CN115318260B - Manganese and cyclodextrin co-modified bamboo charcoal material and preparation method and application thereof - Google Patents
Manganese and cyclodextrin co-modified bamboo charcoal material and preparation method and application thereof Download PDFInfo
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- CN115318260B CN115318260B CN202210885827.XA CN202210885827A CN115318260B CN 115318260 B CN115318260 B CN 115318260B CN 202210885827 A CN202210885827 A CN 202210885827A CN 115318260 B CN115318260 B CN 115318260B
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- cyclodextrin
- manganese
- bamboo charcoal
- charcoal material
- solvent
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- 239000011425 bamboo Substances 0.000 title claims abstract description 162
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 160
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 160
- 241001330002 Bambuseae Species 0.000 title claims abstract description 160
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 160
- 239000003610 charcoal Substances 0.000 title claims abstract description 138
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 88
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000011572 manganese Substances 0.000 title claims abstract description 57
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 114
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 150000002696 manganese Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000001116 FEMA 4028 Substances 0.000 claims description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 12
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 12
- 229960004853 betadex Drugs 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 3
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 3
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 4
- 238000001179 sorption measurement Methods 0.000 abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000003915 air pollution Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001834 photoacoustic spectrum Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 208000019693 Lung disease Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 206010044302 Tracheitis Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- -1 methyl halide Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a manganese and cyclodextrin co-modified bamboo charcoal material, and a preparation method and application thereof. The preparation method of the invention comprises the following steps: fully dispersing manganese salt and bamboo powder in a solvent, and obtaining bamboo powder loaded with manganese element through stirring reaction, filtering, washing and drying; then calcining to obtain manganese-loaded bamboo charcoal; and fully dispersing the cyclodextrin and the bamboo charcoal loaded with manganese element in a solvent, and obtaining the manganese and cyclodextrin co-modified bamboo charcoal material through stirring reaction, filtering, washing and drying. The material obtained by the invention has good adsorption performance on organic matters such as benzene, formaldehyde and the like, and the adsorption experiments all reach the national standard of first-grade carbon package; meanwhile, the formaldehyde-degrading agent has a formaldehyde degrading effect.
Description
Technical Field
The invention relates to a manganese and cyclodextrin co-modified bamboo charcoal material and a preparation method and application thereof, and belongs to the technical field of material synthesis.
Background
The current air pollution becomes a very important problem at home and abroad, and the long-term environment containing high-concentration air pollutants can increase the risk of people suffering from various diseases and influence the physical health of people. Among them, indoor environmental pollution is a typical type of air pollution, and it is considered that human beings have entered a third pollution period characterized by "indoor environmental pollution". The indoor environment pollution problem is complex, the harm is serious, and various diseases such as respiratory diseases, chronic lung diseases, tracheitis, bronchitis, lung cancer and the like are caused. Formaldehyde is colorless and has a pungent odor, is one of main induction sources of indoor environmental pollution, and is mainly shown as sensitization and mutation. Benzene is mainly from paint, wood lacquer and adhesive for interior decoration, and has high toxicity; paints incorporating benzene solvents can emit an aromatic odor that is toxic to humans. In recent years, people pay enough attention to indoor environment improvement, for example, buying a plurality of carbon bags after new house decoration to remove indoor pollution has become a living habit of most people. Carbon bags have been widely used in the field of air purification.
The concept of "treating waste with waste" is an important way of pollution control, carbon materials are widely used for air pollution control, and biochar materials have great potential in pollution control. The biochar is a loose porous solid product generated by high-temperature thermal cracking of biomass (biological organic material) in an anoxic or anaerobic environment, has the characteristics of high porosity, large specific surface area and the like, has wide raw material sources (such as straw, wood, bamboo and the like), and is simple to prepare; but there are numerous biochar products in the market, and the competition pressure is high. Therefore, the development performance is better or the function is obviously different from that of the characteristic carbon bag product of the prior carbon bag, and the method has great significance.
The surface property and the electronic structure of the biochar can be improved by introducing groups containing iron, cobalt, manganese and the like into the biochar. In short, the modification of the biochar by different methods can improve the pore structure, specific surface area and surface functional group number of the biochar, thereby improving the performance of the biochar. However, the existing biochar has the defect of simultaneous adsorption and modification of the benzene and the formaldehyde, and the adsorption of the benzene and the formaldehyde does not reach the national standard of the first-grade carbon package at the same time because the carbon package existing in the market is researched.
Therefore, development of a biochar material with excellent adsorption performance on benzene and formaldehyde is urgently needed to reach the national standard of first-grade carbon package.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a manganese and cyclodextrin co-modified bamboo charcoal material, and a preparation method and application thereof. The manganese and the manganese are introduced into the biochar to obtain the manganese and cyclodextrin co-modified bamboo charcoal material; the material obtained by the invention has good adsorption performance on organic matters such as benzene, formaldehyde and the like, and the adsorption experiments all reach the national standard of first-grade carbon package; meanwhile, the formaldehyde-degrading agent has a formaldehyde degrading effect. The manganese and cyclodextrin co-modification of the invention improves the dispersibility of the material on one hand, and increases the active sites of the material on the other hand, so that the adsorption and degradation performances are greatly improved.
The invention is realized by the following technical scheme:
the bamboo charcoal material is bamboo charcoal loaded with manganese element and modified by manganese and cyclodextrin, wherein the manganese element exists in an oxide state; the bamboo charcoal material is of a porous structure. The obtained bamboo charcoal material maintains some vascular bundle structures of the bamboo powder, and has a three-dimensional stacking structure and a certain pore.
According to the invention, the specific surface area of the bamboo charcoal material is 300-400m 2 /g。
The preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material comprises the following steps:
(1) Fully dispersing manganese salt and bamboo powder in a solvent, and obtaining bamboo powder loaded with manganese element through stirring reaction, filtering, washing and drying; then calcining to obtain manganese-loaded bamboo charcoal;
(2) And fully dispersing the cyclodextrin and the bamboo charcoal loaded with manganese element in a solvent, and obtaining the manganese and cyclodextrin co-modified bamboo charcoal material through stirring reaction, filtering, washing and drying.
Preferably, in the step (1), the manganese salt is potassium permanganate, manganese chloride, manganese bromide, manganese iodide, manganese sulfate or manganese nitrate; preferably, the manganese salt is potassium permanganate.
According to a preferred embodiment of the present invention, in the step (1), the particle size of the bamboo powder is 50 to 80 mesh, preferably 60 mesh. The bamboo powder is commercially available.
According to the invention, in the step (1), the mass-volume ratio of the manganese salt to the solvent is as follows: (0.1-20): (20-1000), unit: g/mL; preferably, the mass volume ratio of the manganese salt to the solvent is as follows: (0.1-20): (100-1000) g/mL; further preferably, the mass volume ratio of manganese salt to solvent is: (0.1-10): (500-1000), unit: g/mL.
According to the invention, in the step (1), the mass ratio of manganese salt to bamboo powder is as follows: (0.1-20): (0.1-60); preferably, the mass ratio of the manganese salt to the bamboo powder is as follows: (0.5-15): (0.1-30); further preferably, the mass ratio of the manganese salt to the bamboo powder is as follows: (1-10): (1-10); most preferably, the mass ratio of manganese salt to bamboo powder is as follows: (1-2): 10.
according to the invention, in the step (1), the stirring reaction temperature is room temperature, and the stirring reaction time is 0.5-36 h; preferably, the stirring reaction time is 10-24 hours; most preferably, the stirring reaction time is 12 hours.
According to a preferred embodiment of the present invention, in step (1), the calcination conditions are: gas protection, wherein the calcination temperature is 200-1000 ℃ and the calcination time is 1-12 h; preferably, the gas is nitrogen, argon, helium or oxygen, the calcination temperature is 500-800 ℃, and the calcination time is 2-4 hours; most preferably, the calcination temperature is 600℃and the calcination time is 2 hours.
Preferably, in step (2), the cyclodextrin is α -cyclodextrin, β -cyclodextrin or γ -cyclodextrin; preferably, the cyclodextrin is beta-cyclodextrin.
According to the invention, in the step (2), the mass-volume ratio of the cyclodextrin to the solvent is (0.1-20): (20-1000), unit: g/mL; preferably, the mass volume ratio of cyclodextrin to solvent is: (0.1-20): (100-1000) g/mL, unit: g/mL; most preferably, the mass volume ratio of cyclodextrin to solvent is: (0.1-10): (500-1000), unit: g/mL.
According to the invention, in the step (2), the mass ratio of the cyclodextrin to the manganese element-loaded bamboo charcoal is as follows: (0.1-20): (0.1-60); preferably, the mass ratio of cyclodextrin to manganese element-loaded bamboo charcoal is as follows: (0.5-15): (0.1-30); most preferably, the mass ratio of cyclodextrin to manganese element-loaded bamboo charcoal is as follows: (0.5-1.5): 2.
according to the invention, in the step (2), the stirring reaction temperature is room temperature, and the stirring reaction time is 0.5-36 h; preferably, the stirring reaction time is 10-24 hours; most preferably, the stirring reaction time is 12 hours.
According to the invention, the drying temperature in the steps (1) and (2) is 50-70 ℃ and the drying time is 5-20 h.
According to the invention, in the steps (1) and (2), the solvent is water or an alcohol solvent; preferably, the alcohol solvent is selected from one or more of ethanol, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, diethylene glycol or dipropylene glycol.
Preferably, in the steps (1) and (2), the solvent is water.
The manganese and cyclodextrin co-modified bamboo charcoal material is applied to adsorption or degradation of formaldehyde or benzene adsorption.
The invention has the technical characteristics and beneficial effects that:
1. the bamboo powder adopted by the invention is one of raw materials for preparing the biochar, and the prepared biochar has a large pore structure and a higher specific surface area, and is beneficial to the adsorption of manganese element and beta-cyclodextrin on the surface or in the pores of the bamboo charcoal. According to the invention, manganese salt and bamboo powder are used as raw materials, and manganese ions are adsorbed and chemically coordinated on the surface or in holes of the bamboo powder through stirring reaction; then, under the high temperature condition, metal ions can be firmly modified on the surface or in holes of the bamboo charcoal; then, under the condition of reaction stirring, cyclodextrin is loaded on the bamboo charcoal; the reaction under the specific conditions of the invention ensures that the cyclodextrin and metal ions are combined with the biochar more firmly, and the cyclodextrin and metal ions are not easy to be de-intercalated. In the preparation method of the invention, the calcining condition is required to be proper; if the temperature is too low, complete carbonization cannot be achieved, and if the temperature is too high, the carbon material structure collapses, and the specific surface area is reduced. In the loading process of manganese and cyclodextrin, the mass ratio of manganese salt to bamboo powder and the mass ratio of cyclodextrin to bamboo charcoal need to ensure that the bamboo charcoal is loaded to the maximum; thereby fully playing the roles of the components.
2. The invention adopts metal ions and beta-cyclodextrin to jointly modify the biochar, so that the biochar is endowed with excellent adsorption performance on organic pollutants. Oxides of manganese having different valence states, e.g. MnO, mn 2 O 3 、Mn 3 O 4 And MnO 2 The method comprises the steps of carrying out a first treatment on the surface of the The manganese oxide has the characteristics of large specific surface area, rich micropore structure and a large number of adsorption sites, and has the characteristics of good catalytic activity, low toxicity and low cost; the catalytic properties of oxides of manganese in different valence states and different crystal structures are also different. The invention adoptsThe specific manganese oxide prepared by the specific method is used as a modifier to carry out surface modification treatment on the bamboo charcoal; the existence of the manganese oxide further expands the pores of the biochar, further increases the adsorption performance and simultaneously generates degradation performance on formaldehyde. The loading of the beta-cyclodextrin ensures that the carbon material has excellent effect on formaldehyde adsorption and increases the adsorption performance of the carbon material on benzene.
3. The raw materials and equipment used in the invention are all the prior art, and the raw materials are cheap and easy to obtain. The obtained composite material has good physical adsorption performance and host-guest inclusion effect of cyclodextrin supermolecules, so that the composite material has good adsorption capacity for complex organic matters (formaldehyde, phenol, benzene, chlorine, methyl halide and the like) and plays an important role in air pollution control.
4. The manganese and cyclodextrin co-modified bamboo charcoal prepared in the invention is defined as high-grade bamboo charcoal, and in order to highlight the excellent performance, manganese modified bamboo charcoal (medium-grade bamboo charcoal) and primary bamboo charcoal obtained by calcining only bamboo powder are prepared. After modification, the adsorption capacity of the high-grade bamboo charcoal on formaldehyde and benzene reaches the national standard of the first-grade carbon package, and the adsorption capacity of the medium-grade bamboo charcoal on benzene does not reach the national standard of the first-grade carbon package because only manganese oxide is loaded. The primary bamboo charcoal does not reach the national standard of primary charcoal package for formaldehyde and benzene. In the dynamic adsorption performance test of the p-benzene, the high-grade bamboo charcoal adsorption column in 45h keeps good performance all the time; and the primary bamboo charcoal and the medium bamboo charcoal lose adsorption effect at 26h and 32h respectively.
Drawings
Fig. 1 is a fourier transform infrared spectrum (FTIR) comparison spectrum of the superior bamboo charcoal, the intermediate bamboo charcoal, and the primary bamboo charcoal, the beta-cyclodextrin, prepared in example 1, prepared in comparative example 1. A detector, RT-DLATGS, was used in a Bruker ALPHA-T Fourier transform infrared spectrometer, germany.
Fig. 2 is a Scanning Electron Microscope (SEM) spectrum, EDS elemental analysis spectrum and mapping graph of the superior bamboo charcoal (a), the intermediate bamboo charcoal (C) prepared in example 1, and the primary bamboo charcoal (B) prepared in comparative example 1. SM-6700F of Japanese electronic JEOL was used.
Fig. 3 is a specific surface area test (BET) pattern of the high-grade bamboo charcoal (a) and the medium-grade bamboo charcoal (C) prepared in example 1, and the primary bamboo charcoal (B) prepared in comparative example 1.
Fig. 4 is a graph showing the static adsorption formaldehyde adsorption performance of the high-grade bamboo charcoal, the medium-grade bamboo charcoal prepared in example 1, and the primary bamboo charcoal prepared in comparative example 1.
Fig. 5 is a graph showing the adsorption performance of the primary bamboo charcoal prepared in comparative example 1 with respect to the static adsorption of benzene by the high-grade bamboo charcoal and the medium-grade bamboo charcoal prepared in example 1.
FIG. 6 is a graph showing formaldehyde degradation properties of the high-grade bamboo charcoal (A) and the medium-grade bamboo charcoal (C) prepared in example 1, and the primary bamboo charcoal (B) prepared in comparative example 1.
FIG. 7 is a graph showing the adsorption performance of the high-grade bamboo charcoal prepared in examples 1 and 14-16 for statically adsorbing formaldehyde (left) and benzene (right).
Detailed Description
The invention is further illustrated by, but not limited to, the following specific examples.
The starting materials used in the examples below were all commercially available products, analytically pure.
Example 1
A preparation method of a manganese and cyclodextrin co-modified bamboo charcoal material comprises the following steps:
(1) 10g of bamboo powder (purchased in the market and with the particle size of 60 meshes) and 1.5g of potassium permanganate are weighed, placed in a beaker, poured with 1000mL of solvent water, fully and uniformly dispersed by ultrasound, stirred in a water bath at room temperature for 12 hours, subjected to suction filtration, respectively washed by absolute ethyl alcohol and deionized water, and dried at the temperature of 60 ℃ for 10 hours to obtain the manganese element-loaded bamboo powder. And after drying, transferring the bamboo powder loaded with the manganese element into a porcelain boat, and calcining by a tube furnace. Introducing nitrogen for 5min before calcining in a tube furnace, and reacting for 2h at 600 ℃ to obtain black solid which is bamboo charcoal (medium-grade bamboo charcoal) loaded with manganese element;
(2) 2g of bamboo charcoal loaded with manganese element and 1g of beta-cyclodextrin are weighed, placed in a beaker, poured into 1000mL of solvent water, fully and uniformly dispersed by ultrasound, stirred in a water bath at room temperature, subjected to reaction time of 12h, subjected to suction filtration, respectively washed by absolute ethyl alcohol and deionized water, and dried at 60 ℃ for 10h to obtain the manganese and cyclodextrin co-modified bamboo charcoal material (high-grade bamboo charcoal).
The manganese and cyclodextrin co-modified bamboo charcoal material obtained in this example and the bamboo charcoal material prepared in comparative example 1 have Fourier Transform Infrared (FTIR) spectra and as shown in fig. 1, scanning Electron Microscope (SEM) and X-ray energy spectrum analysis (EDS) as shown in fig. 2, and as can be seen from fig. 1 and 2, the method of the present invention realizes preparation of manganese and β -cyclodextrin co-modified bamboo charcoal.
The specific surface area test (BET) of the manganese and cyclodextrin co-modified bamboo charcoal material obtained in this example and the bamboo charcoal material prepared in comparative example 1 are shown in FIG. 3, and it can be seen from FIG. 3 that the specific surface area of the bamboo charcoal is increased after manganese loading modification, and then the specific surface area is reduced after calcination and cyclodextrin modification, but still keeps higher level, and accords with the type II adsorption curve.
Example 2:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the step (1) uses manganese chloride to replace potassium permanganate; other steps and conditions were consistent with example 1.
Example 3:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: step (1) replacing potassium permanganate with manganese bromide; other steps and conditions were consistent with example 1.
Example 4:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the step (1) uses manganese sulfate to replace potassium permanganate; other steps and conditions were consistent with example 1.
Example 5:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the step (1) uses manganese nitrate to replace potassium permanganate; other steps and conditions were consistent with example 1.
Example 6:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: step (1) replacing beta-cyclodextrin with alpha-cyclodextrin; other steps and conditions were consistent with example 1.
Example 7:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: step (1) replacing beta-cyclodextrin with gamma-cyclodextrin; other steps and conditions were consistent with example 1.
Example 8:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the solvent in the steps (1) and (2) is ethanol instead of water; other steps and conditions were consistent with example 1.
Example 9:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the stirring reaction time of the step (1) is 24 hours; other steps and conditions were consistent with example 1.
Example 10:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the stirring reaction time of the step (1) is 36 hours; other steps and conditions were consistent with example 1.
Example 11:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the gas introduced into the tubular furnace in the step (1) replaces nitrogen with oxygen; other steps and conditions were consistent with example 1.
Example 12:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the gas introduced into the tubular furnace in the step (1) is argon instead of nitrogen; other steps and conditions were consistent with example 1.
Example 13:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the gas introduced into the tubular furnace in the step (1) is helium instead of nitrogen; other steps and conditions were consistent with example 1.
Example 14:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the calcination temperature in the tube furnace in the step (1) is 500 ℃; other steps and conditions were consistent with example 1.
Example 15:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the calcination temperature in the tube furnace in the step (1) is 700 ℃; other steps and conditions were consistent with example 1.
Example 16:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the calcination temperature in the tube furnace in the step (1) is 800 ℃; other steps and conditions were consistent with example 1.
Example 17:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the reaction time in the tubular furnace is 3 hours; other steps and conditions were consistent with example 1.
Example 18:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the reaction time in the tubular furnace is 4 hours; other steps and conditions were consistent with example 1.
Example 19:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the adding amount of the solvent water in the step (2) is 1500mL; other steps and conditions were consistent with example 1.
Example 20:
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material is as described in example 1, except that: the adding amount of the solvent water in the step (2) is 2000mL; other steps and conditions were consistent with example 1.
Comparative example 1
A preparation method of a bamboo charcoal material comprises the following steps:
bamboo powder (purchased in the market and with the grain size of 60 meshes) is placed in a porcelain boat and calcined by a tube furnace. Nitrogen is introduced into the tube furnace for 5min before calcination, and the reaction is carried out for 2h at 600 ℃ to obtain the bamboo charcoal material (primary bamboo charcoal).
Test example 1: formaldehyde adsorption
The medium-grade, high-grade bamboo charcoal of example 1, and the primary bamboo charcoal of comparative example 1 were subjected to a formaldehyde adsorption test.
Experimental instrument: glass drier, analytical balance, weighing bottle.
The experimental formula comprises the following steps: a mass of 0.5g sample; 1mL formaldehyde, analytically pure.
Weighing 0.5g of sample, and placing the sample into a weighing bottle with constant weight in advance; placing the weighing bottle filled with formaldehyde at a designated position at the bottom of a special tester for bamboo charcoal gas adsorption (formaldehyde is changed into gas, formaldehyde is volatilized automatically at room temperature), placing the weighing bottle filled with the sample on a grid of an adsorbent, adsorbing for 24 hours at room temperature, and performing blank control (namely, placing the weighing bottle not filled with formaldehyde).
The adsorption rate of formaldehyde is calculated according to the formula (as follows), and meanwhile, the effect of the primary bamboo charcoal and the effect of the medium bamboo charcoal are compared, and the comparison chart is shown in fig. 4: the modified bamboo charcoal prepared in the embodiment 1 of the invention is modified by manganese and cyclodextrin, so that the formaldehyde adsorption effect is improved; after cyclodextrin modification, the exposed active sites of manganese element are reduced, so that the formaldehyde adsorption amount is reduced, but the formaldehyde adsorption amount still keeps higher level; the adsorption effect of the obtained high-grade bamboo charcoal on formaldehyde reaches the national standard of first-grade charcoal package (formaldehyde is more than or equal to 100mg/g, GBT 26900-2011).
Formaldehyde adsorption rate is expressed in mg/g:
B＝X×10
wherein:
adsorption rate of X-bamboo charcoal to formaldehyde,%;
m 1 -mass of sample and weighing flask before adsorption in grams (g);
m 2 the mass of the sample and of the weighing flask after 24h of adsorption, in grams (g);
m 3 weight gain in grams (g) for blank test;
m-mass of sample in grams (g);
the adsorption rate of the B-bamboo charcoal to formaldehyde is expressed in milligrams per gram (mg/g);
test example 2: benzene adsorption
The medium-grade, high-grade bamboo charcoal of example 1, and the primary bamboo charcoal of comparative example 1 were subjected to a formaldehyde adsorption test.
Experimental instrument: a special tester for gas adsorption is composed of electrothermal constant-temp blast drier, climatic box and weighing bottle.
The experimental formula comprises the following steps: a sample of 0.5g in mass, 1mL benzene, was analytically pure.
Weighing 0.5g of sample, and placing the sample into a weighing bottle with constant weight in advance; the weighing bottle filled with benzene is placed at a designated position (benzene is changed into gas and the benzene is volatilized automatically at room temperature) at the bottom of a special tester for bamboo charcoal gas adsorption, meanwhile, the weighing bottle filled with the sample is placed on a grid of an absorber, and is adsorbed at a constant temperature of 20 ℃ for 24 hours to be tested, and meanwhile, a blank control (namely the weighing bottle not filled with benzene) is adopted.
The benzene adsorption rate is calculated according to the formula (the formaldehyde calculation formula is the same as the above), and meanwhile, the effects of the primary bamboo charcoal and the advanced bamboo charcoal are compared, and the comparison chart is shown in fig. 5: the modified bamboo charcoal is modified by manganese and cyclodextrin, so that the adsorption effect of benzene is improved; the adsorption effect of the obtained high-grade bamboo charcoal on benzene reaches the national standard of first-grade carbon package (benzene is more than or equal to 60mg/g, GBT 26900-2011).
Meanwhile, the medium and high grade bamboo charcoal of example 1 and the primary bamboo charcoal of comparative example 1 were tested for dynamic adsorption performance on benzene. The high-grade bamboo charcoal is continuously adsorbed for 45 hours, and the good adsorption performance is always kept; and the primary bamboo charcoal and the medium bamboo charcoal lose adsorption effect at 26h and 32h respectively.
Test example 3: formaldehyde degradation
The medium-grade, high-grade bamboo charcoal of example 1, and the primary bamboo charcoal of comparative example 1 were subjected to formaldehyde degradation performance test.
Experimental instrument: a photoacoustic spectrum gas analyzer, a weighing bottle and an analytical balance.
The experimental formula comprises the following steps: a sample of 0.1g in mass, 50ul formaldehyde, was analytically pure.
Weighing 0.1g of sample, placing the sample into a weighing bottle, placing the weighing bottle into a bracket in a container, dripping 50ul of formaldehyde into the bottom position of the instrument, and recording the changes of the concentration of formaldehyde and carbon dioxide in the container by using a photoacoustic spectrum gas analyzer. The degradation experiment temperature is room temperature. Simultaneously, the effect of the primary, medium and high-grade bamboo charcoal is compared, and a comparison chart is shown in fig. 6: according to the modified bamboo charcoal, the degradation effect on formaldehyde is improved through modification of manganese; after the cyclodextrin modification, the degradation effect is not greatly influenced.
Test example 4
The higher bamboo charcoal prepared in examples 14-16 was tested for formaldehyde and benzene adsorption; test methods are as in test example 1 and test example 2.
The test results are shown in fig. 7: from the graph, the calcination temperature has a certain influence on the adsorption performance of the obtained high-grade bamboo charcoal.
Claims (7)
1. The application of the manganese and cyclodextrin co-modified bamboo charcoal material is used for adsorbing or degrading formaldehyde or adsorbing benzene;
the bamboo charcoal material is bamboo charcoal loaded with manganese element, cyclodextrin is modified on the bamboo charcoal, wherein manganese element exists in an oxide state; the bamboo charcoal material is of a porous structure;
the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material comprises the following steps:
(1) Fully dispersing manganese salt and bamboo powder in a solvent, and obtaining bamboo powder loaded with manganese element through stirring reaction, filtering, washing and drying; then calcining to obtain manganese-loaded bamboo charcoal;
the manganese salt is potassium permanganate; the calcination conditions are as follows: gas protection, wherein the calcination temperature is 600-700 ℃ and the calcination time is 2-4 h; the mass ratio of the manganese salt to the bamboo powder is as follows: (1-2): 10; stirring reaction temperature is room temperature, and stirring reaction time is 0.5-36 h;
(2) Fully dispersing cyclodextrin and bamboo charcoal loaded with manganese element in a solvent, and obtaining a manganese and cyclodextrin co-modified bamboo charcoal material through stirring reaction, filtering, washing and drying;
the mass ratio of cyclodextrin to manganese element-loaded bamboo charcoal is as follows: (0.5-1.5): 2; the stirring reaction temperature is room temperature, and the stirring reaction time is 0.5-36 h.
2. The application of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 1, wherein the specific surface area of the bamboo charcoal material is 300-400m 2 /g。
3. The use of the manganese, cyclodextrin co-modification modified bamboo charcoal material according to claim 1, wherein in step (1) one or more of the following conditions are included:
i. the grain size of the bamboo powder is 50-80 meshes;
ii. The mass volume ratio of the manganese salt to the solvent is as follows: (0.1-20): (20-1000), unit: g/mL.
4. The use of a manganese, cyclodextrin co-modification modified bamboo charcoal material according to claim 3, wherein in step (1) one or more of the following conditions are included:
i. the manganese salt is potassium permanganate;
ii. The grain diameter of the bamboo powder is 60 meshes;
and iii, the mass volume ratio of the manganese salt to the solvent is as follows: (0.1-20): (100-1000) g/mL.
5. The use of the manganese, cyclodextrin co-modified bamboo charcoal material according to claim 1, wherein in step (2) one or more of the following conditions are included:
i. the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin;
ii. The mass volume ratio of the cyclodextrin to the solvent is (0.1-20): (20-1000), unit: g/mL.
6. The use of the manganese, cyclodextrin co-modified bamboo charcoal material according to claim 5, wherein in step (2) one or more of the following conditions are included:
i. the cyclodextrin is beta-cyclodextrin;
ii. The mass volume ratio of cyclodextrin to solvent is as follows: (0.1-20): (100-1000) g/mL, unit: g/mL.
7. The use of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 1, wherein in steps (1) and (2), one or more of the following conditions are included:
i. the drying temperature is 50-70 ℃ and the drying time is 5-20 h;
ii. The solvent is water or an alcohol solvent; the alcohol solvent is selected from one or more than two of ethanol, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, diethylene glycol or dipropylene glycol.
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