CN108276523B - Modified cyclodextrin and preparation method and application thereof - Google Patents
Modified cyclodextrin and preparation method and application thereof Download PDFInfo
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- CN108276523B CN108276523B CN201810193990.3A CN201810193990A CN108276523B CN 108276523 B CN108276523 B CN 108276523B CN 201810193990 A CN201810193990 A CN 201810193990A CN 108276523 B CN108276523 B CN 108276523B
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class 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 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 82
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 68
- 229960004853 betadex Drugs 0.000 claims abstract description 68
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 66
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 20
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 20
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims description 31
- 238000007639 printing Methods 0.000 claims description 29
- 238000004043 dyeing Methods 0.000 claims description 28
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 238000006467 substitution reaction Methods 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005694 sulfonylation reaction Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012798 spherical particle Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 229920005615 natural polymer Polymers 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 238000004042 decolorization Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
the invention provides a preparation method of modified cyclodextrin, which relates to the technical field of composite natural polymer flocculants and comprises the following steps of (1) providing acrylamide- β -cyclodextrin, (2) mixing the acrylamide- β -cyclodextrin obtained in the step (1), dimethyl diallyl ammonium chloride, ammonium persulfate, sodium bisulfite and water, and carrying out copolymerization reaction to obtain the modified cyclodextrin.
Description
Technical Field
The invention relates to the technical field of composite natural polymeric flocculant, in particular to modified cyclodextrin and a preparation method and application thereof.
Background
With the rapid development of the textile printing and dyeing industry in China, the dye wastewater becomes one of the most main water pollution sources at present, and the discharge amount of the dye wastewater is about one tenth of the total discharge amount of the industrial wastewater. The waste water comes from bleaching, dyeing, printing and finishing processes in the printing and dyeing processing; it has the characteristics of large amount, high concentration, complex components, high chromaticity and the like. At present, the main mode of sewage treatment is to add sewage treatment agents including corrosion inhibitors, scale inhibitors, flocculating agents, bactericides and the like into the wastewater so that the treated wastewater meets the requirements of water injection quality indexes.
The cyclodextrin modifications of the prior art are generally water-soluble, hydrophobic and ionic. However, the modified cyclodextrin has small specific surface area, few active surface sites and poor adsorbability.
Disclosure of Invention
In view of the above, the invention aims to provide a modified cyclodextrin and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of modified cyclodextrin, which comprises the following steps:
(1) providing acrylamide- β -cyclodextrin;
(2) and (2) mixing the acrylamide- β -cyclodextrin obtained in the step (1), dimethyl diallyl ammonium chloride, ammonium persulfate, sodium bisulfite and water, and carrying out copolymerization reaction to obtain the modified cyclodextrin.
preferably, the mass ratio of the acrylamide- β -cyclodextrin to the dimethyl diallyl ammonium chloride in the step (2) is 1: 1-5.
preferably, the mass ratio of the acrylamide- β -cyclodextrin to the initiator ammonium persulfate in the step (2) is 1: 1-3.
preferably, the mass ratio of the acrylamide- β -cyclodextrin to the initiator sodium bisulfite in the step (2) is 1: 1-3.
Preferably, the temperature of the copolymerization reaction in the step (2) is 30-50 ℃.
Preferably, the time of the copolymerization reaction in the step (2) is 12-30 h.
The invention also provides the modified cyclodextrin obtained by the preparation method in the technical scheme, the modified cyclodextrin is a porous reticular structure built by spherical particles, and the specific surface area of the modified cyclodextrin is 260-320 m2/g。
Preferably, the modified cyclodextrin is used as a flocculating agent.
Preferably, the application is in printing and dyeing wastewater.
Preferably, the pH value of the printing and dyeing wastewater is 3-7.
the invention provides a preparation method of modified cyclodextrin, which comprises the following steps of (1) providing acrylamide- β -cyclodextrin, (2) mixing the acrylamide- β -cyclodextrin obtained in the step (1), dimethyl diallyl ammonium chloride, ammonium persulfate, sodium bisulfite and water, and carrying out copolymerization reaction to obtain the modified cyclodextrin, wherein the acrylamide- β -cyclodextrin is polymerized with dimethyl diallyl ammonium chloride in the presence of initiator ammonium persulfate and sodium bisulfite to obtain the modified cyclodextrin, the modified cyclodextrin is a porous reticular structure built by spherical particles, and the specific surface area of the modified cyclodextrin is 260-320 m2The number of adsorption sites increases. In the range from acidity to neutrality, the modified cyclodextrin has higher adsorption rate on printing and dyeing wastewater with different concentrations (400-1000 mg/L) within 30 min. The data of the examples show that at pH 4, the modified cyclodextrin prepared by the invention has a decolorization rate of 97.21% for printing and dyeing wastewater with a concentration of 600 mg/L.
Drawings
FIG. 1 is an infrared spectrum of β -cyclodextrin, acrylamide- β -cyclodextrin, modified cyclodextrin;
FIG. 2 is an XRD spectrum of β -cyclodextrin, acrylamide- β -cyclodextrin and modified cyclodextrin;
FIG. 3 is an SEM spectrogram of acrylamide- β -cyclodextrin and modified cyclodextrin.
Detailed Description
The invention provides a preparation method of modified cyclodextrin, which comprises the following steps:
(1) providing acrylamide- β -cyclodextrin;
(2) and (2) mixing the acrylamide- β -cyclodextrin obtained in the step (1), dimethyl diallyl ammonium chloride, ammonium persulfate, sodium bisulfite and water, and carrying out copolymerization reaction to obtain the modified cyclodextrin.
in the present invention, the method for preparing acrylamide- β -cyclodextrin (AM- β -CD) preferably comprises:
carrying out sulfonylation reaction on β -cyclodextrin and p-toluenesulfonyl chloride to obtain mono- (6-p-toluenesulfonyl) -cyclodextrin (mono-6-Ots- β -CD);
performing substitution reaction on the mono- (6-p-toluenesulfonyl) -cyclodextrin and ethylenediamine to obtain ethylenediamine- β -cyclodextrin (EDA- β -CD);
and (3) performing substitution reaction on the ethylenediamine- β -cyclodextrin and acryloyl chloride to synthesize acrylamide- β -cyclodextrin (AM- β -CD).
the method comprises the steps of carrying out sulfonylation reaction on β -cyclodextrin and p-toluenesulfonyl chloride to obtain mono- (6-p-toluenesulfonyl) -cyclodextrin, wherein the mass ratio of the β -cyclodextrin to the p-toluenesulfonyl chloride is preferably 1-5: 1, more preferably 1.5-4: 1, and most preferably 2-3.5. in the invention, the β -cyclodextrin and the p-toluenesulfonyl chloride are preferably reacted under the conditions of alkalinity and ice-water bath, in the invention, the alkalinity is preferably 8-13, more preferably 9-12, and most preferably 10-11, the temperature of the ice-water bath is preferably 0-5 ℃, more preferably 1-4 ℃, and most preferably 2-3 ℃.
In the invention, after the sulfonylation reaction is finished, preferably, the sulfonylation reaction product is sequentially filtered and recrystallized to obtain the mono- (6-p-toluenesulfonyl) -cyclodextrin.
after the mono- (6-p-toluenesulfonyl) -cyclodextrin is obtained, the mono- (6-p-toluenesulfonyl) -cyclodextrin and ethylenediamine are preferably subjected to substitution reaction to obtain the ethylenediamine- β -cyclodextrin, in the invention, the molar ratio of the mono- (6-p-toluenesulfonyl) -cyclodextrin to the ethylenediamine is preferably 1: 700-1200, more preferably 1: 750-900, and most preferably 1: 800-850, in the invention, the mono- (6-p-toluenesulfonyl) -cyclodextrin and the ethylenediamine are preferably subjected to substitution reaction under a reflux condition, in the invention, the reflux temperature is preferably 70-90 ℃, more preferably 75-85 ℃, the reflux time is preferably 24-48 h, more preferably 30-45 h, and most preferably 35-40 h, in the invention, the substitution reaction product is preferably subjected to reduced pressure distillation to remove excessive ethylenediamine, and is precipitated in acetone to obtain the ethylenediamine- β -cyclodextrin.
after obtaining the ethylenediamine- β -cyclodextrin, the invention preferably performs a substitution reaction on the ethylenediamine- β -cyclodextrin and acryloyl chloride to obtain the acrylamide- β -cyclodextrin, wherein the mass ratio of the ethylenediamine- β -cyclodextrin to the acryloyl chloride is preferably 1: 1-3, more preferably 1: 1.5-2.5, in the invention, the substitution reaction time is preferably 2-6 h, more preferably 3-5 h, and the substitution reaction temperature is preferably 0-5 ℃, more preferably 1-4 ℃, and most preferably 2-3 ℃.
In the present invention, the acryloyl chloride is preferably dissolved in tetrahydrofuran; the volume ratio of the acryloyl chloride to the tetrahydrofuran is preferably 2: 8.
in the present invention, the reaction of ethylenediamine- β -cyclodextrin and acryloyl chloride is preferably performed in N2the reaction is carried out in a protected methanol-water solution, the mass volume ratio of the ethylenediamine- β -cyclodextrin to the methanol-water solution is preferably 1 g: 3-9 mL, more preferably 1 g: 4-7 mL, and most preferably 1 g: 5-6 mL.
in the invention, the substitution reaction product is preferably subjected to reduced pressure distillation in sequence, ethanol is adopted to separate out a solid, the filtrate is added into acetone for precipitation, and the precipitate is subjected to suction filtration, washing and drying to obtain the acrylamide- β -cyclodextrin.
after the acrylamide- β -cyclodextrin is obtained, the modified cyclodextrin is obtained by mixing the acrylamide- β -cyclodextrin, dimethyl diallyl ammonium chloride (DADMAC), ammonium persulfate, sodium bisulfite and water for copolymerization reaction.
in the invention, the mass ratio of the acrylamide- β -cyclodextrin to the dimethyldiallylammonium chloride is preferably 1: 1-5, more preferably 1: 1.5-4, and most preferably 1: 2-3. in the invention, the mass ratio of the acrylamide- β -cyclodextrin to the ammonium persulfate is preferably 1: 1-3, more preferably 1: 1.5-2.5. in the invention, the mass ratio of the acrylamide- β -cyclodextrin to the sodium bisulfite is preferably 1: 1-3, and more preferably 1: 1.5-2.5.
in the invention, the copolymerization reaction is preferably carried out under the protection of nitrogen, the temperature of the copolymerization reaction is preferably 30-50 ℃, more preferably 32-45 ℃, and most preferably 35-40 ℃, the time of the copolymerization reaction is preferably 12-30 h, more preferably 15-28 h, and most preferably 20-25 h.
After the copolymerization reaction is completed, the invention preferably further comprises purifying the copolymerization reaction product to obtain the modified cyclodextrin. In the present invention, the purification preferably comprises cooling, precipitation, filtration, washing and drying in this order. In the present invention, the precipitation is preferably carried out in acetone. In the present invention, the washing solvent is preferably acetone. In the present invention, the temperature of the drying is preferably 60 ℃. The cooling and filtering method of the present invention is not particularly limited, and those known to those skilled in the art may be used.
The invention also provides the modified cyclodextrin prepared by the preparation method in the technical scheme. In the invention, the modified cyclodextrin has a porous network structure built up by spherical particles, and the specific surface area of the modified cyclodextrin is preferably 260-320 m2/g。
The invention also provides application of the modified cyclodextrin in the technical scheme as a flocculating agent.
In the present invention, the application is preferably an application in printing wastewater. In the invention, the application steps of the modified cyclodextrin as a flocculating agent in the printing and dyeing wastewater preferably comprise: adding modified cyclodextrin into the printing and dyeing wastewater, and oscillating by a shaking table.
In order to obtain the treatment effect on the printing and dyeing wastewater, the absorbance of the supernatant subjected to the oscillation treatment is measured at 416nm by using an ultraviolet-visible spectrophotometer, the treatment effect of the modified cyclodextrin on the printing and dyeing wastewater is expressed by using the decolorization rate, and the calculation formula of the decolorization rate is shown as a formula I.
In the invention, the pH value of the printing and dyeing wastewater is preferably 3-7, and more preferably 3.5-5; the concentration of the dye in the printing and dyeing wastewater is preferably 400-1000 mg/L, more preferably 500-800 mg/L, and most preferably 600 mg/L; in the invention, the shaking time of the shaking table is preferably 15-120 min, more preferably 25-80 min, and most preferably 30-60 min.
In the present invention, the formula of decolorization ratio is preferably:
wherein,
respectively representing the mass concentration of the printing and dyeing wastewater before and after decolorization; v0And V is the volume of the printing and dyeing wastewater before and after decolorization.
The modified cyclodextrins provided by the present invention, the methods for preparing the same, and the uses thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
dissolving 5g β -CD and 1.68g p-toluenesulfonyl chloride in 120mL of 0.75mol/L NaOH, stirring and reacting for 5h at 5 ℃, filtering, recrystallizing and drying to obtain mono-6-Ots- β -CD, reacting 1mol mono-6-Ots- β -CD with 1200mol ethylenediamine at 90 ℃ for 48h, after the reaction is finished, distilling under reduced pressure to remove excessive ethylenediamine, precipitating in acetone to obtain EDA- β -CD, and dissolving 2g EDA- β -CD in 12mL of water-methanol mixed solution (of methanol and water)The volume ratio is 2: 1) n is2stirring for 2h at 5 ℃ under protection, dissolving 2.0mL of acryloyl chloride in 8.0mL of tetrahydrofuran, dropwise adding the reaction solution, reacting for 8h, carrying out reduced pressure distillation, adding 25mL of methanol to precipitate a solid, adding the filtrate into 120mL of acetone to precipitate, carrying out suction filtration, washing, vacuum drying and weighing to obtain AM- β -CD;
adding 15mL of distilled water, 1g of AM- β -CD and 2g of DADMAC into a four-mouth bottle under the protection of nitrogen, dropwise adding a mixed solution of ammonium persulfate and sodium bisulfite (wherein the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1) after dissolving, copolymerizing for 12h at 40 ℃, cooling the obtained mixture to room temperature, pouring the mixture into acetone for precipitation, filtering and washing, and performing vacuum drying at 60 ℃ to obtain the modified cyclodextrin.
the infrared spectrum analysis of β -cyclodextrin, acrylamide-beta-cyclodextrin and modified cyclodextrin is shown in figure 1. it can be seen from figure 1 that the structure of acrylamide-beta-cyclodextrin is 3350cm-1has a characteristic peak of beta-cyclodextrin of (1), and is 630.59cm-1And 1591.75cm-1There is an absorption indicating that both the amino and hydroxyl groups are acylated at the same time. The modified cyclodextrin is 1596cm-1(bending vibration of methyl group in quaternary ammonium group), 761cm-1(C-N stretching vibration in quaternary ammonium group) shows obvious absorption peaks, so that the acrylamide- β -cyclodextrin and cationic monomer DADMAC are indeed subjected to free radical copolymerization, and the product structure is consistent with the expected structure.
the X-ray diffraction analysis is adopted for the crystal forms of β -cyclodextrin, acrylamide- β -cyclodextrin and modified cyclodextrin, and the result is shown in figure 1. As can be seen from figure 2, the recrystallized 2 theta of the β -cyclodextrin has a specific sharp crystal diffraction peak about 18-35 degrees, the diffraction of the acrylamide- β -cyclodextrin is obviously different from that of the β -cyclodextrin, the sharp crystal diffraction peak between 20-40 degrees is weakened, and compared with the β -cyclodextrin, the diffraction characteristic peak of the acrylamide- β -cyclodextrin is reduced, which indicates that the crystal form is changed, the diffraction pattern of the modified cyclodextrin is basically similar to that of the acrylamide- β -cyclodextrin, but the corresponding peak intensity is increased and the peak position has certain displacement, which indicates that the acrylamide- β -cyclodextrin and DMDAAC have interaction to form a new phase.
the surface morphology of the acrylamide- β -cyclodextrin and the modified cyclodextrin is analyzed by adopting SEM, and the result is shown in figure 3, wherein a is an SEM picture of the acrylamide- β -cyclodextrin and b is an SEM picture of the modified cyclodextrin in figure 3, and it can be seen from figure 3 that the acrylamide- β -cyclodextrin is a porous reticular structure and has a loose structure, and the modified cyclodextrin is a porous reticular structure built by spherical particles, so that the surface area is greatly increased, and the adsorption sites are increased.
By using N2The specific surface area of the modified cyclodextrin measured by an adsorption method is 320m2/g。
10mL of printing and dyeing wastewater with the concentration of 600mg/L is adjusted to have the pH value of 4, 0.05g of modified cyclodextrin is added, shaking table oscillation reaction is carried out for 0.5h, supernatant liquid is taken, the absorbance of the supernatant liquid is measured at 416nm by using an ultraviolet-visible spectrophotometer, and the decolorization rate of the modified cyclodextrin on the printing and dyeing wastewater is calculated to be 96.81% by using a decolorization rate indicator.
Example 2
AM- β -CD was prepared according to the method of example 1;
adding 15mL of distilled water, 1g of AM- β -CD and 3g of DADMAC into a four-mouth bottle under the protection of nitrogen, dropwise adding a mixed solution of ammonium persulfate and sodium bisulfite after dissolving (wherein the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1), copolymerizing for 12 hours at 40 ℃, cooling the obtained mixture to room temperature, pouring the mixture into acetone for precipitation, filtering and washing, and performing vacuum drying at 60 ℃ to obtain the modified cyclodextrin.
By using N2The specific surface area of the modified cyclodextrin measured by an adsorption method is 270m2/g。
10mL of printing and dyeing wastewater with the concentration of 600mg/L is adjusted to have the pH value of 4, 0.05g of modified cyclodextrin is added, shaking table oscillation reaction is carried out for 0.5h, supernatant liquid is taken, the absorbance of the supernatant liquid is measured at 416nm by using an ultraviolet-visible spectrophotometer, and the decolorization rate of the modified cyclodextrin on the printing and dyeing wastewater is calculated to be 88.29% by using a decolorization rate indicator.
Example 3
AM- β -CD was prepared according to the method of example 1;
adding 15mL of distilled water, 1g of AM- β -CD and 4g of DADMAC into a four-mouth bottle under the protection of nitrogen, dropwise adding a mixed solution of ammonium persulfate and sodium bisulfite after dissolving (wherein the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1), copolymerizing for 12 hours at 40 ℃, cooling the obtained mixture to room temperature, pouring the mixture into acetone for precipitation, filtering and washing, and performing vacuum drying at 60 ℃ to obtain the product.
By using N2The specific surface area of the modified cyclodextrin measured by an adsorption method is 260m2/g。
10mL of printing and dyeing wastewater with the concentration of 600mg/L is adjusted to have the pH value of 4, 0.05g of modified cyclodextrin is added, shaking table oscillation reaction is carried out for 0.5h, supernatant liquid is taken, the absorbance of the supernatant liquid is measured at 416nm by using an ultraviolet-visible spectrophotometer, and the decolorization rate of the modified cyclodextrin on the printing and dyeing wastewater is calculated to be 76.40% by using a decolorization rate indicator.
Example 4
AM- β -CD was prepared according to the method of example 1;
adding 15mL of distilled water, 1g of AM- β -CD and 2g of DADMAC into a four-mouth bottle under the protection of nitrogen, dropwise adding a mixed solution of ammonium persulfate and sodium bisulfite (wherein the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1) after dissolving, copolymerizing for 24h at 40 ℃, cooling the obtained mixture to room temperature, pouring the mixture into acetone for precipitation, filtering, washing, and drying in vacuum at 60 ℃ to obtain the product.
By using N2The specific surface area of the modified cyclodextrin measured by an adsorption method is 280m2/g。
10mL of printing and dyeing wastewater with the concentration of 600mg/L is adjusted to have the pH value of 4, 0.05g of modified cyclodextrin is added, shaking table oscillation reaction is carried out for 0.5h, supernatant liquid is taken, the absorbance of the supernatant liquid is measured at 416nm by using an ultraviolet-visible spectrophotometer, and the decolorization rate of the modified cyclodextrin on the printing and dyeing wastewater is calculated to be 97.09% by using a decolorization rate indicator.
Example 5
AM- β -CD was prepared according to the method of example 1;
adding 15mL of distilled water, 1g of AM- β -CD and 2g of DADMAC into a four-mouth bottle under the protection of nitrogen, dropwise adding a mixed solution of ammonium persulfate and sodium bisulfite after dissolving (wherein the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1), copolymerizing for 30h at 40 ℃, cooling the obtained mixture to room temperature, pouring the mixture into acetone for precipitation, filtering and washing, and performing vacuum drying at 60 ℃ to obtain the product.
By using N2The specific surface area of the modified cyclodextrin measured by an adsorption method is 290m2/g。
10mL of printing and dyeing wastewater with the concentration of 600mg/L is adjusted to have the pH value of 4, 0.05g of modified cyclodextrin is added, shaking table oscillation reaction is carried out for 0.5h, supernatant liquid is taken, the absorbance of the supernatant liquid is measured at 416nm by using an ultraviolet-visible spectrophotometer, and the decolorization rate of the modified cyclodextrin on the printing and dyeing wastewater is calculated to be 97.21% by using a decolorization rate indicator.
The embodiment shows that the modified cyclodextrin provided by the invention is a porous network structure built by spherical particles, and the specific surface area is as high as 260-320 m2The number of adsorption sites increases. When the pH value is 4, the decolorization rate of the modified cyclodextrin to printing and dyeing wastewater with the concentration of 600mg/L is up to 97.21%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of modified cyclodextrin is characterized by comprising the following steps:
(1) providing acrylamide- β -cyclodextrin;
(2) mixing the acrylamide- β -cyclodextrin obtained in the step (1), dimethyl diallyl ammonium chloride, an initiator and water, and carrying out copolymerization reaction to obtain modified cyclodextrin, wherein the initiator comprises ammonium persulfate and sodium bisulfite;
the preparation method of the acrylamide- β -cyclodextrin comprises the following steps:
carrying out sulfonylation reaction on beta-cyclodextrin and p-toluenesulfonyl chloride to obtain mono- (6-p-toluenesulfonyl) -cyclodextrin, wherein the mass ratio of β -cyclodextrin to the p-toluenesulfonyl chloride is 1-5: 1, the sulfonylation reaction is carried out at the temperature of 0-5 ℃ for 3-8 h, and the pH value of the sulfonylation reaction environment is 8-13;
performing substitution reaction on the mono- (6-p-toluenesulfonyl) -cyclodextrin and ethylenediamine to obtain ethylenediamine- β -cyclodextrin, wherein the molar ratio of the mono- (6-p-toluenesulfonyl) -cyclodextrin to the ethylenediamine is 1: 700-1200, the mono- (6-p-toluenesulfonyl) -cyclodextrin and the ethylenediamine perform substitution reaction under a reflux condition, the reflux temperature is 70-90 ℃, and the reflux time is 24-48 hours;
performing substitution reaction on the ethylenediamine- β -cyclodextrin and acryloyl chloride to synthesize acrylamide- β -cyclodextrin, wherein the mass ratio of the ethylenediamine- β -cyclodextrin to the acryloyl chloride is 1: 1-3, and the temperature of the substitution reaction is 0-5 ℃;
the temperature of the copolymerization reaction is 30-50 ℃; the time of the copolymerization reaction is 12-30 h.
2. the preparation method according to claim 1, wherein the mass ratio of the acrylamide- β -cyclodextrin to the dimethyldiallylammonium chloride in the step (2) is 1: 1-5.
3. the preparation method according to claim 1, wherein the mass ratio of the acrylamide- β -cyclodextrin to the ammonium persulfate in the step (2) is 1: 1-3.
4. the preparation method according to claim 1 or 3, wherein the mass ratio of the acrylamide- β -cyclodextrin to the sodium bisulfite in the step (2) is 1: 1-3.
5. The modified cyclodextrin obtained by the preparation method of any one of claims 1 to 4, wherein the modified cyclodextrin is a porous network structure built up by spherical particles, and the specific surface area of the modified cyclodextrin is 260-320 m2/g。
6. Use of the modified cyclodextrin of claim 5 as a flocculant.
7. Use according to claim 6, characterized in that the use is in printing and dyeing wastewater.
8. The use according to claim 7, wherein the printing and dyeing wastewater has a pH of 3 to 7.
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