CN101844070B - Porous activated carbon fiber adsorbing material of sheath-core composite structure and preparation thereof - Google Patents
Porous activated carbon fiber adsorbing material of sheath-core composite structure and preparation thereof Download PDFInfo
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- CN101844070B CN101844070B CN2010101695207A CN201010169520A CN101844070B CN 101844070 B CN101844070 B CN 101844070B CN 2010101695207 A CN2010101695207 A CN 2010101695207A CN 201010169520 A CN201010169520 A CN 201010169520A CN 101844070 B CN101844070 B CN 101844070B
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Abstract
The invention relates to a porous activated carbon fiber adsorbing material of a sheath-core composite structure and preparation thereof. The structure of the porous activated carbon fiber adsorbing material is as follows: a surface layer is made of macro-porous carbon fiber, and a core layer is made of non-porous carbon fiber; wherein the ratio of the cross-sectional area of the surface layer is controlled to be 10-40 percent, and the cross-section thereof is uniformly provided holes. The preparation comprises the following steps: (1) impregnating carbon fiber in aqueous solution of sodium salt for 2-4 hours, and then placing the carbon fiber in an activation furnace; (2) heating to 800-1100 DEG C under the protection of an inert gas, adding steam, and carrying out constant-temperature activation for 0.5-2 hour(s); and (3) reducing the temperature to be below 200 DEG C, and cutting off the inert gas and the steam, thereby preparing the porous activated carbon fiber adsorbing material. The strength of the adsorbing material provided by the invention is up to 0.3-0.6GPa, and the surface layer thereof is of a porous structure, thereby not only prolonging the service life of the material, but also facilitating the loading of large-sized molecules such as biological cells and the like; and the preparation method can be controlled easily, the activation process is simple, and the invention is suitable for large-scale production.
Description
Technical field
The invention belongs to activated carbon fiber adsorbing material and preparation field thereof, particularly a kind of porous activated carbon fiber adsorbing material and preparation thereof with core-sheath composite structure.
Background technology
NACF (ACF), also claim fibrous activated carbon, is high-efficiency activated sorbing material and environment-friendly engineering material that performance is better than active carbon, and its carbon atom over 50% is positioned at surfaces externally and internally, is built into unique adsorption structure, is called as the superficiality solid.It is by fibrous presoma, through certain program carbonization-activation, forms.More flourishing specific area and narrower pore-size distribution make it have adsorption/desorption speed and larger adsorption capacity faster, and because it can be processed as the different shapes such as felt, cloth, paper easily, and there is the acid and alkali-resistance corrosion resistance characteristic, make one come out just to obtain that people pay close attention to widely and deep research.In fields such as environmental protection, catalysis, medicine, military projects, be used widely at present.
Current fibrous NACF intensity is no more than 0.2GPa substantially, and the eurypyloue ACF intensity index of tool is lower, does not substantially reach 0.1GPa.Different aperture, ACF surface can give activated carbon fiber different absorption properties.Aspect the preparation of macropore, haveing breakthrough at present, basically be to add the reaming catalyst to reach the purpose that obtains macropore in raw material, but in existing preparation technology, the generation of macropore easily causes the loss of intensity, and too low intensity has also had a strong impact on the scope of application and the service life of ACF.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of porous activated carbon fiber adsorbing material and preparation thereof with core-sheath composite structure, this sorbing material intensity can be controlled in 0.3-0.6Gpa, top layer is loose structure, when extending the materials'use life-span, also is conducive to the load biological cell; And the preparation method is easy to control, and activating process is simple, be applicable to large-scale production.
A kind of porous activated carbon fiber adsorbing material with core-sheath composite structure of the present invention, its structure forms and comprises: top layer is the eurypyloue carbon fiber of tool, the carbon fiber that sandwich layer is atresia, the shared sectional area ratio of its mesexine is controlled at 10%-40%, and cross-sectional distribution has hole.
Described carbon fiber is viscose-based carbon fiber, polyacrylonitrile-based carbon fibre or asphalt base carbon fiber, and preferred carbon fiber is viscose-based carbon fiber, and carbon fiber strength is 0.4GPa~0.8Gpa;
Described porous activated carbon fiber adsorbing material, the aperture of its top layer macropore is 50~600nm, specific area reaches 1000~2000m
2/ g.
A kind of preparation method with porous activated carbon fiber adsorbing material of core-sheath composite structure of the present invention comprises:
(1) by above-mentioned impregnated carbon fiber in the aqueous solution of sodium salt 2~4 hours, wherein the concentration of sodium salt was 0.1mol/L~saturated concentration;
(2) above-mentioned carbon fiber is put into to activation furnace, be heated to 800~1100 ℃ under the inert gas shielding condition, heating rate is 5~20 ℃/min, passes into steam constant temperature activation process 0.5~2 hour;
(3) after cooling to 200 ℃, close inert gas and water vapour, make porous activated carbon fiber adsorbing material.
Sodium salt in described step (1) is selected from one or more the mixture in sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium phosphate, sodium chloride, sodium nitrate, sodium sulphate, and concentration is 0.1mol/L~2.0mol/L.
The present invention, on original basis for preparing macropore activated carbon fiber, directly adopts carbon fiber as raw material, and by the concentration of regulation and control salt and size and the position that activation condition carrys out control hole, preparation has the activated carbon fiber adsorbing material of unique texture; The activated carbon fiber that top layer is porous, hole is given the material absorption property, and sandwich layer is the carbon fiber strength skeleton, and this structure has guaranteed that this material has absorption property and higher intensity preferably simultaneously.
Beneficial effect
(1) sorbing material intensity of the present invention can be controlled in 0.3-0.6Gpa, and top layer is loose structure, when extending the materials'use life-span, also is conducive to the load biological cell;
(2) preparation method of this material is easy to control, and activating process is simple, is applicable to large-scale production.
The accompanying drawing explanation
The sorbing material electromicroscopic photograph that Fig. 1 is different hole distributions;
Wherein, (a), for surface hole defect distributes, (b) be the cross section hole distribution;
Fig. 2 is sorbing material of the present invention " core-skin " structural model schematic diagram;
Wherein, the activated carbon fiber that top layer is porous, sandwich layer is carbon fiber;
The material section photo that Fig. 3 is embodiment 1;
The material section photo that Fig. 4 is embodiment 2;
The material section photo that Fig. 5 is embodiment 3;
The material section photo that Fig. 6 is embodiment 4.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The viscose-based carbon fiber that is 0.7GPa by intensity is placed in the Na of 0.1M
3pO
4in solution standing 3 hours, then put into activation furnace, pass into water vapour and N
2, be warmed up to 1000 ℃ with the speed of 20 ℃/min, pass into steam constant temperature activation process 0.5 hour, after cooling to 200 ℃, close inert gas and water vapour, make porous activated carbon fiber adsorbing material.
The electromicroscopic photograph that Fig. 3 is the present embodiment sorbing material, on top layer, aperture is 50nm<aperture<300nm, and intensity reaches 0.4GPa, and specific area is 1030m
2/ g.
Embodiment 2
The viscose-based carbon fiber that is 0.7GPa by intensity is placed in the NaH of 0.2M
2pO
4in solution standing 2 hours, then put into activation furnace, pass into water vapour and N
2, be warmed up to 1000 ℃ with the speed of 10 ℃/min, pass into steam constant temperature activation process 1 hour, after cooling to 200 ℃, close inert gas and water vapour, make porous activated carbon fiber adsorbing material.
The electromicroscopic photograph that Fig. 4 is the present embodiment sorbing material, on top layer, aperture is 100nm<aperture<500nm, and intensity reaches 0.3GPa, and specific area is 1100m
2/ g.
Embodiment 3
The viscose-based carbon fiber that is 0.7GPa by intensity is placed in the Na of 0.1M
2hPO
4in solution standing 4 hours, then put into activation furnace, pass into water vapour and N
2, be warmed up to 1000 ℃ with the speed of 10 ℃/min, pass into steam constant temperature activation process 0.5 hour, after cooling to 200 ℃, close inert gas and water vapour, make porous activated carbon fiber adsorbing material.
The electromicroscopic photograph that Fig. 5 is the present embodiment sorbing material, on top layer, aperture is 50nm<aperture<300nm, and intensity reaches 0.4GPa, and specific area is 1280m
2/ g.
Embodiment 4
The viscose-based carbon fiber that is 0.7GPa by intensity is placed in the NaH of 0.1M
2pO
4and Na
2hPO
4mixed solution in standing 2 hours, then put into activation furnace, pass into water vapour and N
2, be warmed up to 1100 ℃ with the speed of 5 ℃/min, pass into steam constant temperature activation process 0.5 hour, after cooling to 200 ℃, close inert gas and water vapour, make porous activated carbon fiber adsorbing material.
The electromicroscopic photograph that Fig. 6 is the present embodiment sorbing material, on top layer, aperture is 50nm<aperture<200nm, and intensity reaches 0.3GPa, and specific area is 1520m
2/ g.
Claims (1)
1. the preparation method with porous activated carbon fiber adsorbing material of core-sheath composite structure comprises:
The viscose-based carbon fiber that is 0.7GPa by intensity is placed in the NaH of 0.1M
2pO
4and Na
2hPO
4mixed solution in standing 2 hours, then put into activation furnace, pass into water vapour and N
2, be warmed up to 1100 ℃ with the speed of 5 ℃/min, pass into steam constant temperature activation process 0.5 hour, after cooling to 200 ℃, close inert gas and water vapour, make porous activated carbon fiber adsorbing material; On the porous activated carbon fiber adsorbing material top layer, aperture is 50nm<aperture<200nm, and intensity reaches 0.3GPa, and specific area is 1520m
2/ g.
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US20160046491A1 (en) * | 2013-03-22 | 2016-02-18 | Toray Industries, Inc. | Porous carbon material, precursor for porous carbon material, process for producing precursor for porous carbon material, and process for producing porous carbon material |
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CN103320904B (en) * | 2013-06-20 | 2015-03-18 | 中国科学院理化技术研究所 | Steam activation preparation method and preparation device of microporous activated carbon fibers |
US10704172B2 (en) | 2014-04-10 | 2020-07-07 | 3M Innovative Properties Company | Fibers and articles including them |
CN106702538A (en) * | 2016-12-08 | 2017-05-24 | 北京化工大学 | Preparation method of high-performance activated carbon fibers |
CN110013832B (en) * | 2019-03-18 | 2022-03-04 | 广州誉隆智慧科技有限公司 | Carbon fiber modified material for aquaculture water treatment and preparation method thereof |
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CN1762575A (en) * | 2005-09-14 | 2006-04-26 | 东华大学 | Method for preparation of active carbon fibrous absorption material |
CN101337176A (en) * | 2008-08-08 | 2009-01-07 | 东华大学 | Preparation method of macropore activated carbon fiber with intensity more than 0.3GPa |
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JP2596984B2 (en) * | 1988-07-27 | 1997-04-02 | 大阪瓦斯株式会社 | Agglomerated activated carbon fiber aggregate and method for producing the same |
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CN1762575A (en) * | 2005-09-14 | 2006-04-26 | 东华大学 | Method for preparation of active carbon fibrous absorption material |
CN101337176A (en) * | 2008-08-08 | 2009-01-07 | 东华大学 | Preparation method of macropore activated carbon fiber with intensity more than 0.3GPa |
Non-Patent Citations (4)
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Cited By (2)
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US20160046491A1 (en) * | 2013-03-22 | 2016-02-18 | Toray Industries, Inc. | Porous carbon material, precursor for porous carbon material, process for producing precursor for porous carbon material, and process for producing porous carbon material |
US10011487B2 (en) * | 2013-03-22 | 2018-07-03 | Toray Industries, Inc. | Porous carbon material, precursor for porous carbon material, process for producing precursor for porous carbon material, and process for producing porous carbon material |
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