CN104307470A - Preparation method of cellulose fiber-based active carbon fibers with high adsorption capacity as well as product and application of cellulose fiber-based active carbon fibers with high adsorption capacity - Google Patents
Preparation method of cellulose fiber-based active carbon fibers with high adsorption capacity as well as product and application of cellulose fiber-based active carbon fibers with high adsorption capacity Download PDFInfo
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- CN104307470A CN104307470A CN201410520311.0A CN201410520311A CN104307470A CN 104307470 A CN104307470 A CN 104307470A CN 201410520311 A CN201410520311 A CN 201410520311A CN 104307470 A CN104307470 A CN 104307470A
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 48
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 30
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 52
- 239000001913 cellulose Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000001994 activation Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000835 fiber Substances 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 13
- 235000014676 Phragmites communis Nutrition 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 9
- 238000001891 gel spinning Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229940072033 potash Drugs 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 5
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 abstract description 11
- 239000002243 precursor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010041 electrostatic spinning Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000003610 charcoal Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 244000146553 Ceiba pentandra Species 0.000 description 4
- 235000003301 Ceiba pentandra Nutrition 0.000 description 4
- 238000004320 controlled atmosphere Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 244000299507 Gossypium hirsutum Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940085805 fiberall Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of cellulose fiber-based active carbon fibers with the high adsorption capacity. The preparation method comprises the steps of extracting agriculture and forestry byproducts serving as raw materials to obtain cellulose; mixing the obtained cellulose with an N-methylmorpholine-N-oxide to obtain a mixture, heating the mixture in vacuum till the cellulose is completely dissolved to obtain a cellulose solution, and performing electrostatic spinning to obtain cellulose fibers; and carbonizing the cellulose fibers, then mixing the carbonized cellulose fibers with an active agent in a mass ratio of 1 to (1-5), grinding, and performing activation and post-treatment to obtain the active carbon fibers. The cellulose fibers prepared by adopting the special electrostatic spinning process are used as a precursor, carbonized, then physically mixed and activated with the active agent, so that the prepared cellulose fiber-based active carbon fibers have a very good adsorption effect when being applied to water purification treatment.
Description
Technical field
The present invention relates to the technical field of Carbon fibe, be specifically related to preparation method of a kind of cellulose fibre based active carbon fiber of high adsorption capacity and products thereof and application.
Background technology
NACF (ACF), also known as fibrous activated carbon, there is abundant micropore (bore dia is less than 2nm), pore-size distribution is narrower, major part micropore is directly opened on surface, and absorption path is short, and the rate of adsorption is fast, even if still there is good absorption property at low concentration, be widely used in industries such as Water warfare, purification of air, food decolouring, solvent recovery, medical separation.
At present, the preparation of NACF comprises three phases:
One is pretreatment, and pretreatment stage is to make some precursor fibre unlikely fusion and decomposition when high temperature carbonization process, and enters performance and the productive rate that pretreatment can significantly improve NACF;
Two is charings, and charing refers to that precursor fibre heats up heating in an inert atmosphere, the volatilizable non-charcoal component that removal precursor fibre produces in high-temperature process, and residual charcoal is reset, and makes Carbon fibe be partially formed graphite microcrystalline structure;
Three is activation, and activation process utilizes activator to carry out activation process, improves pore structure and the surface chemical structure of NACF.In industrial production, the normal gas activation adopted is easy to operate, and cost is low, but the specific area of obtained fibre active carbon is relatively little, and adopt chemical activation method to obtain specific area is higher, pore-size distribution is narrower NACF.
Organic fiber as NACF presoma mainly contains viscose glue base, polypropylene fine (PAN) base, asphaltic base, phenolic aldehyde base, polyvinyl alcohol (PVA) base etc., above-mentionedly severally all realizes suitability for industrialized production.In recent years, utilize organic-biological material to cause the broad interest of people as the method for precursor power active carbon, on the one hand, this technique is simple, little to ambient influnence, and raw material is renewable; On the other hand, the wide material sources of organic-biological matter, with low cost, especially using the agriculture and forestry by-product of waste resource as raw material, the high value added utilization of this resource can be realized.
As Wang Yuanqing (kapok based active carbon fiber is studied, Donghua University, master thesis, 2007.11) has prepared kapok based active carbon fiber, and have studied the preparation technology of kapok based active carbon fiber, use H respectively
3pO
4, ZnCl
2, K
2cO
3, (NH
4)
2hPO
4these four kinds of activators activation bombax cottons, are investigated activation process under different activation temperatures to the performance impact of the kapok based active carbon fiber of preparation simultaneously.The different activities Carbon fibe of preparation is applied to the absorption of phenol and methylene blue in water, maximum methylene blue adsorption number amount is 156.7mg/g.
Take natural plant fibre as raw material, fiber surface smoother, natural aperture is less, therefore in the mixed process of raw material or charcoal material and chemical activating agent, often causes contact surface to be only limitted to fiber surface, the pore-creating effect of fibrous inside cannot be realized, in addition, the mixed process of raw material or charcoal material and chemical activating agent often adopts infusion method, therefore also needs before activation to be dried completely, this makes preparation process loaded down with trivial details, and cost improves.
Summary of the invention
The invention provides a kind of preparation method of cellulose fibre based active carbon fiber of high adsorption capacity, the cellulose fibre prepared with special dry-wet spinning technique is for presoma, after charing, physical blending, activation is carried out again with activator, the cellulose fibre based active carbon fiber prepared is applied in purifying water process, has splendid treatment effect.
A preparation method for the cellulose fibre based active carbon fiber of high adsorption capacity, step is as follows:
(1) take agriculture and forestry by-product as raw material, after extraction, chemistry absent-mindedness, obtain cellulose;
(2) mixed with N-methylmorpholine-N-oxide (NMMO) by the cellulose that step (1) obtains, heated under vacuum dissolves completely to cellulose, obtains cellulose solution, obtains cellulose fibre through dry-wet spinning;
The technique of described electrostatic spinning is: cellulose solution is injected dry-wet spinning equipment, and pressure set is-0.1Pa, sprays silk and obtains as-spun fibre cellulose fiber, then obtain cellulose fibre through post processing at temperature 90 ~ 98 DEG C after being incubated 4 ~ 6h.
Be specially:
Cellulose solution is injected the static still of wet-dry change spray silk machine, pressure set is-0.1Pa, 4 ~ 6 hours are incubated at temperature 90 ~ 98 DEG C, as-spun fibre cellulose fiber is obtained through twin-screw-measuring pump-spinning pack spray silk, then solidify with deionization coagulating bath, rinse with water to go out residual NMMO afterwards, dehydration both obtained cellulose fibre after drying;
(3) cellulose fibre that obtains of step (2) is after charing process, and mix for 1:1 ~ 5 in mass ratio with activator, after grinding, activated process and post processing obtain described NACF again;
Described activator is potash, potassium hydroxide, NaOH or sodium carbonate.
Described agriculture and forestry by-product to refer in agricultural or forestry and discarded is rich in cellulosic herbaceous plant stem stalk.As preferably, described agriculture and forestry by-product is reed, straw stalk, Wheat Straw or cornstalk.This few class agriculture and forestry by-product contains abundant cellulose.Further preferably, described agriculture and forestry by-product is reed, is that the NACF that the preparation method of raw material in the present invention obtains has better absorption property with reed.
In described agriculture and forestry by-product, cellulosic extraction can take the technological means of this area routine, as alkalinity extraction, is specially: first cleaned by agriculture and forestry by-product, shred after drying, under normal temperature, particle is flooded 4 ~ 24h in alkali lye; Again the particle of impregnation process is placed in alkali lye, boiling 2 ~ 3h obtains cellulose solution, then filters out the cellulose through alkali lye boiling, through washing come unstuck, extrusion dehydration process, obtain cellulose.
Extract the cellulose obtained also to need, through chemistry absent-mindedness, to reduce the adhesion between cellulose, to make the further shredding of cellulose.
Step is: be immersed in NaCO by extracting the cellulose obtained
3in the aqueous solution, then extrusion dehydration; Dilute acid wash again, then extrusion dehydration; Repeat above-mentioned steps, then for subsequent use by shaking up after the cellulose drying of acquisition.
Described NMMO solvent is the state through being distilled to containing a crystallization water.
As preferably, in step (2), the mass fraction of described cellulose solution is 10 ~ 15%.
As preferably, in step (3), described charing treatment temperature is 450 ~ 500 DEG C.Further preferably, charing is treated to: be warming up to 200 DEG C with the heating rate of 10 DEG C/min, and insulation 40min, continues to be warming up to 400 ~ 500 DEG C with the heating rate of 10 DEG C/min, insulation 50min.The temperature that cellulose fibre starts to carbonize is about 200 DEG C, first be warming up to 200 DEG C to save time with fast speed, insulation 40min remains with the form of charcoal in the charing starting stage to make more carbon containing matter, continue to be warming up at a slow speed carbonization temperature to make carbon containing matter can not because of the too fast volatilization of heating rate, the insulation of carbonization temperature ensures that carbon containing matter fully can change into charcoal, select this treatment process to save time, improve charcoal productive rate.
As preferably, in step (3), cellulose fibre after charing process and potash are after 1:1 ~ 2 mix in mass ratio, be warming up to 850 ~ 900 DEG C under an inert atmosphere and carry out activation process, heating rate is 5 DEG C/min, and temperature retention time is 60min, to ensure the energy requirement that activation stage reacts, the aperture of cellulose base NACF is attained full development, there will not be again pore-creating excessive, reduce active carbon specific area and adsorption capacity.
In step (3), described last handling process comprises washing, drying.
According to a cellulose fibre based active carbon fiber prepared by above-mentioned method, specific area is comparatively large, and have abundant microcellular structure, pore size distribution range is narrower; NACF surface is containing abundant functional group simultaneously.
Compared with being the Carbon fibe that obtains of presoma with direct string, with the cellulose fibre after dry-wet spinning be presoma obtain Carbon fibe specific area higher, micropore is abundanter, more excellent to the adsorption capacity of methylene blue, and, its functional group enriches, especially the carboxyl (-COOH) showed increased contained, and methylene blue has alkalescence, can chemical reaction be there is in the two, consume methylene blue, this is also that cellulose base NACF of the present invention is to one of methylene blue reason with high adsorption capacity.
Described cellulose base NACF is applied to Water warfare field, there is the rate of adsorption fast, the advantage that adsorbance is large.
Compared with prior art, tool of the present invention has the following advantages:
The present invention with wide material sources, cheap agriculture and forestry by-product for raw material, the cellulose fibre prepared after dry-wet spinning is presoma, compared with native cellulose, there is a large amount of aperture in the cellulose fiber surface prepared after dry-wet spinning, what this was later stage and activator mix and pore-creating in activation process provides the foundation.
Cellulose fibre in the present invention after charing process directly can carry out solid phase mixing with activator, and substitute conventional infusion process, without the need to aftertreatment technology, the NACF obtained has abundant aperture structure, possesses splendid absorption property.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, but this embodiment not forms any type of any restriction to real protection scope of the present invention.
Embodiment 1
(1) raw material reed cleaned, cut into particle after drying, under normal temperature, particle is flooded 4h in alkali lye;
(2) particle through impregnation process is placed in alkali lye, boiling 2h obtains cellulose solution, then filters out the cellulose through alkali lye boiling, through washing come unstuck, extrusion dehydration process, obtain cellulose;
(3) cellulose that (2) obtain is immersed in NaCO
3in the aqueous solution, then extrusion dehydration;
(4) by the cellulose dilute acid wash that (3) obtain, then extrusion dehydration;
(5) repeat step (3) to carry out secondary aqueous sodium carbonate with (4) and flood and secondary weak acid scrubbing extrusion dehydration, for subsequent use by shaking up after the cellulose drying of acquisition;
(6) cellulose that (5) obtain is placed in NMMO, heated under vacuum to 95 DEG C, until cellulose dissolves completely;
(7) cellulose (6) obtained/NMMO solution injects the static still of wet-dry change spray silk machine, pressure set is-0.1Pa, 4 hours are incubated at temperature 90 DEG C, as-spun fibre cellulose fiber is obtained through twin-screw-measuring pump-spinning pack spray silk, then solidify with deionization coagulating bath, rinse with water to go out residual NMMO afterwards, dehydration both obtained cellulose fibre after drying;
(8) take the cellulose fibre 10g that (7) obtain and be placed in controlled atmosphere generator, under Ar atmosphere, be warming up to 200 DEG C with the heating rate of 10 DEG C/min, insulation 40min, continue to be warming up to 450 DEG C with the heating rate of 10 DEG C/min, insulation 50min;
(9) by gained cellulosic fibrous substrates charcoal material and potash in mass ratio 1:1.0 mixed grinding be placed in controlled atmosphere generator, under Ar atmosphere, be warming up to 850 DEG C with the heating rate of 5 DEG C/min and carry out activation process, insulation 60min;
(10) the cellulose fibre matrix activated carbon after activation is spent deionized water and be stabilized in about 7 to pH value, after drying, both obtain reed fiber of the present invention element based active carbon fiber.
Detection shows: obtained reed fiber element based active carbon fiber has good absorption property to the pollutant in the aqueous solution, and its methylene blue adsorption value is greater than 800mg/g, can be used for Water warfare.
Embodiment 2
(1) raw material reed cleaned, cut into particle after drying, under normal temperature, particle is flooded 24h in alkali lye;
(2) particle through impregnation process is placed in alkali lye, boiling 3h obtains cellulose solution, then filters out the cellulose through alkali lye boiling, through washing come unstuck, extrusion dehydration process, obtain cellulose;
(3) cellulose that (2) obtain is immersed in NaCO
3in the aqueous solution, then extrusion dehydration;
(4) by the cellulose dilute acid wash that (3) obtain, then extrusion dehydration;
(5) repeat step (3) to carry out secondary aqueous sodium carbonate with (4) and flood and secondary weak acid scrubbing extrusion dehydration, for subsequent use by shaking up after the cellulose drying of acquisition;
(6) cellulose that (5) obtain is placed in N-methylmorpholine-N-oxide (NMMO), heated under vacuum to 110 DEG C, until cellulose dissolves completely;
(7) cellulose (6) obtained/NMMO solution injects the static still of wet-dry change spray silk machine, pressure set is-0.1Pa, 6 hours are incubated at temperature 98 DEG C, as-spun fibre cellulose fiber is obtained through twin-screw-measuring pump-spinning pack spray silk, then solidify with deionization coagulating bath, rinse with water to go out residual NMMO afterwards, dehydration both obtained cellulose fibre after drying;
(8) take the cellulose fibre 10g that (7) obtain and be placed in controlled atmosphere generator, under Ar atmosphere, be warming up to 200 DEG C with the heating rate of 10 DEG C/min, insulation 40min, continue to be warming up to 450 DEG C with the heating rate of 10 DEG C/min, insulation 50min; Be warming up to 450 DEG C and carry out charing process;
(9) by gained cellulosic fibrous substrates charcoal material and potash in mass ratio 1:2.0 mixed grinding be placed in controlled atmosphere generator, under Ar atmosphere, be warming up to 900 DEG C with the heating rate of 5 DEG C/min, insulation 60min;
(10) the cellulose fibre matrix activated carbon after activation is spent deionized water and be stabilized in about 7 to pH value, after drying, both obtain reed fiber of the present invention element based active carbon fiber.
Detection shows: obtained reed fiber element based active carbon fiber has good absorption property to the pollutant in the aqueous solution, and its methylene blue adsorption value is greater than 700mg/g, can be used for Water warfare.
Embodiment 3
Except the mass ratio of cellulosic fibrous substrates charcoal material in step (9) and potash changes into except 1:1.5, all the other are with embodiment 1.
Detection shows: obtained reed fiber element based active carbon fiber has good absorption property to the pollutant in the aqueous solution, and its methylene blue adsorption value is greater than 760mg/g, can be used for Water warfare.
Embodiment 4 ~ 6
Except the raw material in step (1) is replaced with except grass stalk, wheat straw bar, cornstalk by reed, all the other are with embodiment 1.
Detection shows: the grass stalk cellulose base NACF prepared respectively, wheat straw rod fibers element based active carbon fiber and cornstalk fiber element based active carbon fiber all have good absorption property to the pollutant in the aqueous solution, its methylene blue adsorption value is all greater than 600mg/g, can be used for Water warfare.
Compared with other NACF prepared in prior art (the most about 500mg/g), NACF prepared by the present invention is in the application of Water warfare field, methylene blue adsorption value is all greater than 600mg/g, and the best can be greater than 800mg/g, and absorption property is very excellent.
Claims (9)
1. a preparation method for the cellulose fibre based active carbon fiber of high adsorption capacity, is characterized in that, comprise the steps:
(1) taking agriculture and forestry by-product as raw material, obtaining cellulose through extracting;
(2) mixed with N-methylmorpholine-N-oxide by the cellulose that step (1) obtains, heated under vacuum dissolves completely to cellulose, obtains cellulose solution, obtains cellulose fibre through dry-wet spinning;
The technique of described dry-wet spinning is: cellulose solution is injected dry-wet spinning equipment, and pressure set is-0.1Pa, sprays silk and obtains as-spun fibre cellulose fiber, then obtain cellulose fibre through post processing at temperature 90 ~ 98 DEG C after being incubated 4 ~ 6h;
(3) cellulose fibre that obtains of step (2) is after charing process, and mix for 1:1 ~ 5 in mass ratio with activator, after grinding, activated process and post processing obtain described NACF again;
Described activator is potash, potassium hydroxide, NaOH or sodium carbonate.
2. the preparation method of the NACF of high adsorption capacity according to claim 1, is characterized in that, described agriculture and forestry by-product is one or more in reed, grass stalk, Wheat Straw, cornstalk.
3. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, is characterized in that, in step (1), extracts the cellulose obtained stand-by after chemistry absent-mindedness, is specially:
NaCO is immersed in by extracting the cellulose obtained
3in the aqueous solution, dilute acid wash, then extrusion dehydration again after extrusion dehydration; Repeat above-mentioned steps, then for subsequent use by shaking up after the cellulose drying of acquisition.
4. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, is characterized in that, in step (2), the mass fraction of described cellulose solution is 10 ~ 15%.
5. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, is characterized in that, in step (3), described charing treatment temperature is 450 ~ 500 DEG C.
6. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 4, it is characterized in that, in step (3), described charing is treated to: be warming up to 200 DEG C with the heating rate of 10 DEG C/min, insulation 40min, continue to be warming up to 400 ~ 500 DEG C with the heating rate of 10 DEG C/min, insulation 50min.
7. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, it is characterized in that, in step (3), cellulose fibre after charing process and potash are after 1:1 ~ 2 mix in mass ratio, be warming up to 850 ~ 900 DEG C under an inert atmosphere and carry out activation process, heating rate is 5 DEG C/min, and temperature retention time is 60min.
8. the cellulose fibre based active carbon fiber prepared of a method according to claim 1.
9. the application of a cellulose fibre based active carbon fiber according to claim 7 in Water warfare field.
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|---|---|---|---|
| CN201410520311.0A CN104307470B (en) | 2014-09-30 | 2014-09-30 | Preparation method of cellulose fibre based active carbon fiber of a kind of high adsorption capacity and products thereof and application |
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