CN1198977C - Method for controlling aperture distribution of phenol aldehyde activated carbon fibers - Google Patents
Method for controlling aperture distribution of phenol aldehyde activated carbon fibers Download PDFInfo
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- CN1198977C CN1198977C CN 03123972 CN03123972A CN1198977C CN 1198977 C CN1198977 C CN 1198977C CN 03123972 CN03123972 CN 03123972 CN 03123972 A CN03123972 A CN 03123972A CN 1198977 C CN1198977 C CN 1198977C
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Abstract
The present invention relates to a method for controlling the aperture distribution of a phenolic-base activated carbon fiber, which has the technical scheme that an aperture forming agent is added to a raw polymer; the activated carbon fiber with different aperture sizes and different distribution can be prepared by controlling the pyrolysis process without activation. The present invention has the advantages of low price of and easy obtainment of the reagent, and simple and time-saving step. When the aperture sizes of the phenolic base activated carbon fiber are optimized, the method has no need of introducing other atoms, particularly metal atoms.
Description
Affiliated field
The invention belongs to the preparation method of absorbent charcoal material, relate to a kind of method of controlling the phenolic resin based activated carbon fiber pore-size distribution specifically.
Background technology
Phenolic resin based activated carbon fiber specific area height, pore-size distribution is narrow, and the adsorption desorption function admirable can be widely used in the absorption of multiple material in the gas, liquid; Because the purity height, content of heteroatoms is few, and especially metallic atom content is few, can be used as catalyst carrier; In addition, because its unique three-dimensional crosslinking structure, and have good electric conductivity, be the desirable electrode material of super electrochemical capacitor.No matter development of modern science and technology is as sorbing material, and catalyst carrier, or electrode material have proposed strict more requirement to the pore size distribution range of phenolic aldehyde matrix activated carbon material.How its pore structure being optimized design, is the problem that numerous scholar pays close attention to.W F Degroot, G N Richards. (Carbon1989,27 (2): 247), F Rodriguez-Reinoso, (Carbon 1995 for M Molina-Sabio, 15) and A Oya 33 (1):, M Kimura (Carbon 1994,32 (1): 107), and peace Tian Yuan, Yu Jing takes charge of (chemistry 1994 for a long time, 49 (9): 664) and other scholars' work show: adopt physical activation method, only can in very limited scope, adjust pore size, though and the catalytic activation effect effect of metal is remarkable, but can introduce metal ion simultaneously in the matrix, limit its scope of application greatly.
Summary of the invention:
The purpose of this invention is to provide a kind of easy, effectively control the aperture, do not introduce the preparation method of the phenolic resin based activated carbon fiber of metal ion again.
The present invention adopts and add pore-foaming agent in raw polymer, by the control pyrolytic process, not activatedly can prepare the activated carbon fiber with different pore sizes and distribution.The most probable aperture is in 0.7～7nm scope, and the most probable aperture is meant its highest hole of shared ratio in pore-size distribution.
Preparation method of the present invention is as follows
(1) with free phenol content≤0.2%, the novolac resin of viscosity 2000～6000 pools is by weight being phenolic resins: organic solvent=3～30: 100 ratio is dissolved in the organic solvent, be heated to boiling, reflux, be stirred to it and dissolve fully, make solution A;
(2) pore-foaming agent is pore-foaming agent by weight: organic solvent=0.1～20: 100 ratio is dissolved in the organic solvent, is heated to boiling, refluxes, is stirred to it to dissolve fully, makes solution B;
(3) with A, B solution is pore-foaming agent by weight: phenolic resins=0.01～30: 100 mixed, be heated to boiling, and reflux, be stirred to two kinds of solution and mix fully, make solution C;
(4) with solution C vacuumize under 50 ℃～120 ℃ temperature;
(5) with above-mentioned institute vacuumize gained material through melt spinning, solidify, make highly cross-linkedization phenolic fibre;
(6) with highly cross-linkedization phenolic fibre at N
2In the atmosphere with the heating rate of 10 ℃/hr～200 ℃/hr. be warming up to 500～1000 ℃, make the phenolic resin based activated carbon fiber of most probable aperture in 0.7～7nm scope.Respectively forming optimum weight ratio in the above-mentioned steps is:
Phenolic resins: organic solvent=10～20: 100.
Pore-foaming agent: organic solvent=0.5～10: 100
Pore-foaming agent: phenolic resins=0.5～25: 100
Described organic solvent is methyl alcohol, ethanol, acetone or chloroform.
Described pore-foaming agent is polyamide, polyethylene glycol, polyvinyl butyral resin or polystyrene.
The concrete grammar of described melt spinning can be referring to document: J.Economy, L.C.Wahrer, " Nonmable Phenolic Fibers ", J.Fire ﹠amp; Flammability Vol.3, Apr., 1972, p114-129, Koichiro Ohtomo, Takatsuki; Thuyoshi Nakamori, Osaka; Process forspinning composite fiber of phenolic resin, U.S.Patent, 3,996,327 (1976).
The curing of described phenolic fibre can be referring to J.Economy, Fibers from Novolacsand Method for Their Production, U.S.Patent Application Ser., 710292 (1968).
The present invention compared with prior art has following advantage:
(1) agents useful for same is cheap and easy to get, and step is simple, save time.
(2) the present invention does not introduce other atom, especially metallic atom when the phenolic resin based activated carbon fiber pore size is optimized design.
The specific embodiment
Embodiment 1
Taking by weighing free phenol content is 0.18%, and the novolac resin 100g of viscosity 2000 pools is measured ethanol 500ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and is heated to boiling, refluxes and stir 2hr, makes solution A.Take by weighing polystyrene 0.5g, measure ethanol 50ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, be heated to boiling, reflux and stir 2hr, make solution B.B solution is sneaked in the A solution, continue to be heated to boiling, reflux and stir 2hr., then at 80 ℃ of following vacuumize 24hr..With above-mentioned vacuumize material melt spinning, its concrete grammar is connected with N for novolac resin is placed
2Protection, the bottom has in the rustless steel container in 0.1～0.8mm hole, is warming up to 120～190 ℃, feeds the N that has pressure
2, material is flowed out from the aperture of container bottom, the speed with fiber 1000m/min. is wrapped on the receipts roll dies again.Then fiber is solidified, be about to spin fiber and immerse and contain in the consolidation liquid of hydrochloric acid and formaldehyde, be warming up to 105 ℃ with the speed of 10 ℃/hr., constant temperature 2hr. under this temperature, question response after finishing takes out fiber, washing, drying promptly can be made into highly cross-linkedization phenolic fibre.Again this phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 600 ℃ with the heating rate of 20 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 1.4nm.
Embodiment 2
Taking by weighing free phenol content is 0.08%, and the novolac resin 200g of viscosity 4300 pools is measured ethanol 800ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 1hr that refluxes make solution A.Take by weighing polyethylene glycol 20g, measure ethanol 100ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 1hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 2hr., then at 60 ℃ of following vacuumize 34hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 900 ℃ with the heating rate of 100 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 2.5nm.
Embodiment 3
Taking by weighing free phenol content is 0.11%, and the novolac resin 100g of viscosity 2200 pools is measured methyl alcohol 500ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 1.5hr that refluxes make solution A.Take by weighing polyamide 20g, measure methyl alcohol 200ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 1.5hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 2hr., then at 60 ℃ of following vacuumize 18hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 950 ℃ with the heating rate of 150 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 3.2nm.
Embodiment 4
Taking by weighing free phenol content is 0.13%, and the novolac resin 100g of viscosity 3700 pools is measured acetone 300ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 1.5hr that refluxes make solution A.Weighing polyvinyl alcohol butyral 5g is measured acetone 100ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 1.5hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 2hr., then at 80 ℃ of following vacuumize 18hr..This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 700 ℃ with the heating rate of 50 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 3.8nm.
Embodiment 5
Taking by weighing free phenol content is 0.18%, and the novolac resin 200g of viscosity 2800 pools is measured chloroform 500ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 1.5hr that refluxes make solution A.Take by weighing polyethylene glycol 30g, measure chloroform 100ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 1.5hr that refluxes make solution B.B solution is sneaked in the A solution, continues heating, refluxes and stir 3hr., then at 120 ℃ of following vacuumize 18hr. with above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 800 ℃ with the heating rate of 30 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 4.5nm.
Embodiment 6
Taking by weighing free phenol content is 0.14%, and the novolac resin 150g of viscosity 4500 pools is measured chloroform 800ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 1.5hr that refluxes make solution A.Take by weighing poly-polystyrene 5g, measure chloroform 100ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 1.5hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 3hr., then at 100 ℃ of following vacuumize 25hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 700 ℃ with the heating rate of 200 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 3.5nm.
Embodiment 7
Taking by weighing free phenol content is 0.19%, and the novolac resin 200g of viscosity 3800 pools is measured ethanol 600ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 3hr that refluxes make solution A.Take by weighing polyethylene glycol 15g, measure ethanol 200ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 3hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 2hr., then at 115 ℃ of following vacuumize 24hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.Again this phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 850 ℃ with the heating rate of 10 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 3.4nm.
Embodiment 8
Taking by weighing free phenol content is 0.10%, and the novolac resin 100g of viscosity 4300 pools is measured chloroform 500ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 3hr that refluxes make solution A.Weighing polyvinyl alcohol butyral 18g is measured chloroform 100ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 3hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 2hr., then at 80 ℃ of following vacuumize 24hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 1000 ℃ with the heating rate of 150 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 5.8nm.
Embodiment 9
Taking by weighing free phenol content is 0.12%, and the novolac resin 100g of viscosity 3500 pools is measured methyl alcohol 400ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 2hr that refluxes make solution A.Take by weighing polystyrene 25g, measure methyl alcohol 200ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 2hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 3hr., then at 80 ℃ of following vacuumize 15hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 600 ℃ with the heating rate of 50 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 2.2nm.
Embodiment 10
Taking by weighing free phenol content is 0.14%, and the novolac resin 100g of viscosity 3000 pools is measured ethanol 500ml, places the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, and heating, the stirring 2hr that refluxes make solution A.Take by weighing polyamide 15g, measure ethanol 100ml, place the there-necked flask that stirring arm, thermocouple and reflux condenser are housed, heating, the stirring 2hr that refluxes make solution B.B solution is sneaked in the A solution, continue heating, reflux and stir 3hr., then at 80 ℃ of following vacuumize 25hr..With above-mentioned vacuumize material melt spinning, curing, make highly cross-linkedization phenolic fibre, concrete grammar is with embodiment 1.This phenolic fibre is fixed on the graphite clamping plate, places in the electric furnace, at N
2Protection down is warming up to 800 ℃ with the heating rate of 150 ℃/hr., makes the phenolic resin based activated carbon fiber that the most probable aperture is 3.2nm.
Claims (6)
1. a method of controlling the phenolic resin based activated carbon fiber pore-size distribution is characterized in that comprising the steps:
(1) with free phenol content≤0.2%, the novolac resin of viscosity 2000～6000 pools is by weight being phenolic resins: organic solvent=3～30: 100 ratio is dissolved in the organic solvent, be heated to boiling, reflux, be stirred to it and dissolve fully, make solution A;
(2) pore-foaming agent is pore-foaming agent by weight: organic solvent=0.1～20: 100 ratio is dissolved in the organic solvent, is heated to boiling, refluxes, is stirred to it to dissolve fully, makes solution B;
(3) with A, B solution is pore-foaming agent by weight: phenolic resins=0.01～30: 100 mixed, be heated to boiling, and reflux, be stirred to two kinds of solution and mix fully, make solution C;
(4) with solution C vacuumize under 50 ℃～120 ℃ temperature;
(5) with above-mentioned institute vacuumize gained material through melt spinning, solidify, make highly cross-linkedization phenolic fibre;
(6) with highly cross-linkedization phenolic fibre at N
2In the atmosphere with the heating rate of 10 ℃/hr～200 ℃/hr.Be warming up to 500～1000 ℃, promptly can be made into the phenolic resin based activated carbon fiber of most probable aperture in 0.7～7nm scope.
2. a kind of method of controlling the phenolic resin based activated carbon fiber pore-size distribution according to claim 1 is characterized in that described novolac resin: the weight ratio of organic solvent is 10～20: 100.
3. a kind of method of controlling the phenolic resin based activated carbon fiber pore-size distribution according to claim 1 is characterized in that described pore-foaming agent: the weight ratio of organic solvent is 0.5～10: 100.
4. a kind of method of controlling the phenolic resin based activated carbon fiber pore-size distribution according to claim 1 is characterized in that pore-foaming agent: the weight ratio of phenolic resins is 0.5～25: 100.
5. according to each described a kind of method of controlling the phenolic resin based activated carbon fiber pore-size distribution of claim 1-4, it is characterized in that described organic solvent is methyl alcohol, ethanol, acetone or chloroform.
6. according to each described a kind of method of controlling the phenolic resin based activated carbon fiber pore-size distribution of claim 1-4, it is characterized in that described pore-foaming agent is polyamide, polyethylene glycol, polyvinyl butyral resin or polystyrene.
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| TWI712561B (en) | 2016-06-02 | 2020-12-11 | 國立大學法人信州大學 | Method for producing deuterium-depleted water, and method for producing deuterium-concentrated water |
| CN108950728B (en) * | 2018-07-27 | 2020-09-25 | 中原工学院 | Wet spinning method for preparing cardanol modified high-ortho phenolic fiber |
| CN115650227B (en) * | 2022-10-24 | 2023-12-22 | 福建韩研环保科技有限公司 | High adsorptivity injection active carbon and preparation method thereof |
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