CN104307470B - Preparation method of cellulose fibre based active carbon fiber of a kind of high adsorption capacity and products thereof and application - Google Patents
Preparation method of cellulose fibre based active carbon fiber of a kind of high adsorption capacity and products thereof and application Download PDFInfo
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- CN104307470B CN104307470B CN201410520311.0A CN201410520311A CN104307470B CN 104307470 B CN104307470 B CN 104307470B CN 201410520311 A CN201410520311 A CN 201410520311A CN 104307470 B CN104307470 B CN 104307470B
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 45
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 27
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- 239000001913 cellulose Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000001994 activation Methods 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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
- 238000012545 processing Methods 0.000 claims abstract description 8
- 238000012805 post-processing Methods 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 21
- 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
- 238000010438 heat treatment Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- 235000014676 Phragmites communis Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000001891 gel spinning Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 244000273256 Phragmites communis Species 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000012190 activator Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 4
- 238000010041 electrostatic spinning Methods 0.000 abstract description 3
- 238000002464 physical blending Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 12
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 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
- 239000002243 precursor Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 238000005470 impregnation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 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
- 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
- 238000007598 dipping method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 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
- 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
- 238000004140 cleaning 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
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 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
- 239000012071 phase Substances 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
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The preparation method of the cellulose fibre based active carbon fiber of a kind of high adsorption capacity of disclosure, first with agriculture and forestry by-product for raw material, obtains cellulose after extracted；Being mixed with N-methylmorpholine-N-oxide by the cellulose obtained, heated under vacuum is completely dissolved to cellulose, obtains cellulose solution, obtains cellulose fibre through electrostatic spinning；Described cellulose fibre, after carbonization processes, mixes for 1:1～5 in mass ratio with activator, obtains described NACF then through activation processing and post processing after grinding.The cellulose fibre that the present invention is prepared with special electrostatic spinning process is for presoma, and after carbonization, then with activator through physical blending, activation, the cellulose fibre based active carbon fiber prepared is applied in purifying water process, has splendid adsorption effect.
Description
Technical field
The present invention relates to the technical field of Carbon fibe, preparation method of cellulose fibre based active carbon fiber being specifically related to a kind 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, it is widely used in industries such as Water warfare, air cleaning, food decolouring, solvent recovery, medical separation.
At present, the preparation of NACF includes three phases:
One is pretreatment, pretreatment stage be in order to make some precursor fibre when high temperature carbonization processes will not fusion and decomposition, and entered pretreatment and can significantly improve performance and the productivity of NACF；
Two is carbonization, and carbonization refers to that precursor fibre heats up heating in an inert atmosphere, removes the volatilizable non-charcoal component that precursor fibre produces in high-temperature process, and the charcoal of residual is reset, and makes Carbon fibe be partially formed graphite microcrystalline structure；
Three is activation, and activation process is to utilize activator to carry out activation processing, improves pore structure and the surface chemical structure of NACF.In commercial production frequently with gas activation easily operate, cost is low, but the specific surface area of fibre active carbon prepared is relatively small, and adopt chemical activation method to prepare specific surface area is higher, pore-size distribution is narrower NACF.
Mainly there are viscose glue base, polypropylene fine (PAN) base, asphaltic base, phenolic aldehyde base, polyvinyl alcohol (PVA) base etc. as the organic fiber of NACF presoma, above-mentioned several all realized industrialized production.In recent years, organic-biological material is utilized to cause the broad interest of people as the method for precursor power activated carbon, on the one hand, this technique is simple, environmental effect is little, 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, it is possible to achieve the high value added utilization of this resource.
As Wang Yuanqing (kapok based active carbon fiber is studied, Donghua University, master thesis, 2007.11) is prepared for kapok based active carbon fiber, and have studied the preparation technology of kapok based active carbon fiber, use H respectively3PO4、ZnCl2、K2CO3、(NH4)2HPO4These four activator activation bombax cotton, is investigated the performance impact to the kapok based active carbon fiber of preparation of the activation processing under different activation temperatures simultaneously.The absorption being applied in water by the different activities Carbon fibe of preparation phenol and methylene blue, maximum methylene blue adsorption number amount is 156.7mg/g.
With natural plant fibre for raw material, fiber surface smoother, natural aperture is less, therefore at raw material or charcoal material in the mixed process with chemical activating agent, often results in contact surface and be only limitted to fiber surface, the pore-creating effect of fibrous inside cannot be realized, additionally, the mixed process of raw material or charcoal material and chemical activating agent often adopts infusion method, therefore also need before activation to be dried completely, this makes preparation process loaded down with trivial details, and cost improves.
Summary of the invention
The preparation method that the invention provides the cellulose fibre based active carbon fiber of a kind of high adsorption capacity, the cellulose fibre prepared with special dry-wet spinning technique is for presoma, after carbonization, 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 kind of preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity, step is as follows:
(1) with agriculture and forestry by-product for raw material, after absent-mindedness extracted, chemical, cellulose is obtained；
(2) being mixed with N-methylmorpholine-N-oxide (NMMO) by the cellulose that step (1) obtains, heated under vacuum is completely dissolved to cellulose, obtains cellulose solution, obtains cellulose fibre through dry-wet spinning；
The technique of described electrostatic spinning is: cellulose solution injects dry-wet spinning equipment, and pressure set is-0.1Pa, and after being incubated 4～6h at temperature 90～98 DEG C, spray webbing obtains as-spun fibre cellulose fiber, obtains cellulose fibre then through post processing.
Particularly as follows:
Cellulose solution is injected in the static still of wet-dry change spray webbing machine, pressure set is-0.1Pa, it is incubated 4～6 hours at temperature 90～98 DEG C, as-spun fibre cellulose fiber is obtained through twin screw-dosing pump-spinning pack spray webbing, then with deionization coagulating bath solidification, rinsing to go out residual NMMO with water afterwards, dehydration had both obtained cellulose fibre after drying；
(3) cellulose fibre that step (2) obtains is after carbonization processes, and mixes for 1:1～5 in mass ratio with activator, obtains described NACF then through activation processing and post processing after grinding；
Described activator is potassium carbonate, potassium hydroxide, sodium hydroxide or sodium carbonate.
Described agriculture and forestry by-product refers to the herbaceous plant stem stalk of rich cellulose discarded in agricultural or forestry.As preferably, described agriculture and forestry by-product is phragmites communis, Caulis et Folium Oryzae stalk, Wheat Straw or corn stalk.These a few class agriculture and forestry by-products contain abundant cellulose.It is preferred that, described agriculture and forestry by-product is phragmites communis, has absorption property more preferably with the NACF that phragmites communis obtains for raw material preparation method in the present invention.
In described agriculture and forestry by-product, cellulosic extraction can take the technological means that this area is conventional, such as alkalinity extraction, particularly as follows: first agriculture and forestry by-product is cleaned, shredded after drying, under room temperature, particle impregnates in alkali liquor 4～24h；Being placed in alkali liquor by the particle of impregnation process again, steaming and decocting 2～3h obtains cellulose solution, is then filtered off the cellulose through alkali liquor steaming and decocting, processes through washing degumming, extrusion dehydration, obtains cellulose.
Extract the cellulose obtained also to need to relax through chemistry, to reduce the adhesion between cellulose, make the further shredding of cellulose.
Step is: be immersed in NaCO by extracting the cellulose obtained3In aqueous solution, then extrusion dehydration；Dilute acid wash again, then extrusion dehydration；Repeat the above steps, then shakes up standby by the cellulose of acquisition after drying.
Described NMMO solvent is through being distilled to the state containing a water of crystallization.
As preferably, in step (2), the mass fraction of described cellulose solution is 10～15%.
As preferably, in step (3), described carbonization treatment temperature is 450～500 DEG C.It is preferred that, carbonization processes and is: be warming up to 200 DEG C with the heating rate of 10 DEG C/min, is incubated 40min, continues to be warming up to 400～500 DEG C with the heating rate of 10 DEG C/min, is incubated 50min.It is about 200 DEG C that cellulose fibre starts the temperature of carbonization, first it is warming up to 200 DEG C with the saving time with fast speed, 40min is so that more carbon containing matter remained with the form of charcoal in the carbonization starting stage in insulation, continue to be warming up to carbonization temperature at a slow speed so that carbon containing matter will not because of the too fast volatilization of heating rate, the insulation of carbonization temperature is to ensure that carbon containing matter can be sufficiently converted into charcoal, select this process technique can save the time, improve charcoal productivity.
As preferably, in step (3), after cellulose fibre after carbonization process mixes for 1:1～2 in mass ratio with potassium carbonate, being warming up to 850～900 DEG C under an inert atmosphere and carry out activation processing, heating rate is 5 DEG C/min, and temperature retention time is 60min, to ensure the energy requirement that activation stage reacts, the aperture making cellulose base NACF attains full development, and does not have again pore-creating excessive, reduces activated carbon specific surface area and absorbability.
In step (3), described last handling process includes washing, dries.
A kind of cellulose fibre based active carbon fiber prepared according to above-mentioned method, specific surface area is relatively big, has abundant microcellular structure, and pore size distribution range is narrower；Abundant functional group is contained on NACF surface simultaneously.
Be directly compared with the Carbon fibe that obtains of presoma with Plant fiber, it is that the Carbon fibe specific surface area that presoma obtains is higher with the cellulose fibre after dry-wet spinning, micropore is abundanter, the absorbability of methylene blue is more excellent, and, its functional group enriches, especially carboxyl (COOH) showed increased contained, and methylene blue has alkalescence, chemical reaction can be there is in the two, consuming methylene blue, this is also that the 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 big.
Compared with prior art, present invention have the advantage that
The present invention is with wide material sources, cheap agriculture and forestry by-product for raw material, after dry-wet spinning, the cellulose fibre of preparation is presoma, compared with native cellulose, there is a large amount of aperture in the cellulose fiber surface of preparation after dry-wet spinning, and this be that the pore-creating in the mixing of later stage and activator and activation process provides the foundation.
In the present invention, the cellulose fibre after carbonization processes can be made directly solid phase mixing with activator, substitutes conventional infusion process, it is not necessary 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 the real protection scope of the present invention is not constituted any type of any restriction by this embodiment.
Embodiment 1
(1) raw material phragmites communis is cleaned, cuts into particle after drying, under room temperature, particle is impregnated in alkali liquor 4h；
(2) being placed in alkali liquor by the particle through impregnation process, steaming and decocting 2h obtains cellulose solution, is then filtered off the cellulose through alkali liquor steaming and decocting, processes through washing degumming, extrusion dehydration, it is thus achieved that cellulose；
(3) cellulose that (2) obtain is immersed in NaCO3In aqueous solution, then extrusion dehydration；
(4) the cellulose dilute acid wash that (3) are obtained, then extrusion dehydration；
(5) repeat step (3) and carry out secondary aqueous sodium carbonate dipping and secondary weak acid scrubbing extrusion dehydration with (4), the cellulose of acquisition is shaken up standby after drying；
(6) being placed in NMMO by the cellulose that (5) obtain, heated under vacuum is to 95 DEG C, until cellulose is completely dissolved；
(7) cellulose (6) obtained/NMMO solution injects in the static still of wet-dry change spray webbing machine, pressure set is-0.1Pa, it is incubated 4 hours at temperature 90 DEG C, as-spun fibre cellulose fiber is obtained through twin screw-dosing pump-spinning pack spray webbing, then with deionization coagulating bath solidification, rinsing to go out residual NMMO with water afterwards, dehydration had both obtained cellulose fibre after drying；
(8) weigh 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, be incubated 40min, continue to be warming up to 450 DEG C with the heating rate of 10 DEG C/min, be incubated 50min；
(9) gained cellulosic fibrous substrates charcoal material and potassium carbonate 1:1.0 mixed grinding in mass ratio are placed in controlled atmosphere generator, under Ar atmosphere, are warming up to 850 DEG C with the heating rate of 5 DEG C/min and carry out activation processing, be incubated 60min；
(10) the cellulose fibre matrix activated carbon after activation is spent deionized water to pH stable about 7, both obtain reed fiber element based active carbon fiber of the present invention after drying.
Detection shows: the pollutant in aqueous solution are had good absorption property by the reed fiber element based active carbon fiber prepared, and its methylene blue adsorption value, more than 800mg/g, can be used for Water warfare.
Embodiment 2
(1) raw material phragmites communis is cleaned, cuts into particle after drying, under room temperature, particle is impregnated in alkali liquor 24h；
(2) being placed in alkali liquor by the particle through impregnation process, steaming and decocting 3h obtains cellulose solution, is then filtered off the cellulose through alkali liquor steaming and decocting, processes through washing degumming, extrusion dehydration, it is thus achieved that cellulose；
(3) cellulose that (2) obtain is immersed in NaCO3In aqueous solution, then extrusion dehydration；
(4) the cellulose dilute acid wash that (3) are obtained, then extrusion dehydration；
(5) repeat step (3) and carry out secondary aqueous sodium carbonate dipping and secondary weak acid scrubbing extrusion dehydration with (4), the cellulose of acquisition is shaken up standby after drying；
(6) being placed in by the cellulose that (5) obtain in N-methylmorpholine-N-oxide (NMMO), heated under vacuum is to 110 DEG C, until cellulose is completely dissolved；
(7) cellulose (6) obtained/NMMO solution injects in the static still of wet-dry change spray webbing machine, pressure set is-0.1Pa, it is incubated 6 hours at temperature 98 DEG C, as-spun fibre cellulose fiber is obtained through twin screw-dosing pump-spinning pack spray webbing, then with deionization coagulating bath solidification, rinsing to go out residual NMMO with water afterwards, dehydration had both obtained cellulose fibre after drying；
(8) weigh 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, be incubated 40min, continue to be warming up to 450 DEG C with the heating rate of 10 DEG C/min, be incubated 50min；It is warming up to 450 DEG C and carries out carbonization process；
(9) gained cellulosic fibrous substrates charcoal material and potassium carbonate 1:2.0 mixed grinding in mass ratio are placed in controlled atmosphere generator, under Ar atmosphere, are warming up to 900 DEG C with the heating rate of 5 DEG C/min, be incubated 60min；
(10) the cellulose fibre matrix activated carbon after activation is spent deionized water to pH stable about 7, both obtain reed fiber element based active carbon fiber of the present invention after drying.
Detection shows: the pollutant in aqueous solution are had good absorption property by the reed fiber element based active carbon fiber prepared, and its methylene blue adsorption value, more than 700mg/g, can be used for Water warfare.
Embodiment 3
Except in step (9), the mass ratio of cellulosic fibrous substrates charcoal material and potassium carbonate changes 1:1.5 into, all the other are with embodiment 1.
Detection shows: the pollutant in aqueous solution are had good absorption property by the reed fiber element based active carbon fiber prepared, and its methylene blue adsorption value, more than 760mg/g, can be used for Water warfare.
Embodiment 4～6
Except being replaced with grass stalk, wheat straw bar, corn stalk except the raw material in step (1) by phragmites communis, all the other are with embodiment 1.
Detection shows: the pollutant in aqueous solution are respectively provided with good absorption property by grass stalk cellulose base NACF, wheat straw rod fibers element based active carbon fiber and the cornstalk fiber element based active carbon fiber prepared respectively, its methylene blue adsorption value is all higher than 600mg/g, can be used for Water warfare.
Compared with other NACF of preparation in prior art (the most about 500mg/g), NACF prepared by the present invention is in Water warfare field is applied, methylene blue adsorption value is all higher than 600mg/g, and the best can more than 800mg/g, and absorption property is very excellent.
Claims (8)
1. the preparation method of the cellulose fibre based active carbon fiber of a high adsorption capacity, it is characterised in that comprise the steps:
(1) with agriculture and forestry by-product for raw material, extracted cellulose is obtained；
(2) being mixed with N-methylmorpholine-N-oxide by the cellulose that step (1) obtains, heated under vacuum is completely dissolved to cellulose, obtains cellulose solution, obtains cellulose fibre through dry-wet spinning；
The mass fraction of described cellulose solution is 10～15%；
The technique of described dry-wet spinning is: cellulose solution injects dry-wet spinning equipment, and pressure set is-0.1Pa, and after being incubated 4～6h at temperature 90～98 DEG C, spray webbing obtains as-spun fibre cellulose fiber, obtains cellulose fibre then through post processing；
(3) cellulose fibre that step (2) obtains processes through carbonization, after cellulose fibre after carbonization process mixes for 1:1～2 in mass ratio with potassium carbonate, it is warming up to 850～900 DEG C under an inert atmosphere and carries out activation processing, obtain described NACF then through post processing.
2. the preparation method of the NACF of high adsorption capacity according to claim 1, it is characterised in that described agriculture and forestry by-product is one or more in phragmites communis, grass stalk, Wheat Straw, corn stalk.
3. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, it is characterised in that in step (1), extracts the cellulose obtained stand-by after chemistry is relaxed, particularly as follows:
It is immersed in Na by extracting the cellulose obtained2CO3In aqueous solution, dilute acid wash, then extrusion dehydration again after extrusion dehydration；Repeat the above steps, then shakes up standby by the cellulose of acquisition after drying.
4. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, it is characterised in that in step (3), described carbonization treatment temperature is 450～500 DEG C.
5. 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 carbonization processes: 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, be incubated 50min.
6. the preparation method of the cellulose fibre based active carbon fiber of high adsorption capacity according to claim 1, it is characterised in that in step (3), the heating rate of activation processing is 5 DEG C/min, and temperature retention time is 60min.
7. the cellulose fibre based active carbon fiber that prepared by a method according to claim 1.
8. a cellulose fibre based active carbon fiber according to claim 7 application in Water warfare field.
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| CN109422263B (en) * | 2017-08-21 | 2021-10-26 | 中国科学院理化技术研究所 | Cellulose porous activated carbon and preparation method and application thereof |
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