CN1150607A - Method for preparing mesopore active carbon fibre - Google Patents
Method for preparing mesopore active carbon fibre Download PDFInfo
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- CN1150607A CN1150607A CN 95119030 CN95119030A CN1150607A CN 1150607 A CN1150607 A CN 1150607A CN 95119030 CN95119030 CN 95119030 CN 95119030 A CN95119030 A CN 95119030A CN 1150607 A CN1150607 A CN 1150607A
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Abstract
The present invention provides a method for preparing mesopore active carbon fibre. The resin and carbon material are mixed according to the mixing ratio of 1:0.001-0.10, then dissolved in dimethyl sulfoxide, and spun into acrylic fibre containing 0.1-10% (wt%) of carbon material by using wet method, then the obtained acrylic fibre is passed through such processes as preoxidation, carbonizing and activation so as to obtain the invented product. Said invention is simple in preparation method and technological process, and its raw material is easily available, and its product contains no metal ion, and its porosity can be up to 50-70%. Said invented product can be used in the fields of catalysis, medicine, electronics and liquid phase adsorption, etc. which need mesopore material.
Description
The present invention relates to a kind of mesopore activated carbon fiber preparation method.
Conventional at present activated carbon fiber (ACF) mostly is the pore type fiber of aperture＜2nm greatly, and its hole directly is opened on fiber surface, makes it have suction, the fast advantage of desorption rate in Gas Phase Adsorption.But the pore type fiber is difficult to use in relating to big molecule field (as catalysis, electronics, medicine and liquid phase adsorption etc.).Therefore oneself becomes one of developing direction of porous carbon material between the flourishing activated carbon fiber of the mesopore of 2-50nm in development.The preparation technology of the composition of precursor, structure and ACF is restricting the pore structure of final ACF jointly, but if want to increase substantially its mesopore content, generally must set about from precursor.The research of the rugged virtuous department in 1993 islands (Japanization association will, 7,807,1993) has reported that adopting the polyacrylonitrile fibril activation that contains titanium dioxide to make middle porosity reaches 53% ACF.People (Carbon, 26 (1), 7,1988) such as J.J.Freeman in 1988 then provide adopt the viscose activation that is soaked with dibastic sodium phosphate obtain in porosity reach the research of 72% ACF.All used the precursor of metal ion in above-mentioned two kinds of methods, so not only increased preparation section, and made and contain more metal ion among the final ACF inevitably, thereby limited its application in fields such as medicine, catalysis.
The object of the present invention is to provide a kind of mesopore activated carbon fiber preparation method of not metal ion.
Mesopore activated carbon fiber preparation method of the present invention, be with resin and carbon material with 1: be dissolved in the dimethyl sulfoxide (DMSO) after the mixed of 0.001-0.10, wet method is spun into the polyacrylonitrile fibre that contains carbon material 0.1-10% (wt), forms through pre-oxidation, charing, activation then.
In said method, described carbon material can be carbon black, graphite powder or active carbon.
Pre-oxidation described in the said method, charing, activation all can adopt conventional technology to finish.
Carbon material all is the material of being made up of carbon substantially, and has the characteristics of particle diameter little (active carbon is through grinding), can be dispersed in the spinning solution of polyacrylonitrile and dimethyl sulfoxide (DMSO) composition, can obtain uniform continuous filament yarn through spinning.The present invention adds such material when the spinning polyacrylonitrile fibril, then through pre-oxidation, charing, the steam activation of routine, porosity is the mesopore activated carbon fiber of 50-70% in making.Method technology of the present invention is simple, and raw material is easy to get, and metal ion not in the product can be used for the field that catalysis, medicine, electronics, liquid phase adsorption etc. need mesopore material.
Embodiment one
Be dissolved in the 270ml dimethyl sulfoxide (DMSO) after 40g polyacrylonitrile (PAN) resin and 0.4g carbon black (commercially available writing used carbon black) mixed, treat fully dissolving after, wet method is spun into the PAN fiber that contains carbon black 1WT%.This fiber was wound on the stainless steel framework of rectangle in 240 ℃ of air pre-oxidation after 4.5 hours, take off to shred and put into the specimen holder that places vertical charing, activation furnace, flow with 260ml/min feeds nitrogen in stove then, when being warming up to 830 ℃ with the speed of 10 ℃/min after 10 minutes, beginning pumps into deionized water with the flow of 0.10ml/min in outlet and steam generator that body of heater links to each other, activation furnace begins constant temperature after still being warming up to 880 ℃ with the speed of 5 ℃/min at this moment.Activate after 30 minutes, close the water measuring pump, activation furnace drops to room temperature in nitrogen protection, and products obtained therefrom is sample A.
Embodiment two
With being dissolved in the 270ml dimethyl sulfoxide (DMSO) after 1.2g carbon black (the same) and the 40gPAN mixed with resin, make the polyacrylonitrile fibre that contains carbon black 3wt% after the spinning, follow-up pre-oxidation, charing, activating process make sample B with embodiment 1.
Embodiment three
The oxidation after 5 hours under the pre-oxidation condition of embodiment 1 of the precursor of embodiment 1; the charing programming rate is 7 ℃/min; nitrogen flow 740ml/min; begin to feed water vapour (flow is with embodiment 1) when being warming up to 850 ℃; constant temperature after still continuing to be warming up to 900 ℃ with 5 ℃/min speed activates and drops to room temperature in nitrogen protection after 25 minutes and get sample C.
Embodiment four
With the 20gPAN resin be dissolved in the 135ml dimethyl sulfoxide (DMSO) after 0.24g graphite powder (commercially available) evenly mixes, treat fully dissolving back wet spinning, method for pre-oxidizing is with embodiment 1.The charing programming rate is 5 ℃/min, during to 850 ℃, begins to feed steam activation 10 minutes, and other condition gets sample D with embodiment 1.
Embodiment five
0.1g active carbon (commercially available, as to grind the back and cross 320 mesh sieves) evenly mixed with the 20gPAN resin be dissolved in the 135ml dimethyl sulfoxide (DMSO), spinning, method for pre-oxidizing are with embodiment 1.Charing, activation method are with embodiment 3, and soak time 35 minutes gets sample E.
Fig. 1 is the adsorption isotherm of ABC sample.
Fig. 2 is the mesopore graph of pore diameter distribution of ABC sample.
Fig. 3 is the adsorption isotherm of DE sample.
Fig. 4 is the mesopore graph of pore diameter distribution of ADE sample.
What list in the table below is the pore structure parameter of A, B, C, D, E sample
Sequence number S
tV
0.95V
MlV
MeV
Me/ V
0.95
m
2/g ml/g ml/g ml/g ％
A 1157.3 0.704 0.346 0.358 50.9
B 568.7 0.426 0.177 0.249 58.5
C 822.1 0.514 0.264 0.250 48.6
D 458.9 0.226 0.146 0.080 35.4
E 909.4 0.449 0.290 0.159 35.4
Annotate: S
tRepresent the BET specific area
V
0.95The pore volume of the adsorbance correspondence that is at 0.95 o'clock is pressed in representative relatively
V
MlRepresent micro pore volume
V
MeRepresent V
0.95Subtract V
MlThe mesopore volume that gets
V
Me/ V
0.95Porosity in the representative
The test of above-mentioned data is to use the ASAP of U.S. Merck ﹠ Co., Inc 2000 absorption instrument employing volumetric method automatically, with nitrogen is that adsorbate adsorbs under liquid nitrogen temperature (77K), adopting the BET method to calculate total surface area by the adsorption isotherm that records, is that 0.95 o'clock nitrogen adsorptive value is converted into the V that the liquid nitrogen volume obtains comprising micropore and mesopore volume by relative pressure
0.95, by aperture surface area and micro pore volume in t method (B, C, Lippens people, J.Cat., 4,319, the 1965) calculating, by V
0.95Subtract micro pore volume and obtain mesopore volume, calculate the mesopore pore-size distribution by B.JH method (E.P Barrett etc., J.Amer.Chem.Soc., 73,373,1951).
Claims (2)
1. mesopore activated carbon fiber preparation method, it is characterized in that resin and carbon material with 1: be dissolved in the dimethyl sulfoxide (DMSO) after the mixed of 0.001-0.10, wet method is spun into the polyacrylonitrile fibre that contains carbon material 0.1-10% (wt), forms through pre-oxidation, charing, activation then.
2. the method for claim 1 is characterized in that described carbon material can be carbon black, graphite powder or active carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119030A CN1059245C (en) | 1995-11-21 | 1995-11-21 | Method for preparing mesopore active carbon fibre |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119030A CN1059245C (en) | 1995-11-21 | 1995-11-21 | Method for preparing mesopore active carbon fibre |
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| Publication Number | Publication Date |
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| CN1150607A true CN1150607A (en) | 1997-05-28 |
| CN1059245C CN1059245C (en) | 2000-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95119030A Expired - Fee Related CN1059245C (en) | 1995-11-21 | 1995-11-21 | Method for preparing mesopore active carbon fibre |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811697A (en) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Method for preparing pressed active carbon |
| CN102505403A (en) * | 2011-09-29 | 2012-06-20 | 大连理工大学 | Method for preparing hierarchically porous activated carbon fiber membrane |
| CN103614806A (en) * | 2013-11-25 | 2014-03-05 | 常熟市金羽纤维制品厂 | Activated carbon fiber cotton |
| CN103909853A (en) * | 2014-04-10 | 2014-07-09 | 江苏同康特种活性炭纤维面料有限公司 | Environment-friendly automobile cushion |
| CN104495838A (en) * | 2014-12-12 | 2015-04-08 | 河南省科学院化学研究所有限公司 | Method for preparing activated carbon |
| CN105544020A (en) * | 2016-01-28 | 2016-05-04 | 东华大学 | Graphene-doped polyacrylonitrile mesopore activated carbon fiber and preparation method thereof |
| CN105603584A (en) * | 2016-01-28 | 2016-05-25 | 东华大学 | Polyacrylonitrile mesoporous activated carbon fiber for super capacitor electrode and preparation method of fiber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1007435B (en) * | 1985-12-20 | 1990-04-04 | 中国纺织大学 | Preparation of spinning polyacrylonitrile fiber or long fiber |
-
1995
- 1995-11-21 CN CN95119030A patent/CN1059245C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811697A (en) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Method for preparing pressed active carbon |
| CN102505403A (en) * | 2011-09-29 | 2012-06-20 | 大连理工大学 | Method for preparing hierarchically porous activated carbon fiber membrane |
| CN102505403B (en) * | 2011-09-29 | 2014-04-02 | 大连理工大学 | Method for preparing hierarchically porous activated carbon fiber membrane |
| CN103614806A (en) * | 2013-11-25 | 2014-03-05 | 常熟市金羽纤维制品厂 | Activated carbon fiber cotton |
| CN103909853A (en) * | 2014-04-10 | 2014-07-09 | 江苏同康特种活性炭纤维面料有限公司 | Environment-friendly automobile cushion |
| CN104495838A (en) * | 2014-12-12 | 2015-04-08 | 河南省科学院化学研究所有限公司 | Method for preparing activated carbon |
| CN104495838B (en) * | 2014-12-12 | 2016-08-17 | 河南省科学院化学研究所有限公司 | A kind of method preparing activated carbon |
| CN105544020A (en) * | 2016-01-28 | 2016-05-04 | 东华大学 | Graphene-doped polyacrylonitrile mesopore activated carbon fiber and preparation method thereof |
| CN105603584A (en) * | 2016-01-28 | 2016-05-25 | 东华大学 | Polyacrylonitrile mesoporous activated carbon fiber for super capacitor electrode and preparation method of fiber |
| CN105603584B (en) * | 2016-01-28 | 2017-12-22 | 东华大学 | Mesoporous activated carbon fiber of electrode of super capacitor polyacrylonitrile and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1059245C (en) | 2000-12-06 |
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