CN100515558C - Composite active carbon fiber with polyvinyl membrane coating on surface and production thereof - Google Patents
Composite active carbon fiber with polyvinyl membrane coating on surface and production thereof Download PDFInfo
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- CN100515558C CN100515558C CNB2005101117121A CN200510111712A CN100515558C CN 100515558 C CN100515558 C CN 100515558C CN B2005101117121 A CNB2005101117121 A CN B2005101117121A CN 200510111712 A CN200510111712 A CN 200510111712A CN 100515558 C CN100515558 C CN 100515558C
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Abstract
A composite hollow activated carbon fiber whose surface is coated by polyvinyl alcohol (PVC) film for selective adsorption to micro-molecular and medium-molecular substances is prepared from the hollow polyacrylonitrile fiber through pretreating with PVC solution, oxidizing, carbonizing, activating, and coating PVC film.
Description
Technical field
The present invention relates to a kind of surface-coated has the composite active carbon fibre and the preparation method of the hollow morphosis of polyvinyl alcohol film.
Background technology
Active hollow charcoal fiber (ACHF) is a kind of novel sorbing material, (ACF) compares with NACF, have hollow, porous, self-support, aperture size and hole count and can characteristics such as control by the processing conditions of fibriilar manufacturing and charing, activation process, very little volume just can have very big specific area, can be used for absorption, separation, purifying and the dialysis etc. of liquid or admixture of gas, widen its application in fields such as catalysis, biology, medicine, electronics and liquid phase adsorption.But in processing ACHF, some bigger hole and defectives also can appear in fiber surface, for reducing hole and the defective that fiber surface exists, and improve it and select separation property, be coated on the surface of the active hollow charcoal fiber of PAN base with polyvinyl alcohol, and under suitable temperature drying and forming-film, heat-treat in certain temperature then, promptly obtain the composite active carbon fibre that surface-coated has the hollow morphosis of polyvinyl alcohol film.
At present, Chinese scholars mostly adopts the CVD method to carry out coating at carbon fiber surface to reach above purpose.The CVD method has coating densification and thickness advantage of uniform.Chen Lining has carried out the work of CVD method coating SiC on the charcoal fiber.People such as Cao Feng adopt sol-gel process to apply mullite solution and inorganicization at carbon fiber surface, obtain the fibre single thread surface distributed with combine good oxide coating.Ceng Qingbing adopts sol-gel process to apply TiO at carbon fiber surface
2, improved the non-oxidizability and the resistance to elevated temperatures of charcoal fiber.People such as Y.Z.Wan have applied metal level at carbon fiber surface, improve the heat endurance and the fracture strength of fiber.People such as Ick-Cheun Kim have applied polyoxygenated aryl ether hydrogen phosphide (PEPO) at carbon fiber surface, strengthen the interfacial adhesion power with the vinyl esters branch.In this patent, adopt dip coating, improved the structural form on film surface, the advantage of inorganic material and organic material is integrated at NACF surface-coated high-polymer membrane.
Summary of the invention
The purpose of this invention is to provide a kind of surface-coated has the composite active carbon fibre of the hollow morphosis of polyvinyl alcohol (PVA) film.The composite active carbon fibre of described hollow morphosis is made up of the macropore of micropore, 2~50nm mesopore and the aperture>50nm~90nm of aperture<2nm, the high polymer that applies can also be polyvinylpyrrolidone, polyvinyl acetate, polyacrylate, polymethacrylates, poly-(methyl) acrylamide or poly ester etc. except polyvinyl alcohol.
Purpose of the present invention also provides the preparation method of the composite active carbon fibre of the hollow morphosis that a kind of surface-coated has polyvinyl alcohol film.
Surface-coated of the present invention has the composite active carbon fibre of the hollow morphosis of polyvinyl alcohol film, and compared with the NACF before uncoated, its specific area descends to some extent, the adsorption rate of medium molecular substance is sharply descended, as VB
12Adsorption rate to small-molecule substance slightly descends, as creatinine; But still remain on more than 90% generally.
Surface-coated of the present invention has the preparation method of composite active carbon fibre of the hollow morphosis of polyvinyl alcohol film, be that the polyacrylonitrile doughnut is carried out preliminary treatment with the aqueous solution of phosphide, with after pre-oxidation, charing, activation form with the surface-coated of poly-vinyl alcohol solution at last NACF.
Concrete preparation method changes water once for the raw material doughnut 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, feed nitrogen then, repeat to vacuumize and logical nitrogen several, under nitrogen protection, with the heating rate heating of 10 ℃/min, carbonization temperature is 500-1000 ℃, and carbonization time is 10-110 minute; Charing is carried out activation processing after finishing 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 the NACF that applies without PVA solution.
To be immersed in concentration without the PAN-ACHF that PVA solution applies and be 10~30min in 1~5% the PVA solution, take out then, dry naturally, dry by the fire 5hr at 100~200 ℃, this coating procedure can repeat 1~5 time, obtains the composite active carbon fibre that finished product-surface-coated has the hollow morphosis of PVA film then.
PVA has highly hydrophilic, good stain resistance and film forming makes it become one of excellent material of making superthin layer.Contain great amount of hydroxy group on its strand, its compound with regular structure, and be strict linear structure, so its chemical property is stable, the mechanical strength height of material, the hydrogen bond that exists between the molecule make it that enough heat endurances be arranged.PVA has good water-solubility, and good filming performance is arranged, and can form smooth top layer, very tough, tear-resistant film, also have extraordinary solvent resistance, thus more and more widely become one of hydrophilic film material, and be applied to this field of utilized thin film composite membranes.
Surface-coated of the present invention has the composite active carbon fibre of the hollow morphosis of PVA film, NACF compared with the preparation in early stage without the high molecular polymer coating, hole and defective that the NACF surface exists have been reduced, improved the mechanical strength of fiber, can carry out selective absorption to small-molecule substance and medium molecular substance, the high-adsorption active carbon fibre of applied widely, good moldability, good purification, and be the simple preparation method of a kind of technology.
Description of drawings
The specific area of the composite active carbon fibre after Fig. 1 applies with variable concentrations PVA;
Composite active carbon fibre after Fig. 2 applies with variable concentrations PVA is to the adsorption rate of small-molecule substance (creatinine) and medium molecular substance (VB12);
Fig. 3 applies the specific area of the composite active carbon fibre behind the different number of times;
Fig. 4 applies composite active carbon fibre behind the different number of times to the adsorption rate of small-molecule substance (creatinine) and medium molecular substance (VB12).
In the accompanying drawing, the abscissa of Fig. 1 is the concentration of PVA solution, and ordinate is a specific area; The abscissa of Fig. 2 is the concentration of PVA solution, and ordinate is an adsorption rate; The abscissa of Fig. 3 is to apply number of times, and ordinate is a specific area; The abscissa of Fig. 4 is to apply number of times, and ordinate is an adsorption rate.
The specific embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
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 the NACF of the hollow morphosis of uncoated.
With early stage the PAN-ACHF for preparing to be immersed in concentration respectively be 10min in 0~3% the PVA solution, take out then, dry naturally, dry by the fire 5hr at 130 ℃, when temperature is reduced to room temperature, take out doughnut, be the composite active carbon fibre that finished product-surface-coated has the hollow morphosis of polyvinyl alcohol film.
The specific area of above-mentioned NACF changes as shown in Figure 1, and adsorption rate changes as shown in Figure 2.
Be that the PVA solution of 2% (wt%) carries out 0,1,2,3 time respectively to the PAN-ACHF surface that prepared early stage and applies with concentration.After each the coating, all, treat repeatedly to apply again after temperature is reduced to room temperature, prepare the composite active carbon fibre that surface-coated has the PVA film of different-thickness respectively at 130 ℃ of baking 5hr.
The specific area of above-mentioned NACF changes as shown in Figure 3, and adsorption rate changes as shown in Figure 4.The test of above-mentioned specific surface area 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.The test of adsorption rate data is to use Shanghai Techcomp Instrument Ltd., and UV/VIS 7500 type ultraviolet-visible spectrophotometers are tested.
Claims (3)
1. a surface-coated has the composite active carbon fibre of the hollow morphosis of polyvinyl alcohol film, it is characterized in that the composite active carbon fibre of described hollow morphosis is made up of the macropore of micropore, 2~50nm mesopore and the aperture>50nm~90nm of aperture<2nm.
2. a kind of surface-coated as claimed in claim 1 has the preparation method of composite active carbon fibre of the hollow morphosis of polyvinyl alcohol film, it 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 carries out obtaining in activation processing 20-100 minute NACF; Subsequently with the surface-coated of poly-vinyl alcohol solution to NACF.
3. a kind of surface-coated as claimed in claim 2 has the preparation method of composite active carbon fibre of the hollow morphosis of polyvinyl alcohol film, it is characterized in that described is that polyacrylonitrile radical active carbon fiber with the hollow morphosis of uncoated is immersed in the poly-vinyl alcohol solution that concentration is 1-5% 10-30 minute with poly-vinyl alcohol solution to the surface-coated of NACF, take out then, dry naturally, dried by the fire 5 hours at 100-200 ℃, this coating procedure repeats 1-5 time.
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CN100509621C (en) * | 2006-04-12 | 2009-07-08 | 中国科学院金属研究所 | Layer combination controllable carbon material with nano pole of different scale, preparation method and application |
US8598073B2 (en) * | 2009-04-20 | 2013-12-03 | Corning Incorporated | Methods of making and using activated carbon-containing coated substrates and the products made therefrom |
CN105536744A (en) * | 2015-12-11 | 2016-05-04 | 苏州贝多环保技术有限公司 | Composite oil absorption material and preparation method thereof |
CN111554444A (en) * | 2020-05-09 | 2020-08-18 | 陕西科技大学 | PVA/carbonized hollow wood fiber composite material and preparation method and application thereof |
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Non-Patent Citations (8)
Title |
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活化温度对聚丙烯腈基活性中空炭纤维结构和吸附性能的影响. 孙俊芬等.合成纤维工业,第27卷第5期. 2004 |
活化温度对聚丙烯腈基活性中空炭纤维结构和吸附性能的影响. 孙俊芬等.合成纤维工业,第27卷第5期. 2004 * |
添加PVP和涂覆聚合物对PAN基中空纤维炭膜性能的影响. 白金锋等.燃料化学学报,第25卷第1期. 1997 |
添加PVP和涂覆聚合物对PAN基中空纤维炭膜性能的影响. 白金锋等.燃料化学学报,第25卷第1期. 1997 * |
用磷酸盐预处理制备PAN基活性中空炭纤维. 孙俊芬等.离子交换与吸附,第20卷第4期. 2004 |
用磷酸盐预处理制备PAN基活性中空炭纤维. 孙俊芬等.离子交换与吸附,第20卷第4期. 2004 * |
预处理条件对PAN基中空活性炭纤维性能的影响. 吴光香等.纺织科学研究,第3期. 2003 |
预处理条件对PAN基中空活性炭纤维性能的影响. 吴光香等.纺织科学研究,第3期. 2003 * |
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