CN108862274A - A kind of preparation method and applications of cellulose base level porous carbon materials - Google Patents
A kind of preparation method and applications of cellulose base level porous carbon materials Download PDFInfo
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- CN108862274A CN108862274A CN201810782746.0A CN201810782746A CN108862274A CN 108862274 A CN108862274 A CN 108862274A CN 201810782746 A CN201810782746 A CN 201810782746A CN 108862274 A CN108862274 A CN 108862274A
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- cellulose base
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 72
- 239000001913 cellulose Substances 0.000 title claims abstract description 72
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 117
- 241000208202 Linaceae Species 0.000 claims abstract description 54
- 235000004431 Linum usitatissimum Nutrition 0.000 claims abstract description 54
- 239000002002 slurry Substances 0.000 claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004202 carbamide Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000002087 whitening effect Effects 0.000 claims abstract description 29
- 238000010009 beating Methods 0.000 claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000011133 lead Substances 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 4
- 240000008564 Boehmeria nivea Species 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation method and applications of cellulose base level porous carbon materials.This approach includes the following steps：(1) whitening flax slurry is beaten, beating degree is 60~90 ° of SR, is then centrifuged for being dehydrated, makes its solid content 30~50%, obtains high beating degree flax pulp fiber；(2) potassium hydroxide, urea and high beating degree flax pulp are dissolved in water after mixing, then dry moisture, obtain KOH/ urea/flax pulp cellulose base presoma；(3) KOH/ urea/flax pulp cellulose base presoma is subjected to high temperature cabonization under vacuum conditions, salt acid etch, washing, suction filtration is then used, is finally dried in vacuo, obtains cellulose base level porous carbon materials.The present invention generates synergistic effect activated carbon material using potassium hydroxide and urea, and the level porous activated carbon for preparing high-specific surface area has significant effect to the absorption of heavy metal in water ion, can be applied to the fields such as heavy metal ion adsorbed and electrode material.
Description
Technical field
The invention belongs to field of functional materials, in particular to the preparation method of a kind of cellulose base level porous carbon materials and
It is applied.
Background technique
With the rapid industrial development in our country, industrial wastewater discharge increases, and Heavy Metals in Waters is seriously polluted, and microorganism
Can not degrade heavy metal again.The heavy metal ion contents such as Mercury in Water Body, cadmium, chromium, lead, copper are exceeded can health to the mankind and society
Development cause damages.So how reducing the heavy metal pollution in water body and recycling the heavy metal in water is current society
The great difficult problem of meeting.The heavy metal ion in removal water body mainly has chemical precipitation method, electrolysis method, hyperfiltration, film point now
From method, ion-exchange etc..But in place of chemiadsorption and electrolysis method all Shortcomings, they are not suitable for handling low concentration weight
Metal ion waste water is difficult to control the concentration of heavy metal ion within critical field, and the processing cost of electrolysis method is higher.
Although membrane separation method and ionic adsorption method effect are pretty good, influenced by environment and impurities in water, maintenance cost
It is relatively high.And cost is relatively low due to it, large amount of adsorption, strong operability, regeneration treatment facilitate etc. that advantages are extensive for absorption method
Applied in Industrial Wastewater Treatment.
Active porous charcoal not only has pore structure very rich and huge specific surface area as adsorbent, and
There are the functional groups such as hydroxyl abundant, carboxyl, carbonyl on its surface, there is good hydrophily and chemical modification.Therefore it provides
The level porous carbon materials of a kind of high-specific surface area and heavy metal ion for removing in water body has important practical significance.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, it is porous to provide a kind of cellulose base level
The preparation method of carbon material.
Another object of the present invention is to provide the cellulose base level porous carbon materials that the method is prepared.The carbon
Material has pore structure very rich and huge specific surface area, and the carbon material surface adulterates a large amount of N, O member
Element has good hydrophily and chemical modification.
Another object of the present invention is to provide the application of the cellulose base level porous carbon materials.
The purpose of the invention is achieved by the following technical solution：A kind of preparation side of cellulose base level porous carbon materials
Method includes the following steps：
(1) whitening flax slurry is beaten, beating degree is 60~90 ° of SR, is then centrifuged for being dehydrated, makes its solid content 30
~50% (solid content is mass percent of the oven-dry weight of slurry relative to aqueous slurry), it is fine to obtain high beating degree flax pulp
Dimension；
(2) high beating degree flax pulp obtained in potassium hydroxide, urea and step (1) is dissolved in water after mixing,
Moisture is dried again, obtains KOH/ urea/flax pulp cellulose base presoma；
(3) KOH/ urea obtained in step (2)/flax pulp cellulose base presoma is subjected to high temperature under vacuum conditions
Then carbonization uses salt acid etch, washing, suction filtration, is finally dried in vacuo, obtains cellulose base level porous carbon materials.
The slurry of whitening flax described in step (1) is that the whitening flax of content of cellulose 92%~97% (w/w) is starched.
Mashing described in step (1) is to be beaten using PFI fiberizer；Its beating degree is preferably 60~80 ° of SR.
The absolute dry mass ratio of potassium hydroxide described in step (2) and high beating degree flax pulp fiber is 1~6:1；It is preferred that
It is 2~5:1.
The absolute dry mass ratio of urea described in step (2) and high beating degree flax pulp fiber is 1~4:1.
Water described in step (2) is preferably deionized water.
Water described in step (2) and high beating degree whitening flax slurry absolute dry mass ratio are 40:1.
Drying moisture described in step (2) is to dry moisture in 105 DEG C of baking ovens.
High temperature cabonization described in step (3) is to be carbonized in electron tubes type sintering furnace high temperature；The condition of its high temperature cabonization
For：600~900 DEG C are warming up to the heating rate of 2~10 DEG C/min, then keeps the temperature 1~4h；Preferably：Under nitrogen protection,
600~900 DEG C are warming up to the heating rate of 2~8 DEG C/min, then keeps the temperature 1~4h.
The flow velocity of the nitrogen is 50~250cm3/min；
The concentration of hydrochloric acid described in step (3) is 0.5~2mol/L.
The time of salt acid etch described in step (3) is preferably 1h.
A kind of cellulose base level porous carbon materials, are prepared by method described in any of the above embodiments.
The cellulose base level porous carbon materials are in the fields such as heavy metal adsorption, purification of waste water, electrode material
Using.
The present invention has the following advantages and effects with respect to the prior art：
(1) meet environmentally protective theory by raw material of whitening flax slurry in the present invention, raw material sources are extensive, simple process side
Just, it and is widely used.The fibre of bigger serface can be obtained using potassium hydroxide and urea collaboration activated cellulose base presoma
Wei Su base time porous carbon materials have hydroxyl abundant, carboxyl, carbonyl etc. on its surface of carbon material obtained after high temperature cabonization
Functional group, and a large amount of N, O elements are adulterated, so that carbon material increased activity, has significant inhale to heavy metal in water ion
Attached effect.
(2) potassium hydroxide and urea generate synergistic effect in the present invention, and activated carbon material prepares the level of high-specific surface area
Porous activated carbon has significant effect, simple process, porous carbon materials energy obtained to the absorption of heavy metal in water ion
It is widely used in the fields such as heavy metal ion adsorbed and electrode material.
Detailed description of the invention
Fig. 1 is the cellulose base level porous carbon materials N that embodiment 3 is prepared2Isothermal adsorption desorption curve and aperture point
Butut；Wherein, figure A is N2Isothermal adsorption desorption curve graph；Figure B is graph of pore diameter distribution.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Whitening flax slurry is purchased from Feng Yuan (Xingtai) extraordinary Paper Co., Ltd, other raw materials and examination in preparation method of the present invention
Agent can be from buying on the market.
Embodiment 1
A kind of preparation method of cellulose base level porous carbon materials, includes the following steps：
(1) the whitening flax slurry that content of cellulose is 92.5% (w/w) is beaten through PFI fiberizer height, beating degree is
60 ° of SR, are then dehydrated with supercentrifuge, equilibrium water conten, measure slurry solid content, and solid content is the 30.78% (over dry of slurry
Measure the mass percent relative to aqueous slurry).
It (2) is 2 according to the high beating degree whitening flax slurry absolute dry mass ratio obtained in potassium hydroxide, urea and step (1):
1:1 mixes three.Addition is appropriate, and (deionized water is 40 with whitening flax slurry absolute dry mass ratio:1) deionized water is completely dissolved
Potassium hydroxide and urea are uniformly mixed slurry and solution.The mixed system is put into drying moisture in 105 DEG C of baking ovens to be consolidated
The KOH/ urea of phase/flax pulp cellulose base presoma.
(3) KOH/ urea/flax pulp cellulose base presoma is put into electron tubes type sintering furnace, vacuumizes, is passed through nitrogen
Gas shielded, air-flow 50cm3/min；Then 600 DEG C are warming up to 2 DEG C/min, it is porous to obtain cellulose base level after heat preservation 1h
Carbon；Then 0.5mol/L salt acid etch 1h (room temperature) is used at room temperature, and the time is 1 hour), washing filters, and vacuum drying obtains
Cellulose base level porous carbon materials.
Embodiment 2
A kind of preparation method of cellulose base level porous carbon materials, includes the following steps：
(1) the whitening flax slurry that content of cellulose is 94% (w/w) is beaten through PFI fiberizer height, beating degree is 70 °
Then SR is dehydrated with supercentrifuge, equilibrium water conten, measures slurry solid content, and solid content is the 35.34% (oven-dry weight of slurry
Mass percent relative to aqueous slurry).
It (2) is 3 according to potassium hydroxide, urea and high beating degree whitening flax slurry absolute dry mass ratio:2:1 mixes three.
Appropriate amount of deionized water is added, and (deionized water is 40 with whitening flax slurry absolute dry mass ratio:1) it is completely dissolved potassium hydroxide and urea,
It is uniformly mixed slurry and solution.The mixed system is put into drying moisture in 105 DEG C of baking ovens and obtains KOH/ urea/Asia of solid phase
Ramie pulp fiber element base presoma.
(3) KOH/ urea/flax pulp cellulose base presoma is put into electron tubes type sintering furnace, vacuumizes, is passed through nitrogen
Gas shielded, air-flow 100cm3/min；Then 700 DEG C are warming up to 4 DEG C/min, it is porous to obtain cellulose base level after heat preservation 2h
Carbon；Then 1mol/L salt acid etch 1h is used at room temperature, and washing filters, and vacuum drying obtains cellulose base level porous carbon
Material.
Embodiment 3
A kind of preparation method of cellulose base level porous carbon materials, includes the following steps：
(1) the whitening flax slurry that content of cellulose is 95.5% (w/w) is beaten through PFI fiberizer height, beating degree is
80 ° of SR, are then dehydrated with supercentrifuge, equilibrium water conten, measure slurry solid content, and solid content is the 40.86% (over dry of slurry
Measure the mass percent relative to aqueous slurry).
It (2) is 4 according to potassium hydroxide, urea and high beating degree whitening flax slurry absolute dry mass ratio:3:1 mixes three.
Appropriate amount of deionized water is added, and (deionized water is 40 with whitening flax slurry absolute dry mass ratio:1) it is completely dissolved potassium hydroxide and urea,
It is uniformly mixed slurry and solution.The mixed system is put into drying moisture in 105 DEG C of baking ovens and obtains KOH/ urea/Asia of solid phase
Ramie pulp fiber element base presoma.
(3) KOH/ urea/flax pulp cellulose base presoma is put into electron tubes type sintering furnace, vacuumizes, is passed through nitrogen
Gas shielded, air-flow 150cm3/min；Then 800 DEG C are warming up to the heating rate of 5 DEG C/min, obtain cellulose after keeping the temperature 3h
Base time porous carbon；Then 1.5mol/L salt acid etch 1h is used at room temperature, and washing filters, and vacuum drying obtains cellophane base layer
Secondary porous carbon materials.
Embodiment 4
A kind of preparation method of cellulose base level porous carbon materials, includes the following steps：
(1) the whitening flax slurry that content of cellulose is 97% (w/w) is beaten through PFI fiberizer height, beating degree is 80 °
Then SR is dehydrated with supercentrifuge, equilibrium water conten, measures slurry solid content, and solid content is the 45.75% (oven-dry weight of slurry
Mass percent relative to aqueous slurry).
It (2) is 5 according to potassium hydroxide, urea and high beating degree whitening flax slurry absolute dry mass ratio:4:1 mixes three.
Appropriate amount of deionized water is added, and (deionized water is 40 with whitening flax slurry absolute dry mass ratio:1) it is completely dissolved potassium hydroxide and urea,
It is uniformly mixed slurry and solution.The mixed system is put into drying moisture in 105 DEG C of baking ovens and obtains KOH/ urea/Asia of solid phase
Ramie pulp fiber element base presoma.
(3) KOH/ urea/flax pulp cellulose base presoma is put into electron tubes type sintering furnace, vacuumizes, is passed through nitrogen
Gas shielded, air-flow 200cm3/min；Then 900 DEG C are warming up to 8 DEG C/min, it is porous to obtain cellulose base level after heat preservation 4h
Carbon；Then 2mol/L salt acid etch 1h is used at room temperature, and washing filters, and vacuum drying obtains cellulose base level porous carbon
Material.
Comparative example 1
A kind of preparation method of cellulose base porous carbon materials, includes the following steps：
(1) the whitening flax slurry that content of cellulose is 95.5% (w/w) is beaten through PFI fiberizer height, beating degree is
80 ° of SR, are then dehydrated with supercentrifuge, equilibrium water conten, measure slurry solid content, and solid content is the 40.86% (over dry of slurry
Measure the mass percent relative to aqueous slurry).
It (2) is 4 according to potassium hydroxide and high beating degree whitening flax slurry absolute dry mass ratio:1 mixes the two.It is added appropriate
(deionized water is 40 with whitening flax slurry absolute dry mass ratio to deionized water:1) it is completely dissolved potassium hydroxide, keeps slurry and solution mixed
It closes uniform.The mixed system is put into drying moisture in 105 DEG C of baking ovens and obtains the KOH/ flax pulp cellulose base presoma of solid phase.
(3) KOH/ flax pulp cellulose base presoma is put into electron tubes type sintering furnace, is vacuumized, be passed through nitrogen guarantor
Shield, air-flow 150cm3/min；Then 800 DEG C are warming up to the heating rate of 5 DEG C/min, obtain cellophane base layer after keeping the temperature 3h
Secondary porous carbon；Then 1.5mol/L salt acid etch 1h is used at room temperature, and washing filters, and it is more that vacuum drying obtains cellulose base level
Hole carbon material.
Comparative example 2
A kind of preparation method of cellulose base porous carbon materials, includes the following steps：
(1) the whitening flax slurry that content of cellulose is 95.5% (w/w) is beaten through PFI fiberizer height, beating degree is
80 ° of SR, are then dehydrated with supercentrifuge, equilibrium water conten, measure slurry solid content, and solid content is the 40.86% (over dry of slurry
Measure the mass percent relative to aqueous slurry).
It (2) is 3 according to urea and high beating degree whitening flax slurry absolute dry mass ratio:1 mixes the two.Be added in right amount go from
(deionized water is 40 with whitening flax slurry absolute dry mass ratio to sub- water:1) it is completely dissolved urea, is uniformly mixed slurry and solution.
The mixed system is put into drying moisture in 105 DEG C of baking ovens and obtains urea/flax pulp cellulose base presoma of solid phase.
(3) urea/flax pulp cellulose base presoma is put into electron tubes type sintering furnace, is vacuumized, be passed through nitrogen guarantor
Shield, air-flow 150cm3/min；Then 800 DEG C are warming up to the heating rate of 5 DEG C/min, obtain cellophane base layer after keeping the temperature 3h
Secondary porous carbon；Then 1.5mol/L salt acid etch 1h is used at room temperature, and washing filters, and it is more that vacuum drying obtains cellulose base level
Hole carbon material.
Effect example
The absorption property test of cellulose base level porous carbon materials and specific surface area and pore-size distribution test.
To the heavy metal ion for the cellulose base level porous carbon materials that Examples 1 to 4 and comparative example 1~2 are prepared
Absorption property and specific surface area and pore-size distribution are tested.
Heavy metal ion adsorbed performance test：Prepare the Pb of 100mg/L2+Standard solution.The carbon materials abrasive lapping that will be prepared
Cheng Fen weighs the ground carbon material of 6mg and is added separately in the lead ion solution of 100mg/L (solution 20ml), at 25 DEG C
Under conditions of, adsorption test is carried out with the speed stirring 60min of 150r/min with magnetic stirring apparatus.By solution after the completion of absorption
It is put into centrifuge and 10min is centrifuged with the rate of 3000r/min, take supernatant liquor later.It is analyzed with atomic absorption spectrophotometer
Pb in solution2+Concentration.
Heavy metal ion adsorbed amount Q (mg/g), calculation formula are：Q=(C0-CT) × V/m is (in formula：C0To adsorb preceding solution
Heavy metal ion Pb2+Mass concentration, CTFor solution heavy metal ion Pb after absorption2+Mass concentration, V indicate Pb2+Solution body
Product, m are the quality of cellulose base level porous carbon).Test result is shown in Table 1.
Specific surface area and pore-size distribution test：Sample (cellulose base level porous carbon materials) is placed on before test sample
It deaerates 10 hours at 150 DEG C, eliminates the volatile materials of material surface.Compared automatically using 2460 type of Micomeritics ASAP
Surface area and Porosimetry are analyzed.The specific surface area and pore-size distribution of porous carbon materials are with BET (Brunaure-
Emmett-Teller) theoretical calculation method obtains, and the results are shown in Table 1.
Cellulose base level porous carbon materials are to Pb made from 1. Examples 1 to 4 of table, comparative example 1~22+Adsorbance and ratio
Test result is as follows for surface area and pore-size distribution
| Sample | Pb2+Adsorbance (mg/g) | Specific surface area (m2/g) | Average pore size (nm) |
| Embodiment 1 | 21.52 | 1245.89 | 2.4519 |
| Embodiment 2 | 25.36 | 1460.35 | 2.2347 |
| Embodiment 3 | 31.09 | 1603.56 | 1.9186 |
| Embodiment 4 | 30.46 | 1513.49 | 1.9453 |
| Comparative example 1 | 19.34 | 1078.94 | 2.9781 |
| Comparative example 2 | 18.35 | 578.43 | 3.8675 |
Comparative example 1 is the independent activated cellulose base presoma of potassium hydroxide in table 1, and comparative example 2 is that urea individually activates fibre
Tie up plain base presoma；It may thus be appreciated that being obviously improved fiber using potassium hydroxide and urea simultaneously come activated cellulose base forerunner's physical efficiency
The specific surface area of plain base porous carbon materials, and a large amount of micropores are generated, increase the activity of carbon material, is promoted heavy metal ion adsorbed
Effect.In addition, with the Quality advance of potassium hydroxide, the specific surface area first increases and then decreases of cellulose base porous carbon materials, this
It is to generate more micropore because suitable potassium hydroxide can carry out suitable pore-creating to carbon material；Excessive potassium hydroxide can be broken
Bad pore structure makes the hole result of carbon material collapse, macropore and it is mesoporous increase, to reduce the specific surface area of carbon material.
Fig. 1 is the N of cellulose base level porous carbon materials prepared by the best embodiment 3 of effect2Isothermal adsorption desorption is bent
Line and pore-size distribution, it can be seen from the figure that the carbon material belongs to as defined in International Union of Pure and Applied Chemistry (IUPAC)
IVth class hysteresis loop, and most of the carbon material is micropore, is had a small amount of mesoporous.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of cellulose base level porous carbon materials, which is characterized in that include the following steps：
(1) by whitening flax slurry be beaten, beating degree be 60~90 ° of SR, be then centrifuged for being dehydrated, make its solid content 30~
50%, obtain high beating degree flax pulp fiber；
(2) high beating degree flax pulp obtained in potassium hydroxide, urea and step (1) is dissolved in water after mixing, then dried
Solid carbon dioxide point, obtains KOH/ urea/flax pulp cellulose base presoma；
(3) KOH/ urea obtained in step (2)/flax pulp cellulose base presoma is subjected to pyrocarbon under vacuum conditions
Change, then uses salt acid etch, washing, suction filtration, be finally dried in vacuo, obtain cellulose base level porous carbon materials.
2. the preparation method of cellulose base level porous carbon materials according to claim 1, it is characterised in that：
The condition of high temperature cabonization described in step (3) is：600~900 DEG C are warming up to the heating rate of 2~10 DEG C/min,
Then 1~4h is kept the temperature.
3. the preparation method of cellulose base level porous carbon materials according to claim 2, it is characterised in that：
The condition of high temperature cabonization described in step (3) is：Under nitrogen protection, it is warming up to the heating rate of 2~8 DEG C/min
600~900 DEG C, then keep the temperature 1~4h；
The flow velocity of the nitrogen is 50~250cm3/min。
4. the preparation method of cellulose base level porous carbon materials according to claim 1, it is characterised in that：
The absolute dry mass ratio of potassium hydroxide described in step (2) and high beating degree flax pulp fiber is 1~6:1；
The absolute dry mass ratio of urea described in step (2) and high beating degree flax pulp fiber is 1~4:1.
5. the preparation method of cellulose base level porous carbon materials according to claim 1, it is characterised in that：
The slurry of whitening flax described in step (1) is that the whitening flax of content of cellulose 92%~97% (w/w) is starched.
6. the preparation method of cellulose base level porous carbon materials according to claim 1, it is characterised in that：Step (3)
Described in hydrochloric acid concentration be 0.5~2mol/L.
7. the preparation method of cellulose base level porous carbon materials according to claim 1, it is characterised in that：
Water described in step (2) and high beating degree whitening flax slurry absolute dry mass ratio are 40:1.
8. the preparation method of cellulose base level porous carbon materials according to claim 1, it is characterised in that：
Drying described in step (2) is to dry in 105 DEG C of baking ovens；
The time of salt acid etch described in step (3) is 1h.
9. a kind of cellulose base level porous carbon materials, it is characterised in that：Pass through method according to any one of claims 1 to 8
It is prepared.
10. cellulose base level porous carbon materials as claimed in claim 9 are led in heavy metal adsorption, purification of waste water or electrode material
Application in domain.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109850894A (en) * | 2019-03-20 | 2019-06-07 | 西安理工大学 | A kind of method and application preparing porous carbon materials using useless corrugation paper fiber as raw material |
| CN110526243A (en) * | 2019-07-29 | 2019-12-03 | 桂林理工大学 | A kind of preparation method and applications of the biomass porous carbon of supercapacitor |
| CN110697705A (en) * | 2019-10-18 | 2020-01-17 | 中国铝业股份有限公司 | Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure |
| CN110714352A (en) * | 2019-10-15 | 2020-01-21 | 齐鲁工业大学 | Preparation method of self-supporting porous carbon fiber network material |
| CN111196601A (en) * | 2020-01-19 | 2020-05-26 | 桂林理工大学 | Super capacitor electrode material and preparation method and application thereof |
| CN111634910A (en) * | 2020-06-22 | 2020-09-08 | 桂林理工大学 | Super capacitor electrode material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692379A (en) * | 2014-12-24 | 2015-06-10 | 无限极（中国）有限公司 | Hemp-stem active carbon and preparation method, forming method and application thereof |
| CN105480975A (en) * | 2016-02-25 | 2016-04-13 | 黑龙江省科学院大庆分院 | Method for preparing high-specific-surface-area porous carbon with hemp stems as carbon source |
| CN106629655A (en) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Application and preparation method of biomass-based nitrogen-doped porous carbon |
| CN107442068A (en) * | 2017-08-29 | 2017-12-08 | 华南理工大学 | Micro- mesoporous activated carbon/the SiO of nanometer is prepared using black liquid2Composite and its application |
-
2018
- 2018-07-17 CN CN201810782746.0A patent/CN108862274B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692379A (en) * | 2014-12-24 | 2015-06-10 | 无限极（中国）有限公司 | Hemp-stem active carbon and preparation method, forming method and application thereof |
| CN105480975A (en) * | 2016-02-25 | 2016-04-13 | 黑龙江省科学院大庆分院 | Method for preparing high-specific-surface-area porous carbon with hemp stems as carbon source |
| CN106629655A (en) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Application and preparation method of biomass-based nitrogen-doped porous carbon |
| CN107442068A (en) * | 2017-08-29 | 2017-12-08 | 华南理工大学 | Micro- mesoporous activated carbon/the SiO of nanometer is prepared using black liquid2Composite and its application |
Non-Patent Citations (1)
| Title |
|---|
| MIROSŁAW KWIATKOWSKI: "Analysis of the microporous structure of the low-cost activated carbon fibres obtained from flax and jute cloth", 《JOURNAL OF MATHEMATIC CHEMISTRY》 * |
Cited By (10)
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| CN109850894A (en) * | 2019-03-20 | 2019-06-07 | 西安理工大学 | A kind of method and application preparing porous carbon materials using useless corrugation paper fiber as raw material |
| CN110526243A (en) * | 2019-07-29 | 2019-12-03 | 桂林理工大学 | A kind of preparation method and applications of the biomass porous carbon of supercapacitor |
| CN110714352A (en) * | 2019-10-15 | 2020-01-21 | 齐鲁工业大学 | Preparation method of self-supporting porous carbon fiber network material |
| CN110697705A (en) * | 2019-10-18 | 2020-01-17 | 中国铝业股份有限公司 | Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure |
| CN110697705B (en) * | 2019-10-18 | 2021-02-05 | 中国铝业股份有限公司 | Rapid preparation method of asphalt-based activated carbon with hierarchical pore structure |
| CN111196601A (en) * | 2020-01-19 | 2020-05-26 | 桂林理工大学 | Super capacitor electrode material and preparation method and application thereof |
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| CN113683088A (en) * | 2021-07-27 | 2021-11-23 | 西安交通大学 | Cellulose-based three-dimensional porous carbon material and preparation method and application thereof |
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