CN112705169A - Modified beta-cyclodextrin polymer, preparation method and application in dye adsorption - Google Patents
Modified beta-cyclodextrin polymer, preparation method and application in dye adsorption Download PDFInfo
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- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class 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 title claims abstract description 50
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 46
- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 22
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 22
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 22
- 229960004853 betadex Drugs 0.000 claims abstract description 22
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical class N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims abstract description 18
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical group ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- DKQPXAWBVGCNHG-UHFFFAOYSA-N 2,2,4,4,6,6-hexafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound FP1(F)=NP(F)(F)=NP(F)(F)=N1 DKQPXAWBVGCNHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- XNZZEQCBAGUFMT-UHFFFAOYSA-N 2,2,4,4,6-pentafluoro-6-phenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound FP1(F)=NP(F)(F)=NP(F)(OC=2C=CC=CC=2)=N1 XNZZEQCBAGUFMT-UHFFFAOYSA-N 0.000 claims abstract description 5
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000975 dye Substances 0.000 description 35
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 16
- 229960000907 methylthioninium chloride Drugs 0.000 description 16
- 229940107698 malachite green Drugs 0.000 description 7
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了改性β‑环糊精聚合物及制备方法与在染料吸附中的应用，其制备方法为：将β‑环糊精与环三磷腈衍生物进行加热反应；加热反应体系中添加缚酸剂，环三磷腈衍生物为六氯环三磷腈、六氟环三磷腈、乙氧基(五氟)环三磷腈或五氟(苯氧基)环三磷腈。采用本发明提供的改性β‑环糊精聚合物作为吸附材料能够克服传统吸附材料吸附容量低、吸附时间长及再生困难的问题。
The invention discloses a modified β-cyclodextrin polymer and a preparation method and application in dye adsorption. The preparation method comprises the following steps: heating and reacting β-cyclodextrin and a cyclotriphosphazene derivative; An acid binding agent is added, and the cyclotriphosphazene derivative is hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene, ethoxy(pentafluoro)cyclotriphosphazene or pentafluoro(phenoxy)cyclotriphosphazene. Using the modified β-cyclodextrin polymer provided by the present invention as the adsorption material can overcome the problems of low adsorption capacity, long adsorption time and difficult regeneration of traditional adsorption materials.
Description
Technical Field
The invention belongs to the field of environmental chemistry, and relates to a modified beta-cyclodextrin polymer, a preparation method and application thereof in dye adsorption.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Dyes are a class of substances that can color fibers and are widely used in the production of textiles, leather, food, rubber, coatings, and the like. In addition to the normal processing with water, 12% of the dye is discharged as waste water during the production and use process. The dye wastewater has the characteristics of complex components, high chromaticity and difficult degradation, and can cause serious pollution to surface water and underground water if not treated after being discharged. The main components and partial metabolites in the dye wastewater generally have high biological toxicity, which causes canceration and distortion of organisms. In addition, the organic dye has color to prevent light penetration and interfere the photosynthesis of aquatic plant. Most dyes are difficult to degrade, can stably exist in the ecological environment for a long time, cause persistent pollution, and are harmful to the living environment and the body health of human beings. Therefore, the removal of dyes from wastewater has also become a major concern in the field of environmental remediation.
The method for removing the dye from the waste water is generally an oxidation method, a membrane filtration method, an adsorption method, an ion method, or the like. The adsorption method is the most effective and commonly used method for removing the dye in the wastewater at present, has the advantages of low cost, high speed, large capacity and repeatable adsorbent, and becomes the most effective and commonly used method for decoloring the wastewater. The traditional adsorbents mainly comprise diatomite, activated carbon, coke, resin, cellulose, zeolite and the like, and the traditional adsorbents generally have the defects of low adsorption capacity, difficult regeneration and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a modified beta-cyclodextrin polymer, a preparation method and application in dye adsorption.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one hand, a preparation method of a modified beta-cyclodextrin polymer, which comprises the steps of carrying out heating reaction on beta-cyclodextrin and a cyclotriphosphazene derivative; adding an acid-binding agent into the heating reaction system, wherein the cyclotriphosphazene derivative is hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene, ethoxy (pentafluoro) cyclotriphosphazene or pentafluoro (phenoxy) cyclotriphosphazene.
The invention modifies beta-cyclodextrin through a cyclotriphosphazene derivative, and realizes coupling through removing hydrogen halide through halogen in the cyclotriphosphazene derivative and hydrogen of beta-cyclodextrin hydroxyl, thereby forming the porous polymer.
In another aspect, a modified beta-cyclodextrin polymer is obtained by the above-described preparation method.
In a third aspect, the modified beta-cyclodextrin polymer is used for dye adsorption.
In a fourth aspect, the dye adsorbent comprises an adsorption active ingredient, wherein the adsorption active ingredient is the modified beta-cyclodextrin polymer.
In a fifth aspect, a method for adsorbing a dye in water, the modified beta-cyclodextrin polymer or the dye adsorbent is added into water containing the dye for adsorption.
In a sixth aspect, a method for regenerating a dye adsorbent, wherein an ethanol solution of acetic acid is used to desorb the modified β -cyclodextrin polymer or the dye adsorbent adsorbed by the adsorption method.
The invention has the beneficial effects that:
the invention adopts the cyclotriphosphazene derivative to modify beta-cyclodextrin, and realizes the coupling of the beta-cyclodextrin and the cyclotriphosphazene derivative by removing hydrogen on hydroxyl of the beta-cyclodextrin and halogen atoms on the cyclotriphosphazene derivative in the form of hydrogen halide under the action of an acid binding agent to form the porous polymer. The connection mode among beta-cyclodextrin molecules and the stacking mode of the beta-cyclodextrin are changed through modification of the cyclotriphosphazene, so that the adsorption performance of the modified beta-cyclodextrin polymer on the dye in water is remarkably improved.
The modified beta-cyclodextrin polymer provided by the invention has good thermal stability and acid-base stability as an adsorbing material, and has high adsorption capacity for dyes, wherein the adsorption capacity for methylene blue is over 1000mg/g, and the removal rate can reach 99% at most.
The preparation method is simple, the used raw materials are easy to obtain, the yield is high, the energy is saved, the environment is protected, no special processing is needed, and the mass production and industrial popularization are easy.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a transmission electron micrograph of a polymer prepared in example 1 of the present invention.
FIG. 2 is an X-ray powder diffraction pattern of the polymer prepared in example 2 of the present invention.
FIG. 3 is an X-ray energy spectrum of the polymer prepared in example 2 of the present invention.
FIG. 4 is a graph showing changes over time in the UV-visible spectrum of methylene blue added in Experimental example 1 of the present invention.
FIG. 5 is a graph showing changes over time in the UV-visible spectrum of malachite green added in Experimental example 2 of the present invention.
Fig. 6 is a graph showing the regeneration efficiency of the adsorbent in experimental example 2 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to overcome the problems of low adsorption capacity, long adsorption time and difficult regeneration of the traditional adsorption material, the invention provides a modified beta-cyclodextrin polymer, a preparation method and application thereof in dye adsorption.
The invention provides a preparation method of a modified beta-cyclodextrin polymer, which comprises the following steps of carrying out heating reaction on beta-cyclodextrin and a cyclotriphosphazene derivative; adding an acid-binding agent into the heating reaction system, wherein the cyclotriphosphazene derivative is hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene, ethoxy (pentafluoro) cyclotriphosphazene or pentafluoro (phenoxy) cyclotriphosphazene.
The invention modifies beta-cyclodextrin through a cyclotriphosphazene derivative, and realizes coupling through removing hydrogen halide through halogen in the cyclotriphosphazene derivative and hydrogen of beta-cyclodextrin hydroxyl, thereby forming the porous polymer.
The use of hexachlorocyclotriphosphazene can reduce the production cost because of the lower price of hexachlorocyclotriphosphazene among hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene, ethoxy (pentafluoro) cyclotriphosphazene, and pentafluoro (phenoxy) cyclotriphosphazene.
In some examples of this embodiment, the mass ratio of the beta-cyclodextrin to the cyclotriphosphazene derivative is 1:1 to 5.
In some examples of this embodiment, the solvent of the solvothermal reaction system is N, N-dimethylformamide and/or tetrahydrofuran. When the mixed solvent of N, N-dimethylformamide and tetrahydrofuran is adopted, the effect is better.
In some embodiments of this embodiment, the acid scavenger is potassium carbonate.
In some examples of this embodiment, the mass ratio of the beta-cyclodextrin to the acid-binding agent is 1: 0.9-2.
In some examples of this embodiment, the method of heating the reaction is a reflux method or a solvothermal method.
In some examples of this embodiment, the heating reaction temperature is 80-160 ℃ and the reaction time is 2-72 hours.
In another embodiment of the present invention, there is provided a modified β -cyclodextrin polymer obtained by the above-mentioned preparation method.
In a third embodiment of the present invention, there is provided a use of the above modified β -cyclodextrin polymer in dye adsorption. The dye provided by the invention is methylene blue, malachite green, rhodamine 6G and rhodamine B, wherein experiments show that the dye has a better adsorption effect on the methylene blue.
In a fourth embodiment of the present invention, a dye adsorbent is provided, which comprises an adsorption active ingredient, wherein the adsorption active ingredient is the modified beta-cyclodextrin polymer.
In a fifth embodiment of the present invention, a method for adsorbing a dye in water is provided, wherein the modified β -cyclodextrin polymer or the dye adsorbent is added to water containing the dye for adsorption.
In a sixth embodiment of the present invention, a method for regenerating a dye adsorbent is provided, wherein the modified β -cyclodextrin polymer or the dye adsorbent adsorbed by the adsorption method is desorbed by an ethanol solution of acetic acid.
In some embodiments of this embodiment, the volume fraction of acetic acid in the ethanolic solution of acetic acid is 4-6%.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
Mixing and dissolving 0.1g of beta-cyclodextrin and 0.2g of hexachlorocyclotriphosphazene in 10mL of N, N-dimethylformamide, adding 0.15g of potassium carbonate, placing in a 25mL of polytetrafluoroethylene reaction kettle, carrying out thermal reaction for 24 hours in a constant-temperature solvent at 120 ℃, cooling, centrifuging, washing and drying after the reaction is finished to obtain a light yellow solid.
Example 2
Mixing 0.2g of beta-cyclodextrin and 0.4g of hexachlorocyclotriphosphazene, dissolving in 25mL of N, N-dimethylformamide, adding 0.2g of potassium carbonate, placing in a 50mL of polytetrafluoroethylene reaction kettle, carrying out thermal reaction for 48 hours in a constant-temperature solvent at 120 ℃, cooling, centrifuging, washing and drying to obtain a black solid after the reaction is finished.
Example 3
Mixing 0.2g of beta-cyclodextrin and 0.6g of hexachlorocyclotriphosphazene, dissolving in 40mL of N, N-dimethylformamide, adding 0.3g of potassium carbonate, placing in a 100mL round-bottom flask, carrying out reflux reaction at 120 ℃ for 48 hours at constant temperature, after the reaction is finished, cooling, centrifuging, washing and drying to obtain a light yellow solid.
Example 4
Mixing and dissolving 0.1g of beta-cyclodextrin and 0.3g of hexachlorocyclotriphosphazene in 6mL of N, N-dimethylformamide and 3mL of tetrahydrofuran, adding 0.15g of potassium carbonate, transferring into a 25mL of polytetrafluoroethylene reaction kettle, carrying out thermal reaction for 24 hours in a constant-temperature solvent at 120 ℃, cooling, centrifuging, washing and drying after the reaction is finished to obtain a light yellow solid.
The transmission electron micrograph of the polymer prepared in example 1 is shown in fig. 1, which shows that the prepared polymer is microspheres with the size of about 2-10 μm.
The X-ray powder diffraction pattern of the polymer prepared in example 2 is shown in FIG. 2, and the polymer only shows a wide diffraction peak, is in an amorphous state, and has a diffraction angle of 15-40 degrees. As shown in FIG. 3, the polymer mainly contains elements such as O, C, P, K, N, Cl, and the contents of the elements are 37.33%, 40.57%, 11.27%, 5.16%, 4.25% and 1.41%, respectively. This demonstrates that the hydrogen on the hydroxyl group of β -cyclodextrin is mainly coupled to the chlorine on hexachlorocyclotriphosphazene during the reaction by removal of HCl to form the porous polymer.
Experimental example 1
The pale yellow solid obtained in example 3 was used as an adsorbent to adsorb and remove the dye, and methylene blue was used as an example. Under the condition of normal temperature, a proper amount of adsorbent is added into a methylene blue solution, the total volume is 100mL, wherein the concentration of the methylene blue is 32mg/L, and the concentration of the adsorbent is 30 mg/L. As shown in the ultraviolet-visible spectrum of fig. 4, the ultraviolet-visible spectrum intensity of methylene blue is sharply reduced after 5 minutes of adding the adsorbent, and the removal rate can reach 97.3% after 5 hours of adsorption.
Experimental example 2
The pale yellow solid obtained in example 4 was used as an adsorbent to adsorb and remove the dye, and malachite green was used as an example. Under the condition of normal temperature, a proper amount of adsorbent is added into a methylene blue solution, the total volume is 100mL, wherein the concentration of malachite green is 30mg/L, and the concentration of the adsorbent is 30 mg/L. As shown in the ultraviolet-visible spectrum of fig. 5, the ultraviolet-visible spectrum intensity of malachite green is sharply reduced after 5 minutes of adding the adsorbent, and the removal rate can reach 95.1% after 4 hours of adsorption.
Experimental example 3
The measurement of the adsorption capacity was carried out using the pale yellow solid obtained in example 4 as an adsorbent.
(1) Rhodamine B and rhodamine 6G, the volume of the solution is 20mL, the concentration of the dye is 160mg/L, the adsorbent is 3mg, and the adsorption time is 4 hours. The adsorption capacity of the rhodamine B is 869.3mg/g, and the removal rate is 81.5 percent; the adsorption capacity of rhodamine 6G is 1048.8mg/G, and the removal rate is 98.3%.
(2) Methylene blue and malachite green, the volume of the solution is 20mL, the dye concentration is 180mg/L, the adsorbent is 3mg, and the adsorption time is 4 hours. The adsorption capacity of methylene blue is 1144.1mg/g, and the removal rate is 95.0%; the malachite green adsorption capacity is 1126.9mg/g, and the removal rate is 93.9%.
Experimental example 4
The polymer prepared in example 1, which absorbed methylene blue, was thoroughly washed with deionized water, and then the polymer was put into an ethanol solution containing 5% (V/V) acetic acid to perform desorption and recovery of methylene blue. The desorbed polymer was reused in a methylene blue adsorption experiment (adsorbent: 10mg, aqueous methylene blue solution: 100mL, 100 mg/L). The same procedure was repeated 5 times.
As shown in fig. 6, after five times of repeated use, the adsorption efficiency of methylene blue can still be maintained above 90%, which proves good regeneration performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified beta-cyclodextrin polymer is characterized in that beta-cyclodextrin and a cyclotriphosphazene derivative are subjected to heating reaction; adding an acid-binding agent into the heating reaction system, wherein the cyclotriphosphazene derivative is hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene, ethoxy (pentafluoro) cyclotriphosphazene or pentafluoro (phenoxy) cyclotriphosphazene.
2. The preparation method of the modified beta-cyclodextrin polymer as claimed in claim 1, wherein the mass ratio of the beta-cyclodextrin to the cyclotriphosphazene derivative is 1: 1-5;
or the mass ratio of the beta-cyclodextrin to the acid-binding agent is 1: 0.9-2.
3. The process for producing a modified β -cyclodextrin polymer according to claim 1, wherein the solvent of the solvothermal reaction system is N, N-dimethylformamide and/or tetrahydrofuran;
or the acid-binding agent is potassium carbonate.
4. The method for preparing a modified beta-cyclodextrin polymer according to claim 1, wherein the heating reaction is carried out at a temperature of 80 to 160 ℃ for 2 to 72 hours.
5. A modified beta-cyclodextrin polymer obtained by the production method according to any one of claims 1 to 4.
6. Use of the modified β -cyclodextrin polymer of claim 5 for dye adsorption.
7. A dye adsorbent, characterized by comprising an adsorption active ingredient, wherein the adsorption active ingredient is the modified beta-cyclodextrin polymer of claim 5.
8. A method for adsorbing a dye in water, which comprises adding the modified β -cyclodextrin polymer of claim 5 or the dye adsorbent of claim 7 to water containing a dye for adsorption.
9. A method for regenerating a dye adsorbent, characterized in that the modified β -cyclodextrin polymer or the dye adsorbent adsorbed by the adsorption method according to claim 8 is desorbed using an ethanol solution of acetic acid.
10. The method for regenerating a dye adsorbent according to claim 9, wherein the volume fraction of acetic acid in the ethanol solution of acetic acid is 4 to 6%.
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| CN113750968A (en) * | 2021-08-02 | 2021-12-07 | 东华大学 | A kind of water-insoluble cyclodextrin-based metal organic framework material and preparation method thereof |
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| US5276088A (en) * | 1990-05-21 | 1994-01-04 | Toppan Printing Co., Ltd. | Method of synthesizing cyclodextrin polymers |
| CN108355629A (en) * | 2018-01-09 | 2018-08-03 | 中国地质大学（武汉） | A kind of carbon nano-fiber composite material of uniform load carbonaceous particle and its application |
| CN109806851A (en) * | 2019-03-25 | 2019-05-28 | 东华大学 | A kind of cyclodextrin porous material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5276088A (en) * | 1990-05-21 | 1994-01-04 | Toppan Printing Co., Ltd. | Method of synthesizing cyclodextrin polymers |
| CN108355629A (en) * | 2018-01-09 | 2018-08-03 | 中国地质大学（武汉） | A kind of carbon nano-fiber composite material of uniform load carbonaceous particle and its application |
| CN109806851A (en) * | 2019-03-25 | 2019-05-28 | 东华大学 | A kind of cyclodextrin porous material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113750968A (en) * | 2021-08-02 | 2021-12-07 | 东华大学 | A kind of water-insoluble cyclodextrin-based metal organic framework material and preparation method thereof |
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