CN1328425C - Active carbon fiber in hollow morphological structure, and preparation method - Google Patents
Active carbon fiber in hollow morphological structure, and preparation method Download PDFInfo
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- CN1328425C CN1328425C CNB2005100305458A CN200510030545A CN1328425C CN 1328425 C CN1328425 C CN 1328425C CN B2005100305458 A CNB2005100305458 A CN B2005100305458A CN 200510030545 A CN200510030545 A CN 200510030545A CN 1328425 C CN1328425 C CN 1328425C
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Abstract
The present invention relates to activated carbon fiber adopting a hollow structure and a preparing method of the activated carbon fiber, wherein the pore size distribution of middle holes and large holes is from 2 to 90 nm, and the pore size distribution of the middle holes is mainly from 2 to 5 nm. Medical polyacrylonitrile hollow fiber is adopted as raw material and is soaked for pre-processing in solution containing phosphide, and then, the medical polyacrylonitrile hollow fiber is preoxidized, carbonized and activated to form the activated carbon fiber adopting a hollow structure. The polyacrylonitrile group activated carbon fiber produced by adopting the method has a large specific surface area, and the content and the specific surface area of middle pores in the carbon fiber are high and large, so that the carbon fiber has a high rate of adsorbing small molecule substances and middle molecule substances. The method of the present invention has the advantages of simple technology and low investment. The product of the present invention has the advantages of favorable adsorbing performance, wide range of application and favorable purifying effect and can be suitable for the fields needing adsorbing purification, such as air purification, water purification, organic substance adsorbing purification, blood purification, etc.
Description
Technical field
The present invention relates to a kind of active carbon fibre peacekeeping preparation method with hollow morphosis.
Background technology
Activated carbon fiber (ACF) is the carbon material adsorbing material that grows up on charcoal fiber basis, is to be raw material with the organic fiber, forms through the high temperature carbonization activation.ACF compares with traditional active carbon, and have following characteristics: specific area is big; Pore-size distribution is concentrated; Adsorption desorption speed is fast, can have multiple processing forms such as felt, cloth, paper; Adsorption effect and adsorption density are irrelevant, and be effective especially to the trace materials absorption of ppb level, that is adsorption efficiency height under the low concentration.Active hollow charcoal fiber (ACHF) is then started late, it is a kind of novel sorbing material, compare with ACF, have that hollow, porous, oneself support, the aperture can characteristics such as control by the processing conditions of fibrillation and charing, activation process, very little volume just can have very big specific area, can be used for absorption, separation and the dialysis etc. of liquid or admixture of gas, widen its application in fields such as catalysis, medicine, electronics and liquid phase adsorption.
Chen Lu in 1999 (number of patent application: 97120296.6) reported that adopting solid polyacrylonitrile fibre is the method for raw material production activated carbon fiber, but pre-oxygen silk inorganic salts NaCO
3Soak, but this method has been used the pre-oxygen silk of metal ion, made and contain more metal ion among the final ACF inevitably, thereby limited its application in fields such as medicine, catalysis.(number of patent application: 95119030.X) wait the people to report that the mixed material that adopts resin and carbon material prepares the method for mesopore activated carbon fiber, the middle porosity in the prepared mesopore activated carbon fiber is 50-70% to Zhang Yinzhi in 1997.Liu Zhi benevolence in 1994 (number of patent application: 94108414.0) reported the method that to adopt wooden basic viscose nonwoven fabric or wooden basic viscose paper be the feedstock production high-adsorption active carbon fibre.1997 once Chinese reported that (number of patent application: 97108889.6) adopting natural fabric is the method that raw material (as sisal fiber) prepares activated carbon fiber.Above-described various fiber is solid fibers, and the fibrous inside of solid construction contains less hole, when the pre-oxidation of carrying out the later stage, charing and activating process, has influenced the infiltration of gas, causes structure " core-skin " structure different with performance easily.
Summary of the invention
The purpose of this invention is to provide a kind of activated carbon fiber with hollow morphosis.
Purpose of the present invention also provides a kind of preparation method with activated carbon fiber of hollow morphosis.
Activated carbon fiber with hollow morphosis of the present invention, wherein, the pore-size distribution of mesopore and macropore is 2～90nm.Except that micropore, the aperture is made up of the mesopore of 2～50nm and the macropore of aperture＞50nm～90nm, and wherein, the pore-size distribution of mesopore mainly concentrates on 2～5nm, and the content ratio that accounts for all mesopores is greater than 95%.
Preparation method with activated carbon fiber of hollow morphosis of the present invention is that the polyacrylonitrile doughnut is carried out preliminary treatment with the aqueous solution of phosphide, with after pre-oxidation, charing, activation form.
Concrete preparation method need change water once for raw fiber being cleaned and is immersed in the distilled water 1～3 day every a few hours, to remove glycerine and other auxiliary agent of fiber surface, puts into centrifuge then to dry, and dries naturally in air, is placed on then and fills P
2O
5Drier in be dried to constant weight and weighing; Be to soak doughnut in the phosphide aqueous solution of 2-10% weight (wt) to carry out preliminary treatment in 10-120 minute with concentration subsequently, take out the back and in air, dries naturally, be placed on then and fill P
2O
5Drier in to constant weight and weighing; Put into baking oven again with 200-300 ℃, heat and doughnut carried out pre-oxidation in 0.5-6 hour; Carrying out charing again handles, the doughnut of preliminary treatment and pre-oxidation is put into the quartz ampoule of tube furnace, take out air in the quartz ampoule with vavuum pump, begin to feed nitrogen, under nitrogen protection, with the heating rate heating of 10 ℃/min, carbonization temperature is 500-1000 ℃, and carbonization time is 10-110 minute; Charing finishes, and carries out activation processing again, and the doughnut after the charing continues to lead to CO under 600-1000 ℃ of condition in this stove
2Gas activates, and soak time is 20-100 minute; Activation finishes, and closes CO
2Gas is taken out CO in the quartz ampoule with vavuum pump
2Gas feeds nitrogen again, and when the nitrogen pressure in the quartz ampoule was 1 atmospheric pressure, nitrogen was closed at shutoff quartz ampoule two ends, when temperature is reduced to room temperature in quartz ampoule, takes out doughnut, is finished product-the have activated carbon fiber of hollow form.
At the phosphide described in the said method can be ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, phosphoric acid or metaphosphoric acid etc.
Doughnut among the present invention has the structural form of hollow, adopts the manufacturing process of dry-jet wet-spinning, thereby there is more microcellular structure in resulting fibrous inside, and its cross section is double finger-like pore structure, and the surface of fiber has abundant hole.This architectural characteristic has determined the later stage ACHF of preparation also to have abundant pore structure, thereby BET specific area and adsorption rate all be greatly improved, and centering relative molecular mass material especially is as VB
12Deng adsorption rate be significantly improved.
Activated carbon fiber with hollow morphosis of the present invention, possess than solid activated carbon fiber and more to many advantage, be a kind of small-molecule substance and medium molecular substance all to be had high absorption property, the activated carbon fiber of the high adsorption hollow morphosis of applied widely, good moldability, good purification.And be the simple preparation method of a kind of technology.
Description of drawings
Fig. 1 is that a kind of mesopore and macropore diameter with activated carbon fiber of hollow morphosis distributes;
Fig. 2 is the adsorption isotherm with activated carbon fiber of hollow morphosis;
Fig. 3 has the mesopore of different samples of activated carbon fiber of hollow morphosis and the graph of pore diameter distribution of macropore.
In the accompanying drawing, the abscissa of Fig. 1 is a relative pressure, and ordinate is the absorption pore volume; The abscissa of Fig. 2 is the aperture, and ordinate is to increase progressively pore volume; The abscissa of Fig. 3 is the aperture, and ordinate is to increase progressively pore volume.
The specific embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
Embodiment 1
Get polyacrylonitrile doughnut raw material 1.5g and at room temperature put into (the NH that concentration is 4% weight (wt)
4)
2HPO
4Soaked 30 minutes in the aqueous solution, after treating in air, to dry naturally, put into baking oven, in air, 230 ℃, to heat 2 hours, pre-oxidation finishes; Then pre-oxidized fibers is put into the quartz ampoule of tube furnace, be heated to 900 ℃ under nitrogen protection, 900 ℃ of heating 70 minutes, charing finished; Then furnace temperature is reduced to 800 ℃ naturally, feed CO
2Gas, 800 ℃ of heating 40 minutes, activation finished, and closes CO
2Gas is taken out CO in the quartz ampoule with vavuum pump
2Gas feeds nitrogen again, and when the nitrogen pressure in the quartz ampoule was 1 atmospheric pressure, nitrogen was closed at shutoff quartz ampoule two ends, when temperature is reduced to room temperature in quartz ampoule, takes out doughnut, is finished product-the have activated carbon fiber of hollow form.
Embodiment 2
Above-mentioned activated carbon fiber is to small-molecule substance (creatinine) and medium molecular substance (VB
12) adsorption rate as shown in the table: at 37 ℃, creatinine and VB
12The aqueous solution in Static Adsorption 24 hours.
| Title | Creatinine | VB 12 |
| Adsorption rate (%) | 99 | 84 |
Embodiment 3
The BET specific area and the middle pore specific surface area of above-mentioned activated carbon fiber are respectively
| BET specific area (m 2·g -1) | Middle pore specific surface area (m 2·g -1) | |
| Sample | 1422 | 1234 |
Embodiment 4
The adsorption isotherm of above-mentioned activated carbon fiber as shown in Figure 1.Mesopore and macropore diameter distribute as shown in Figure 2.
The test of above-mentioned data is to use U.S. Merck ﹠ Co., Inc to adsorb instrument Tristar 3000 automatically and adopts multipoint method, is to adsorb under the absorption proton liquid nitrogen temperature (77K) with nitrogen, adopts the BET method to calculate total surface area by recording adsorption isotherm, by t method (people such as B.C.Lippens, J.Cat., 4,319,1985) pore specific surface area in the calculating, by BJH method (people such as E.P.Barrett, J.Amer.Chem.Soc., 73,373,1951) calculating mesopore and macropore diameter distributes.
Embodiment 5
Get polyacrylonitrile doughnut raw material 1.5g and at room temperature put into (the NH that concentration is 4wt%
4)
2HP0
4Soaked 30 minutes in the aqueous solution, after treating in air, to dry naturally, put into baking oven, in air, 230 ℃, to heat 2 hours, pre-oxidation finishes; Then pre-oxidized fibers is put into the quartz ampoule of tube furnace, be heated to 900 ℃ under nitrogen protection, 900 ℃ of heating 30 minutes, charing finished; Then furnace temperature is reduced to 800 ℃ naturally, feed CO
2Gas, 800 ℃ of heating 40 minutes, activation finished, and closes CO
2Gas is taken out CO in the quartz ampoule with vavuum pump
2Gas feeds nitrogen again, and when the nitrogen pressure in the quartz ampoule was 1 atmospheric pressure, nitrogen was closed at shutoff quartz ampoule two ends, when temperature is reduced to room temperature in quartz ampoule, takes out doughnut, is finished product-have the activated carbon fiber of hollow form, is sample A.
Embodiment 6
The raw material 1.5g of embodiment 5 is at room temperature put into (the NH that concentration is 4wt%
4) H
2PO
4Soaked 30 minutes in the aqueous solution, treat in air, to dry naturally.Pre-oxidation, charing, activation method get sample B with embodiment 5.
Embodiment 7:
The raw material 1.5g of embodiment 5 is at room temperature put into (the NH that concentration is 4wt%
4)
3PO
4Soaked 30 minutes in the aqueous solution, treat in air, to dry naturally.Pre-oxidation, charing, activation method get sample C with embodiment 5.
Embodiment 8
The raw material 1.5g of embodiment 5 is at room temperature put into the H that concentration is 4wt%
3PO
4Soaked 30 minutes in the aqueous solution, treat in air, to dry naturally.Pre-oxidation, charing, activation method get sample D with embodiment 5.
Embodiment 9
The raw material 1.5g of embodiment 5 is at room temperature put into the HPO that concentration is 4wt%
3Soaked 30 minutes in the aqueous solution, in air, dry naturally.Pre-oxidation, charing, activation method get sample E with embodiment 5.
Fig. 3 is the mesopore of A, B, C, D, E sample and the graph of pore diameter distribution of macropore.
What list in the table below is the productive rate, shrinkage factor, BET specific area, middle pore specific surface area of A, B, C, D, E sample, to creatinine and VB
12Adsorption rate
The test of above-mentioned data is to use U.S. Merck ﹠ Co., Inc to adsorb instrument Tristar 3000 automatically and adopts multipoint method, is to adsorb under the absorption proton liquid nitrogen temperature (77K) with nitrogen, adopts the BET method to calculate total surface area by recording adsorption isotherm, by t method (people such as B.C.Lippens, J.Cat., 4,319,1985) pore specific surface area in the calculating, by BJH method (people such as E.P.Barrett, J.Amer.Chem.Soc., 73,373,1951) calculating mesopore and macropore diameter distributes.
| Sample | A | B | C | D | E |
| Productive rate/% | 39.6 | 40.3 | 40 | 45.2 | 42.5 |
| Shrinkage factor/% | 52.0 | 49.3 | 49.3 | 49.3 | 49.3 |
| BET specific area/m 2·g -1 | 766 | 659 | 705 | 451 | 428 |
| Middle pore specific surface area/m 2·g -1 | 174 | 104 | 93 | 71 | 75 |
| Adsorption rate/% to creatinine | 93.8 | 97.3 | 89.5 | 89.5 | 97.6 |
| To VB 12Adsorption rate/% | 97.7 | 93.4 | 94.3 | 94.7 | 97.2 |
Claims (5)
1. the activated carbon fiber with hollow morphosis is characterized in that the main activated carbon fiber that is mainly the hollow morphosis of 2～5nm by pore-size distribution.
2. a kind of preparation method with activated carbon fiber of hollow morphosis as claimed in claim 1 is characterized in that the phosphide aqueous solution soaking of cleaning and the dry medical grade polypropylene nitrile doughnut concentration of crossing is 2-10% weight was carried out preliminary treatment in 10-120 minute, dried; Keep down doughnut being carried out pre-oxidation in 0.5-6 hour at 200-300 ℃ again; The doughnut of preliminary treatment and pre-oxidation is carried out charing handle under nitrogen protection, with 10 ℃/minute heating rates heating, when carbonization temperature is 500-1000 ℃ charing 10-110 minute; Doughnut after the charing continues logical CO under 600-1000 ℃ of condition
2Gas carried out activation processing 20-100 minute.
3. method as claimed in claim 2 is characterized in that described phosphide is ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, phosphoric acid or metaphosphoric acid.
4. method as claimed in claim 2 is characterized in that described activated carbon fiber of carrying out the hollow form after the activation processing makes reactor reduce to room temperature and normal pressure under nitrogen protection.
5. want 2 described methods as right, it is characterized in that the described polyacrylonitrile doughnut that cleaned is meant soaks 1～3 day in distilled water, constantly change water, the dry then polyacrylonitrile doughnut of crossing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7934284B2 (en) | 2003-02-11 | 2011-05-03 | Braun Gmbh | Toothbrushes |
| US7941886B2 (en) | 2003-09-19 | 2011-05-17 | Braun Gmbh | Toothbrushes |
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|---|---|---|---|---|
| US8313723B2 (en) | 2005-08-25 | 2012-11-20 | Nanocarbons Llc | Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers |
| US20070178310A1 (en) | 2006-01-31 | 2007-08-02 | Rudyard Istvan | Non-woven fibrous materials and electrodes therefrom |
| EP2125617A1 (en) | 2007-02-14 | 2009-12-02 | University Of Kentucky Research Foundation Inc. | Methods of forming activated carbons |
| EP2441865B1 (en) * | 2009-06-10 | 2015-02-18 | Mitsubishi Rayon Co., Ltd. | Acrylonitrile swollen yarn for carbon fiber, precursor fiber bundle, flame-proof fiber bundle, carbon fiber bundle, and production methods thereof |
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| CN107385559A (en) * | 2017-08-11 | 2017-11-24 | 南通金康弘纺织品有限公司 | A kind of preparation method of NACF |
| CN109537106B (en) * | 2018-11-09 | 2021-05-18 | 中国科学院山西煤炭化学研究所 | Method for preparing precursor fiber, pre-oxidized fiber or carbon fiber of carbon fiber with special-shaped section by high-speed dry jet spinning |
| CN109887760A (en) * | 2019-02-27 | 2019-06-14 | 清华大学 | A kind of active carbon of high conductivity and its preparation and purposes |
| CN111172627B (en) * | 2020-01-14 | 2022-09-27 | 安徽工程大学 | Hollow-structure biomass activated carbon fiber and preparation method thereof |
| CN112553711A (en) * | 2020-12-15 | 2021-03-26 | 中南大学 | Rapid preoxidation method for polyacrylonitrile fiber precursor |
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| JPS6426723A (en) * | 1987-07-17 | 1989-01-30 | Mitsubishi Rayon Co | Finely porous hollow carbon membrane fiber and production thereof |
| JPH0398624A (en) * | 1989-09-11 | 1991-04-24 | Mitsubishi Rayon Co Ltd | Carbon fiber-based porous hollow fiber membrane and its preparation |
| US5089135A (en) * | 1988-01-20 | 1992-02-18 | Mitsubishi Rayon Co., Ltd. | Carbon based porous hollow fiber membrane and method for producing same |
| JP3098624B2 (en) * | 1992-08-27 | 2000-10-16 | 株式会社日立製作所 | Liquid crystal display |
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- 2005-10-14 CN CNB2005100305458A patent/CN1328425C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6426723A (en) * | 1987-07-17 | 1989-01-30 | Mitsubishi Rayon Co | Finely porous hollow carbon membrane fiber and production thereof |
| US5089135A (en) * | 1988-01-20 | 1992-02-18 | Mitsubishi Rayon Co., Ltd. | Carbon based porous hollow fiber membrane and method for producing same |
| JPH0398624A (en) * | 1989-09-11 | 1991-04-24 | Mitsubishi Rayon Co Ltd | Carbon fiber-based porous hollow fiber membrane and its preparation |
| JP3098624B2 (en) * | 1992-08-27 | 2000-10-16 | 株式会社日立製作所 | Liquid crystal display |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7934284B2 (en) | 2003-02-11 | 2011-05-03 | Braun Gmbh | Toothbrushes |
| US8695149B2 (en) | 2003-02-11 | 2014-04-15 | Braun Gmbh | Toothbrushes |
| US7941886B2 (en) | 2003-09-19 | 2011-05-17 | Braun Gmbh | Toothbrushes |
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