose as raw material, proceed in the enclosed high pressure reactor of inner liner polytetrafluoroethylene by after the cmc soln sonic oscillation of different concns, control temperature and time carry out hydro-thermal carbonization reaction.Reaction system is naturally cooled to room temperature, after distilled water and absolute ethanol washing, obtains presoma charcoal ball.A certain amount of presoma charcoal ball is placed in tube furnace at N
2the lower temperature programming of protection, controls temperature rise rate, activation temperature and soak time, logical N after activation
2naturally cool to room temperature, obtain micron-size spherical gac, prepared ball shape active carbon specific surface area can reach 1000m
2about/g, mean pore size is between 2 ~ 4nm.
Advantage of the present invention is:
1, raw material of the present invention is biological material carboxymethyl cellulose; material surface contains abundant oxygen-containing functional group; and it is cheap; abundance; there is huge economic development value; with carboxymethyl cellulose for high performance Carbon Materials prepared by your raw material, the use value of raw material can be improved, alleviate the crisis of fossil energy to a certain extent.
2, the present invention uses hydro-thermal charring process, and this method equipment is simple to operation, production technique environmental protection, and controls the pattern of product, particle diameter and dispersiveness by regulation and control reaction conditions.
3, the present invention uses CO
2activation method processes charcoal ball presoma, and whole technological operation is simple, and environmental protection, does not add any element, does not damage the spherical morphology of presoma, obtains higher specific surface area and good pore texture simultaneously.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope (SEM) photograph of presoma charcoal ball; The scanning electron microscope (SEM) photograph of Fig. 2 micron-size spherical gac.
Embodiment:
Below the invention process is described in further detail:
The method of high-specific surface area micron-size spherical gac is prepared by carboxymethyl cellulose, it is characterized in that: take carboxymethyl cellulose as raw material, proceed in the enclosed high pressure reactor of inner liner polytetrafluoroethylene by after the cmc soln sonic oscillation of different concns, control temperature and time carry out hydro-thermal carbonization reaction.Reaction system is naturally cooled to room temperature, after distilled water and absolute ethanol washing, obtains presoma charcoal ball.A certain amount of presoma charcoal ball is placed in tube furnace at N
2the lower temperature programming of protection, controls temperature rise rate, activation temperature and soak time, logical N after activation
2naturally cool to room temperature, obtain micron-size spherical gac, prepared ball shape active carbon specific surface area can reach 1000m
2about/g, mean pore size is between 2 ~ 4nm.
Below, the present invention will be further detailed by embodiment, but it is not limited to any one or similar example of these embodiments.
Embodiment 1:
(1) by 40mL cmc soln (1.5g40mL H
2o) sonic oscillation 30min, proceeding to volume is in the enclosed high pressure reactor of the inner liner polytetrafluoroethylene of 50mL, hydro-thermal charing 10h at 200 DEG C, repeatedly wash to washings through distilled water and dehydrated alcohol (content is no less than 99.7%) after being cooled to room temperature and clarify, gained black powder dries 6h at 105 DEG C, obtains charcoal ball material.
(2) charcoal ball is placed in tube furnace at N as presoma
2the lower temperature programming to 800 DEG C of protection, temperature rise rate is 5 DEG C/min, then keeps temperature to carry out CO
2activation, soak time is 2h, logical N after activation
2naturally cool to room temperature, obtain ball shape active carbon.
(3) BET specific surface area obtaining ball shape active carbon is 637.64m
2/ g, micropore specific area accounts for 77.17% of BET specific surface area, and total pore volume is 0.5188cm
3/ g, mean pore size is 3.25nm.
Embodiment 2:
(1) by 40mL cmc soln (1.5g40ml H
2o) sonic oscillation 30min, proceeding to volume is in the enclosed high pressure reactor of the inner liner polytetrafluoroethylene of 50mL, hydro-thermal charing 10h at 200 DEG C, repeatedly wash to washings through distilled water and dehydrated alcohol (content is no less than 99.7%) after being cooled to room temperature and clarify, gained black powder dries 6h at 105 DEG C, obtains charcoal ball material.
(2) charcoal ball is placed in tube furnace at N as presoma
2the lower temperature programming to 850 DEG C of protection, temperature rise rate is 5 DEG C/min, then keeps temperature to carry out CO
2activation, soak time is 2h, logical N after activation
2naturally cool to room temperature, obtain ball shape active carbon.
The BET specific surface area obtaining ball shape active carbon is 1005.85m
2/ g, micropore specific area accounts for 68.07% of BET specific surface area, and total pore volume is 0.6982cm
3/ g, mean pore size is 2.78nm.
Claims (6)
1. prepared the method for high-specific surface area micron-size spherical gac by carboxymethyl cellulose for one kind, it is characterized in that: take carboxymethyl cellulose as raw material, proceed in the enclosed high pressure reactor of inner liner polytetrafluoroethylene by after the cmc soln sonic oscillation of different concns, control temperature and time carry out hydro-thermal carbonization reaction.Reaction system is naturally cooled to room temperature, after distilled water and absolute ethanol washing, obtains presoma charcoal ball.A certain amount of presoma charcoal ball is placed in tube furnace at N
2the lower temperature programming of protection, controls temperature rise rate, activation temperature and soak time, logical N after activation
2naturally cool to room temperature, obtain micron-size spherical gac, prepared ball shape active carbon specific surface area can reach 1000m
2about/g, mean pore size is between 2 ~ 4nm.
2. according to a kind of method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose according to claim 1, it is characterized in that: take carboxymethyl cellulose as raw material, before hydro-thermal carbonization reaction, is 0.8 ~ 2g/40mL H by concentration
2the cmc soln of O carries out sonic oscillation, and ultrasonic power is 800 ~ 1000W, and ultrasonic time is 1 ~ 1.5h.
3. according to a kind of method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose according to claim 1, it is characterized in that: the cmc soln after sonic oscillation is proceeded in the enclosed high pressure reactor of inner liner polytetrafluoroethylene and carry out hydro-thermal carbonization reaction, temperature of reaction is 180 ~ 240 DEG C, and the reaction times is 6 ~ 12h.
4. according to a kind of method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose according to claim 1, it is characterized in that: a certain amount of presoma charcoal ball is placed in tube furnace and carries out CO
2activation, at N
2the lower temperature programming of protection, controls temperature rise rate 3 ~ 6 DEG C of min
-1, activation temperature is 800 ~ 950 DEG C, and soak time is 2 ~ 4h, logical N after activation
2naturally cool to room temperature, obtain micron-size spherical gac.
5., according to a kind of method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose according to claim 1, it is characterized in that: CO
2gac spherical morphology prepared by activation keeps very well, and dispersiveness is also fine, and particle diameter is less than 2 μm.
6., according to a kind of method being prepared high-specific surface area micron-size spherical gac by carboxymethyl cellulose according to claim 1, it is characterized in that: CO
2micron-size spherical gac prepared by activation, specific surface area can reach 1000m
2about/g, mean pore size is between 2 ~ 4nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883805A (en) * | 2016-04-20 | 2016-08-24 | 南昌航空大学 | Preparation method of camellia seed shell based carbon microspheres with high specific surface area |
| CN106336214A (en) * | 2016-08-29 | 2017-01-18 | 天长市中德电子有限公司 | NiZn soft magnetic ferrite material with high flexural strength |
| CN108187614A (en) * | 2017-12-26 | 2018-06-22 | 华中科技大学 | A kind of biomass porous carbon sorbent preparation method and product for flue gas demercuration |
| CN108383118A (en) * | 2018-05-25 | 2018-08-10 | 常州大学 | A kind of physically activated preparation method of the microporous carbon of superhigh specific surface area |
| CN109158082A (en) * | 2018-09-25 | 2019-01-08 | 华中科技大学 | A kind of demercuration method activated online based on porous charcoal |
| CN109923066A (en) * | 2016-12-21 | 2019-06-21 | 株式会社吴羽 | Spheric active carbon and its manufacturing method |
| CN112108118A (en) * | 2020-09-21 | 2020-12-22 | 黄河水利职业技术学院 | Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883805A (en) * | 2016-04-20 | 2016-08-24 | 南昌航空大学 | Preparation method of camellia seed shell based carbon microspheres with high specific surface area |
| CN105883805B (en) * | 2016-04-20 | 2018-01-12 | 南昌航空大学 | A kind of preparation method of the high-specific surface area carbosphere based on tea seed shell base |
| CN106336214A (en) * | 2016-08-29 | 2017-01-18 | 天长市中德电子有限公司 | NiZn soft magnetic ferrite material with high flexural strength |
| CN109923066A (en) * | 2016-12-21 | 2019-06-21 | 株式会社吴羽 | Spheric active carbon and its manufacturing method |
| CN109923066B (en) * | 2016-12-21 | 2022-06-28 | 株式会社吴羽 | Spherical activated carbon and method for producing same |
| CN108187614A (en) * | 2017-12-26 | 2018-06-22 | 华中科技大学 | A kind of biomass porous carbon sorbent preparation method and product for flue gas demercuration |
| CN108383118A (en) * | 2018-05-25 | 2018-08-10 | 常州大学 | A kind of physically activated preparation method of the microporous carbon of superhigh specific surface area |
| CN109158082A (en) * | 2018-09-25 | 2019-01-08 | 华中科技大学 | A kind of demercuration method activated online based on porous charcoal |
| CN109158082B (en) * | 2018-09-25 | 2020-05-19 | 华中科技大学 | Demercuration method based on porous carbon online activation |
| CN112108118A (en) * | 2020-09-21 | 2020-12-22 | 黄河水利职业技术学院 | Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof |
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Application publication date: 20150204 |