CN115318260A - 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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- CN115318260A CN115318260A CN202210885827.XA CN202210885827A CN115318260A CN 115318260 A CN115318260 A CN 115318260A CN 202210885827 A CN202210885827 A CN 202210885827A CN 115318260 A CN115318260 A CN 115318260A
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- manganese
- cyclodextrin
- bamboo charcoal
- modified
- solvent
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- 239000011425 bamboo Substances 0.000 title claims abstract description 171
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 170
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 170
- 241001330002 Bambuseae Species 0.000 title claims abstract description 170
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 170
- 239000003610 charcoal Substances 0.000 title claims abstract description 145
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 96
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 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 80
- 239000011572 manganese Substances 0.000 title claims abstract description 71
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 150000002696 manganese Chemical class 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000001116 FEMA 4028 Substances 0.000 claims description 13
- 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 13
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 13
- 229960004853 betadex Drugs 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-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
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- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 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
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 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
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 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 description 2
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 114
- 238000001179 sorption measurement Methods 0.000 abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
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- 238000006731 degradation reaction Methods 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
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- 241000282414 Homo sapiens Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 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
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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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
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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
- B01J20/28—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
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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
- B01J20/28—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
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- 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 Kinetics & Catalysis (AREA)
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- 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 comprises the following steps: fully dispersing manganese salt and bamboo powder in a solvent, and carrying out stirring reaction, filtering, washing and drying to obtain bamboo powder loaded with manganese elements; then, calcining to obtain bamboo charcoal loaded with manganese element; and fully dispersing the cyclodextrin and the bamboo charcoal loaded with the manganese element in a solvent, and carrying out stirring reaction, filtering, washing and drying 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 adsorption experiments all reach the national standard first-grade carbon packet standard; 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 problem which is paid much attention at home and abroad, and the risk of various diseases for people is increased and the health of people is influenced if people are in an environment containing high-concentration air pollutants for a long time. Among them, indoor environmental pollution is a typical type of air pollution, and people think that human beings have entered a third pollution period characterized by "indoor environmental pollution". The indoor environmental pollution is complex and serious, and has caused many diseases such as respiratory diseases, chronic lung diseases, tracheitis, bronchitis, lung cancer and the like. Formaldehyde is colorless and pungent gas, is one of main induction sources of indoor environmental pollution, and is mainly characterized by sensitization and mutagenesis to human health. Benzene mainly comes from coatings, wood paints and adhesives for indoor decoration and has high toxicity; the paint added with the benzene series solvent can emit aromatic odor to poison people. In recent years, people pay attention to improvement of indoor environment, and for example, when a new house is decorated, buying a plurality of carbon bags to remove indoor pollution becomes a life habit of most people. Carbon packets have been widely used in the field of air purification.
The concept of treating waste by waste is an important mode of pollution treatment, and the carbon material is widely used for air pollution treatment, wherein the biochar material plays a great potential in the aspect of pollution treatment. 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 the market has a plurality of biochar products, and the competitive pressure is high. Therefore, the development performance is better or the function is obviously different from the characteristic carbon bag product of the existing carbon bag, and the method has great significance.
The surface property and the electronic structure of the biochar can be improved by introducing iron-containing, cobalt-containing, manganese-containing and other groups on the biochar. In short, the biological carbon is modified by different methods, so that the pore structure, the specific surface area and the number of surface functional groups of the biological carbon can be improved, and the performance of the biological carbon can be improved. However, the existing biochar has the defect of simultaneous adsorption and modification of benzene and formaldehyde, and the adsorption of benzene and formaldehyde does not reach the national standard of the first-grade carbon packet at the same time due to the research of the existing carbon packet in the market.
Therefore, the research and development of a biochar material which simultaneously has excellent adsorption performance to benzene and formaldehyde are urgently needed to reach the national standard first-grade carbon package standard.
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. According to the invention, the modified bamboo charcoal material is modified by the co-modification of the cyclodextrin and the cyclodextrin by introducing the cyclodextrin and the manganese into the biochar; the material obtained by the invention has good adsorption performance on organic matters such as benzene, formaldehyde and the like, and adsorption experiments all reach the national standard first-grade carbon packet standard; meanwhile, the formaldehyde degrading agent has a formaldehyde degrading effect. The co-modification of manganese and cyclodextrin 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 degradation performance is greatly improved.
The invention is realized by the following technical scheme:
a bamboo charcoal material modified by co-modification of manganese and cyclodextrin is characterized in that the bamboo charcoal material is obtained by modifying cyclodextrin on bamboo charcoal loaded with manganese, wherein the manganese 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 bamboo powder, integrally presents a three-dimensional stacking structure and has certain pores.
According to the invention, the specific surface area of the bamboo charcoal material is preferably 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 carrying out stirring reaction, filtering, washing and drying to obtain bamboo powder loaded with manganese elements; then, calcining to obtain bamboo charcoal loaded with manganese elements;
(2) And fully dispersing the cyclodextrin and the bamboo charcoal loaded with the manganese element in a solvent, and carrying out stirring reaction, filtering, washing and drying to obtain the manganese and cyclodextrin co-modified bamboo charcoal material.
Preferably, in 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.
Preferably, in step (1), the bamboo powder has a particle size of 50-80 mesh, preferably 60 mesh. The bamboo powder is commercially available.
Preferably, in step (1), the mass-to-volume ratio of the manganese salt to the solvent is: (0.1-20): (20 to 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 the manganese salt to the solvent is as follows: (0.1-10): (500-1000), unit: g/mL.
According to the invention, in the step (1), the mass ratio of the manganese salt to the bamboo powder is as follows: (0.1-20): (0.1 to 60); preferably, the mass ratio of the manganese salt to the bamboo powder is as follows: (0.5 to 15): (0.1 to 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 the manganese salt to the bamboo powder is as follows: (1-2): 10.
preferably, 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 h; most preferably, the reaction time is 12 hours with stirring.
Preferably, according to the present invention, in step (1), the calcination conditions are: under the protection of gas, the calcining temperature is 200-1000 ℃, and the calcining time is 1-12 h; preferably, the gas is nitrogen, argon, helium or oxygen, the calcining temperature is 500-800 ℃, and the calcining time is 2-4 h; most preferably, the calcination temperature is 600 ℃ and the calcination time is 2h.
Preferably, according to the present invention, in the step (2), the cyclodextrin is α -cyclodextrin, β -cyclodextrin or γ -cyclodextrin; preferably, the cyclodextrin is β -cyclodextrin.
According to the invention, in the step (2), the mass-to-volume ratio of the cyclodextrin to the solvent is (0.1-20): (20 to 1000), unit: g/mL; preferably, the mass-to-volume ratio of cyclodextrin to solvent is: (0.1-20): (100-1000) g/mL, unit: g/mL; most preferably, the mass-to-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 to 60); preferably, the mass ratio of the cyclodextrin to the manganese element-loaded bamboo charcoal is as follows: (0.5 to 15): (0.1 to 30); most preferably, the mass ratio of the cyclodextrin to the bamboo charcoal loaded with manganese elements is as follows: (0.5-1.5): 2.
preferably, 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 h; most preferably, the reaction time is 12h with stirring.
According to the invention, the drying temperature in the steps (1) and (2) is preferably 50-70 ℃, and the drying time is preferably 5-20 h.
According to the present invention, in the steps (1) and (2), the solvent is water or an alcohol solvent; preferably, the alcohol solvent is one or a mixture of more than two of ethanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, diethylene glycol or dipropylene glycol.
Preferably, in the steps (1) and (2), the solvent is water.
The application of the manganese and cyclodextrin co-modified bamboo charcoal material is used for adsorbing or degrading formaldehyde or adsorbing benzene.
The invention has the following technical characteristics and beneficial effects:
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 and beta-cyclodextrin on the surface or in pores of the bamboo charcoal. 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 condition of high temperature, metal ions can be firmly decorated on the surface or in the holes of the bamboo charcoal; then loading cyclodextrin onto the bamboo charcoal under the condition of reaction and stirring; the reaction under the specific condition of the invention ensures that the cyclodextrin and the metal ions are combined with the biochar more firmly and are not easy to be de-intercalated. In the preparation method, the calcination condition needs to be proper; if the temperature is too low, the carbon material cannot be completely carbonized, and if the temperature is too high, the structure of the carbon material collapses, so that 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 the maximization of bamboo charcoal load; thereby fully exerting the functions of all the components.
2. According to the invention, the metal ions and the beta-cyclodextrin are adopted to modify the biochar together, so that the biochar has excellent adsorption performance on organic pollutants. Oxides of manganese having different valences, e.g. MnO, mn 2 O 3 、Mn 3 O 4 And MnO 2 (ii) a The manganese oxide not only has the characteristics of large specific surface area, rich microporous structure and a large number of adsorption sites, but also has the characteristics of good catalytic activity, low toxicity and low cost; the catalytic performance of oxides of manganese with different valence states and different crystal structures is also different. The invention adopts specific manganese oxide prepared by a specific method as a modifier to carry out surface modification treatment on bamboo charcoal; due to the existence of the manganese oxide, the cavity of the biochar is further expanded, the adsorption performance is further improved, and the degradation performance is generated on formaldehyde. The beta-cyclodextrin is loaded, so that the carbon material has an excellent effect on formaldehyde adsorption, and meanwhile, the adsorption performance of the carbon material on benzene is improved.
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 cyclodextrin supermolecule host-guest inclusion effect, so that the composite material has good adsorption capacity on complex organic matters (formaldehyde, phenol, benzene, chlorine, methyl halide and the like) and plays an important role in air pollution control.
4. The modified bamboo charcoal co-modified by manganese and cyclodextrin prepared in the invention is defined as high-grade bamboo charcoal, and in order to highlight the excellent performance, the modified bamboo charcoal modified by manganese (middle-grade bamboo charcoal) and primary bamboo charcoal obtained by calcining bamboo powder are prepared at the same time. After modification, the adsorption capacity of the high-grade bamboo charcoal to formaldehyde and benzene reaches the national standard of the first-grade charcoal bag, and the adsorption capacity of the middle-grade bamboo charcoal to benzene does not reach the national standard of the first-grade charcoal bag because only manganese oxide is loaded on the middle-grade bamboo charcoal. The primary bamboo charcoal does not reach the national standard of first-grade charcoal bag for formaldehyde and benzene. In the test of the dynamic adsorption performance of the benzene, the adsorption column of the high-grade bamboo charcoal keeps good performance for 45 hours; while the primary bamboo charcoal and the middle bamboo charcoal lose adsorption effect respectively in 26h and 32 h.
Drawings
Fig. 1 is a fourier transform infrared spectroscopy (FTIR) comparison spectrum of the high bamboo charcoal, the middle bamboo charcoal prepared in example 1, the primary bamboo charcoal prepared in comparative example 1, and beta-cyclodextrin. Adopts German Bruker ALPHA-T Fourier transform infrared spectrometer and detector RT-DLATGS.
Fig. 2 is a Scanning Electron Microscope (SEM) spectrum, an EDS elemental analysis spectrum, and mapping chart of the high bamboo charcoal (a), the middle bamboo charcoal (C), and the primary bamboo charcoal (B), prepared in example 1, and comparative example 1. SM-6700F from Japanese Electron JEOL was used.
Fig. 3 is a specific surface area test (BET) spectrum of the high bamboo charcoal (a), the middle bamboo charcoal (C) prepared in example 1, and the primary bamboo charcoal (B) prepared in comparative example 1.
Fig. 4 is a graph of static formaldehyde adsorption performance of the high-grade bamboo charcoal and the middle-grade bamboo charcoal prepared in example 1 and the primary bamboo charcoal prepared in comparative example 1.
Fig. 5 is a graph showing the static adsorption performance of benzene on the high-grade bamboo charcoal, the middle-grade bamboo charcoal prepared in example 1 and the primary bamboo charcoal prepared in comparative example 1.
Fig. 6 is a formaldehyde degradation performance graph of the high bamboo charcoal (a), the middle 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 advanced bamboo charcoal prepared in examples 1 and 14 to 16 for static adsorption of formaldehyde (left) and benzene (right).
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the following examples are all commercially available products and were analytically pure.
Example 1
A preparation method of a manganese and cyclodextrin co-modified bamboo charcoal material comprises the following steps:
(1) Weighing 10g of bamboo powder (purchased in the market, with the particle size of 60 meshes) and 1.5g of potassium permanganate, putting the bamboo powder and the potassium permanganate into a beaker, pouring 1000mL of solvent water, performing ultrasonic full dispersion uniformly, stirring the mixture in a water bath at room temperature, reacting for 12 hours, performing suction filtration on the stirred solution, respectively washing the solution with absolute ethyl alcohol and deionized water, and drying the solution at the temperature of 60 ℃ for 10 hours to obtain the manganese-element-loaded bamboo powder. After drying, the bamboo powder loaded with manganese element is transferred to a porcelain boat and calcined by a tube furnace. Introducing nitrogen for 5min before calcining in a tubular furnace, reacting at 600 ℃ for 2h to obtain black solid, namely the manganese element-loaded bamboo charcoal (middle-grade bamboo charcoal);
(2) Weighing 2g of bamboo charcoal loaded with manganese elements and 1g of beta-cyclodextrin, placing the bamboo charcoal and the beta-cyclodextrin in a beaker, pouring 1000mL of solvent water, performing ultrasonic full dispersion uniformly, stirring the mixture in a water bath at room temperature for 12h, performing suction filtration on the stirred solution, respectively washing the solution with absolute ethyl alcohol and deionized water, and drying the solution at 60 ℃ for 10h to obtain the manganese and cyclodextrin co-modified bamboo charcoal material (high-grade bamboo charcoal).
The fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscope (SEM) and X-ray energy spectrum analysis (EDS) 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. 1, and fig. 2 show that the method of the present invention realizes the preparation of manganese and β -cyclodextrin co-modified bamboo charcoal.
Specific surface area tests (BET) of the bamboo charcoal material modified by co-modification of manganese and cyclodextrin obtained in the embodiment and the bamboo charcoal material prepared in the 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 a higher level, and conforms to a type II adsorption curve.
Example 2:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: step (1) using manganese chloride to replace potassium permanganate; the other steps and conditions were identical to those of example 1.
Example 3:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: step (1) manganese bromide is used for replacing potassium permanganate; the other steps and conditions were identical to those of example 1.
Example 4:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: step (1), manganese sulfate is used for replacing potassium permanganate; the other steps and conditions were identical to those of example 1.
Example 5:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: step (1) manganese nitrate is used for replacing potassium permanganate; the other steps and conditions were identical to those of example 1.
Example 6:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: replacing beta-cyclodextrin with alpha-cyclodextrin; the other steps and conditions were identical to those of example 1.
Example 7:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: replacing beta-cyclodextrin with gamma-cyclodextrin; the other steps and conditions were identical to those of example 1.
Example 8:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the solvent in the steps (1) and (2) is ethanol instead of water; the other steps and conditions were identical to those of example 1.
Example 9:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: stirring and reacting for 24 hours in the step (1); the other steps and conditions were identical to those of example 1.
Example 10:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: stirring and reacting for 36 hours in the step (1); the other steps and conditions were identical to those of example 1.
Example 11:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: replacing nitrogen with oxygen in the gas introduced into the tubular furnace in the step (1); the other steps and conditions were identical to those of example 1.
Example 12:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: replacing nitrogen with argon in the gas introduced into the tubular furnace in the step (1); the other steps and conditions were identical to those of example 1.
Example 13:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: replacing nitrogen with helium in the gas introduced into the tubular furnace in the step (1); the other steps and conditions were identical to those of example 1.
Example 14:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the calcining temperature in the tubular furnace is 500 ℃; the other steps and conditions were identical to those of example 1.
Example 15:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the calcining temperature in the tubular furnace is 700 ℃; the other steps and conditions were identical to those of example 1.
Example 16:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: in the step (1), the calcining temperature in the tubular furnace is 800 ℃; the other steps and conditions were identical to those of example 1.
Example 17:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the reaction time in the tubular furnace in the step (1) is 3h; the other steps and conditions were identical to those of example 1.
Example 18:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the reaction time in the tubular furnace in the step (1) is 4h; the other steps and conditions were identical to those of example 1.
Example 19:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the adding amount of the solvent water in the step (2) is 1500mL; the other steps and conditions were identical to those of example 1.
Example 20:
a method for preparing a manganese and cyclodextrin co-modified bamboo charcoal material, as described in example 1, except that: the adding amount of the solvent water in the step (2) is 2000mL; the other steps and conditions were identical to those of example 1.
Comparative example 1
A method for preparing bamboo charcoal material comprises the following steps:
placing bamboo powder (commercially available, particle size of 60 mesh) in a porcelain boat, and calcining with a tube furnace. Introducing nitrogen for 5min before calcining in a tubular furnace, and reacting at 600 deg.C for 2h to obtain bamboo charcoal material (primary bamboo charcoal).
Test example 1: formaldehyde adsorption
The middle-grade and high-grade bamboo charcoal in example 1 and the primary bamboo charcoal in comparative example 1 were subjected to formaldehyde adsorption test.
An experimental instrument: glass desiccator, analytical balance, weighing bottle.
The experimental formula is as follows: a mass of 0.5g of sample; 1mL of formaldehyde, analytically pure.
Weighing 0.5g of sample and putting the sample into a weighing bottle with constant weight in advance; and (3) placing the weighing bottle filled with formaldehyde at a specified position at the bottom of the bamboo charcoal gas adsorption special tester (formaldehyde becomes gas and the formaldehyde automatically volatilizes at room temperature), meanwhile, placing the weighing bottle filled with the sample on a grid of the adsorption tester, adsorbing for 24 hours at room temperature for testing, and simultaneously carrying out blank control (namely, not placing the weighing bottle filled with formaldehyde).
The formaldehyde adsorption rate is calculated according to the formula (as follows), and the effect of the primary bamboo charcoal and the effect of the intermediate bamboo charcoal are compared, and the comparison graph is shown in figure 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; through cyclodextrin modification, the active sites exposed by manganese elements are reduced, so that the formaldehyde adsorption quantity is reduced, but a higher level is still maintained; the adsorption effect of the obtained high-grade bamboo charcoal on formaldehyde reaches the national standard first-grade charcoal bag standard (formaldehyde is more than or equal to 100mg/g, GBT 26900-2011).
The formaldehyde adsorption rate is expressed in mg/g:
B＝X×10
in the formula:
the adsorption rate of X-bamboo charcoal to formaldehyde,%;
m 1 -mass in grams (g) of sample and weighing flask before adsorption;
m 2 -mass in grams (g) of sample and weighing flask after 24h of adsorption;
m 3 -blank weight gain in grams (g);
m-mass of the sample in grams (g);
b, the adsorption rate of the bamboo charcoal to the formaldehyde is milligram per gram (mg/g);
test example 2: benzene adsorption
The middle-grade and high-grade bamboo charcoal in example 1 and the primary bamboo charcoal in comparative example 1 were subjected to formaldehyde adsorption test.
An experimental instrument: a special tester for gas adsorption, an electric heating constant-temperature air blast drying box, a climate box and a weighing bottle.
The experimental formula is as follows: sample 0.5g, 1mL benzene, analytically pure.
Weighing 0.5g of sample and putting the sample into a weighing bottle with constant weight in advance; placing the weighing bottle filled with benzene at the specified position at the bottom of the bamboo charcoal gas adsorption special tester (benzene becomes gas, benzene volatilizes automatically at room temperature), placing the weighing bottle filled with the sample on a grid of the adsorption tester, adsorbing for 24h at constant temperature of 20 ℃ for testing, and simultaneously performing blank control (namely not placing the weighing bottle filled with benzene).
The benzene adsorption rate is calculated according to the formula (same as the above formaldehyde calculation formula), and the effects of the primary bamboo charcoal and the advanced bamboo charcoal are compared, and the comparison graph is shown in fig. 5: the modified bamboo charcoal is modified by manganese and cyclodextrin, so that the adsorption effect on benzene is improved; the adsorption effect of the obtained high-grade bamboo charcoal on benzene reaches the national standard first-grade charcoal bag standard (benzene is more than or equal to 60mg/g, GBT 26900-2011).
Meanwhile, the middle-grade and high-grade bamboo charcoals in example 1 and the primary bamboo charcoals in comparative example 1 were tested for their dynamic adsorption performance to benzene. The high-grade bamboo charcoal continuously adsorbs for 45 hours, and the good adsorption performance is always kept; while the primary bamboo charcoal and the middle bamboo charcoal lose adsorption effect respectively in 26h and 32 h.
Test example 3: formaldehyde degradation
The middle-grade and high-grade bamboo charcoal in example 1 and the primary bamboo charcoal in comparative example 1 were subjected to formaldehyde degradation performance test.
An experimental instrument: a photoacoustic spectrometry gas analyzer, a weighing bottle and an analytical balance.
The experimental formula is as follows: sample mass 0.1g, 50ul formaldehyde, analytically pure.
Weighing 0.1g of sample, putting the sample into a weighing bottle, putting the weighing bottle into a support in a container, dripping 50ul of formaldehyde into the bottom of the apparatus, and recording the concentration change of the formaldehyde and the carbon dioxide in the container by using a photoacoustic spectrometry gas analyzer. The degradation experiment temperature was room temperature. Meanwhile, the effects of the primary, intermediate and advanced bamboo charcoal are compared, and the comparison graph is shown in fig. 6: the modified bamboo charcoal improves the degradation effect on formaldehyde through manganese modification; after the cyclodextrin modification, the degradation effect is not greatly influenced.
Test example 4
The high-grade bamboo charcoal prepared in examples 14 to 16 was tested for adsorbing formaldehyde and benzene; the test methods were as in test example 1 and test example 2.
The test results are shown in fig. 7: as can be seen from the figure, the calcination temperature has a certain influence on the adsorption performance of the obtained high-grade bamboo charcoal.
Claims (10)
1. A bamboo charcoal material modified by co-modification of manganese and cyclodextrin is characterized in that the bamboo charcoal material is obtained by modifying cyclodextrin on bamboo charcoal loaded with manganese, wherein the manganese exists in an oxide state; the bamboo charcoal material is of a porous structure.
2. The manganese and cyclodextrin co-modified bamboo charcoal material as claimed in claim 1, wherein the specific surface area of the bamboo charcoal material is 300-400m 2 /g。
3. The preparation method of the bamboo charcoal material co-modified by manganese and cyclodextrin according to any one of claims 1 or 2, comprising the steps of:
(1) Fully dispersing manganese salt and bamboo powder in a solvent, and carrying out stirring reaction, filtering, washing and drying to obtain bamboo powder loaded with manganese elements; then, calcining to obtain bamboo charcoal loaded with manganese elements;
(2) Fully dispersing cyclodextrin and bamboo charcoal loaded with manganese elements in a solvent, and performing stirring reaction, filtering, washing and drying to obtain the bamboo charcoal material modified by co-modification of manganese and cyclodextrin.
4. The preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 3, wherein the step (1) comprises one or more of the following conditions:
i. the manganese salt is potassium permanganate, manganese chloride, manganese bromide, manganese iodide, manganese sulfate or manganese nitrate; preferably, the manganese salt is potassium permanganate;
ii. The particle size of the bamboo powder is 50-80 meshes, preferably 60 meshes;
iii, the mass volume ratio of the manganese salt to the solvent is as follows: (0.1-20): (20 to 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 the manganese salt to the solvent is as follows: (0.1-10): (500-1000), unit: g/mL.
5. The preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 3, wherein the step (1) comprises one or more of the following conditions:
i. the mass ratio of the manganese salt to the bamboo powder is as follows: (0.1-20): (0.1 to 60); preferably, the mass ratio of the manganese salt to the bamboo powder is as follows: (0.5 to 15): (0.1 to 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 the manganese salt to the bamboo powder is as follows: (1-2): 10;
ii. 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 h; most preferably, the stirring reaction time is 12 hours;
iii, the calcining conditions are as follows: under the protection of gas, the calcining temperature is 200-1000 ℃, and the calcining time is 1-12 h; preferably, the gas is nitrogen, argon, helium or oxygen, the calcining temperature is 500-700 ℃, and the calcining time is 2-4 h; most preferably, the calcination temperature is 600 ℃ and the calcination time is 2h.
6. The preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 3, wherein the step (2) comprises one or more of the following conditions:
i. the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin; preferably, the cyclodextrin is beta-cyclodextrin;
ii. The mass volume ratio of the cyclodextrin to the solvent is (0.1-20): (20 to 1000), unit: g/mL; preferably, the mass-to-volume ratio of cyclodextrin to solvent is: (0.1-20): (100-1000) g/mL, unit: g/mL; most preferably, the mass-to-volume ratio of cyclodextrin to solvent is: (0.1-10): (500-1000), unit: g/mL.
7. The preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material as claimed in claim 3, wherein 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 to 60); preferably, the mass ratio of the cyclodextrin to the manganese element-loaded bamboo charcoal is as follows: (0.5 to 15): (0.1 to 30); most preferably, the mass ratio of the cyclodextrin to the bamboo charcoal loaded with manganese elements is as follows: (0.5-1.5): 2.
8. the preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 3, wherein 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 h; most preferably, the reaction time is 12h with stirring.
9. The preparation method of the manganese and cyclodextrin co-modified bamboo charcoal material according to claim 3, wherein the steps (1) and (2) comprise one or more of the following conditions:
i. the drying temperature is 50-70 ℃, and the drying time is 5-20 h;
ii. The solvent is water or an alcohol solvent; preferably, the alcohol solvent is selected from one or a mixture of more than two of ethanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, diethylene glycol or dipropylene glycol; preferably, the solvent is water.
10. The use of the modified bamboo charcoal material co-modified with manganese and cyclodextrin according to any one of claims 1 or 2, for adsorbing or degrading formaldehyde, or for adsorbing benzene.
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