CN115536138B - Cyclodextrin cross-linked chitosan embedded nitrifying bacteria wastewater treatment agent and preparation method thereof - Google Patents
Cyclodextrin cross-linked chitosan embedded nitrifying bacteria wastewater treatment agent and preparation method thereof Download PDFInfo
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- CN115536138B CN115536138B CN202211029175.6A CN202211029175A CN115536138B CN 115536138 B CN115536138 B CN 115536138B CN 202211029175 A CN202211029175 A CN 202211029175A CN 115536138 B CN115536138 B CN 115536138B
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- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 100
- 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 89
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 53
- 241000894006 Bacteria Species 0.000 title claims abstract description 33
- 230000001546 nitrifying effect Effects 0.000 title claims abstract description 33
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 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 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 10
- -1 acrylic ester Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 150000002148 esters Chemical class 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000001116 FEMA 4028 Substances 0.000 claims description 9
- 229960004853 betadex Drugs 0.000 claims description 9
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 9
- 229940106681 chloroacetic acid Drugs 0.000 claims description 9
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001580 bacterial effect Effects 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000009360 aquaculture Methods 0.000 abstract description 4
- 244000144974 aquaculture Species 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 230000000813 microbial effect Effects 0.000 abstract description 2
- 230000002522 swelling effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 25
- 238000005406 washing Methods 0.000 description 25
- 238000001914 filtration Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the technical field of water treatment, and discloses a cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent and a preparation method thereof, wherein an acrylic ester matrix and rich carboxyl groups are introduced into a cyclodextrin matrix, and then the cyclodextrin matrix is subjected to graft copolymerization with carboxymethyl chitosan and acrylamide in an ammonium persulfate and sodium bisulphite redox system to obtain functionalized cyclodextrin grafted chitosan which is used as a microbial carrier for embedding and loading nitrifying bacteria and is applied to the treatment of heavy metal ions and ammonia nitrogen pollutants in a water body environment; the functional cyclodextrin grafted chitosan contains rich carboxyl and amide groups, has good hydrophilicity, excellent swelling property in aqueous solution, high adsorption rate on metal ions such as Pb 2+ and good removal effect; the nitrifying bacteria can be loaded to effectively degrade ammonia nitrogen pollutants in agricultural wastewater and aquaculture water.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Background
Agricultural wastewater, industrial sewage, aquaculture water and the like contain a large amount of heavy metal and ammonia nitrogen pollutants, which can cause water quality deterioration, environmental pollution and serious damage to ecological environment and economic development, natural biological materials such as chitosan and cyclodextrin have green pollution-free, low-cost and easy-to-obtain and excellent adsorption performance, and have wide application prospects in the aspects of water pollution treatment and improvement of aquaculture water environment development, such as research on adsorption of chromium and cadmium in water by chitosan crosslinked beta-cyclodextrin, and chitosan crosslinked beta-cyclodextrin high polymer is synthesized and can be applied to adsorption removal of chromium and cadmium in water.
The biodegradation method can effectively treat pollutants such as metal ions, ammonia nitrogen and the like in a water body environment, can utilize chitosan, cyclodextrin and the like as microorganism carriers, for example, the application of cyclodextrin modified reticular polyurethane foam microorganism immobilization carriers in water treatment is disclosed, beta-cyclodextrin modified reticular polyurethane foam plastic is utilized as microorganism immobilization carriers, and high ammonia nitrogen simulated wastewater can be effectively treated after nitrifying bacteria are loaded.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent which is used for treating heavy metal ions and ammonia nitrogen pollutants in a water body environment.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: a cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent is prepared by the following steps:
(1) Adding beta-cyclodextrin into a sodium hydroxide solution, then dropwise adding an acetonitrile solution of p-toluenesulfonyl chloride, and reacting to obtain p-toluenesulfonyl-beta-cyclodextrin; then adding the mixture into ethylenediamine to carry out heating reaction, thus obtaining ethylenediamine-based cyclodextrin.
(2) Adding ethylenediamine-based cyclodextrin into tetrahydrofuran, dispersing uniformly, then dropwise adding glycidyl methacrylate, heating to react to 60-90 ℃, reacting 6-18 h, then removing the solvent by rotary evaporation, and washing the product with ethanol to obtain the acrylic ester-based cyclodextrin.
(3) Adding the acrylic ester cyclodextrin into a sodium hydroxide solution, stirring uniformly, adding chloroacetic acid, heating to react at 40-60 ℃, reacting at 5-20 h, dropwise adding a hydrochloric acid solution to adjust the pH of the solution to 6 after the reaction, and filtering the solvent, thereby washing with distilled water to obtain the acrylic ester carboxyl cyclodextrin.
(4) Adding carboxymethyl chitosan, acrylic ester carboxyl cyclodextrin and acrylamide into distilled water, uniformly stirring, then dropwise adding 0.8-1.5% of ammonium persulfate and 0.4-0.8% of sodium bisulfite, heating to 55-70 ℃ in nitrogen atmosphere, stirring for reaction for 3-6 h, filtering the solvent after the reaction, and washing with distilled water to obtain the functionalized cyclodextrin grafted chitosan.
(5) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding a bacterial suspension of nitrifying bacteria, dropwise adding 2-4% of glutaraldehyde aqueous solution, reacting at room temperature for 3-8 h, filtering a solvent after the reaction, and washing with distilled water to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Preferably, the mass ratio of the ethylenediamine cyclodextrin to the glycidyl methacrylate in the step (2) is 1:0.8-3.
Preferably, the concentration of the sodium hydroxide solution in the step (3) is 1-3%.
Preferably, the mass ratio of the acrylate cyclodextrin to the chloroacetic acid in the step (3) is 1:1.5-6.
Preferably, the mass ratio of the carboxymethyl chitosan, the acrylic ester carboxyl cyclodextrin and the acrylamide in the step (4) is 1:0.5-3:0.1-0.4.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
The method comprises the steps of utilizing glycidyl methacrylate to carry out ring-opening reaction with ethylenediamine cyclodextrin, then carrying out substitution reaction on hydroxyl and imino groups generated by the ring-opening reaction with chloroacetic acid under the catalysis of sodium hydroxide to obtain acrylic ester carboxyl cyclodextrin, thereby introducing an acrylic ester matrix and rich carboxyl groups into a cyclodextrin matrix, then carrying out graft copolymerization with carboxymethyl chitosan and acrylamide in an ammonium persulfate and sodium bisulphite redox system to obtain functionalized cyclodextrin grafted chitosan, and carrying out functional modification on chitosan and cyclodextrin by simple and efficient molecular design and synthesis means, wherein the functionalized cyclodextrin grafted chitosan is used as a microbial carrier to carry out embedding load on nitrifying bacteria, and is applied to the treatment of heavy metal ions and ammonia nitrogen pollutants in a water body environment.
The functional cyclodextrin grafted chitosan contains rich carboxyl and amide groups, has good hydrophilicity, excellent swelling property and dispersibility in aqueous solution, strong chelating property on metal ions such as Pb 2+, high adsorption rate and good removal effect; the nitrifying bacteria can be loaded to effectively degrade ammonia nitrogen pollutants in agricultural wastewater and aquaculture water.
Drawings
FIG. 1 is a route diagram for the preparation of acrylate carboxyl cyclodextrins.
FIG. 2 is an infrared spectrum of the acrylate-based cyclodextrin and the acrylate-carboxyl cyclodextrin obtained in example 1.
Detailed Description
Example 1
(1) Adding 5g beta-cyclodextrin into 1% sodium hydroxide solution, then dropwise adding acetonitrile solution containing 1g of p-toluenesulfonyl chloride, and reacting to obtain p-toluenesulfonyl-beta-cyclodextrin; then adding the mixture into ethylenediamine of 40 mL for heating reaction to obtain ethylenediamine cyclodextrin.
(2) Adding 3g of ethylenediamine cyclodextrin into tetrahydrofuran, dispersing uniformly, then dripping 2.4 of glycidyl methacrylate of g, heating to react to 90 ℃, reacting 6 h, removing the solvent by rotary evaporation, and washing the product with ethanol to obtain the acrylic ester cyclodextrin.
(3) Adding 3 g of acrylic ester cyclodextrin into 1% of sodium hydroxide solution, stirring uniformly, adding 4.5 of g of chloroacetic acid, heating to react at 60 ℃, reacting 5 of h, dripping hydrochloric acid solution to adjust the pH of the solution to 6 after the reaction, filtering the solvent, and washing with distilled water to obtain the acrylic ester carboxyl cyclodextrin.
(4) Adding 2g of carboxymethyl chitosan, 1 g of acrylic ester carboxyl cyclodextrin and 0.2 g of acrylamide into distilled water, uniformly stirring, then dropwise adding 0.025 g of ammonium persulfate and 0.013 g of sodium bisulphite, heating to 60 ℃ in a nitrogen atmosphere, stirring for reaction 3h, filtering a solvent after the reaction, and washing with distilled water to obtain the functionalized cyclodextrin grafted chitosan.
(5) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding 10 6 CFU/mL of nitrifying bacteria bacterial suspension, dropwise adding 2% glutaraldehyde aqueous solution, reacting at room temperature for 5: 5 h, filtering a solvent after the reaction, and washing with distilled water to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Example 2
(1) Adding 3g parts of ethylenediamine cyclodextrin into tetrahydrofuran, dispersing uniformly, then dripping 5 g of glycidyl methacrylate, heating to react to 90 ℃, reacting 6 h, removing the solvent by rotary evaporation, and washing the product with ethanol to obtain the acrylic ester cyclodextrin.
(2) Adding 3 g of acrylic ester cyclodextrin into 2% sodium hydroxide solution, stirring uniformly, adding 10.6 g of chloroacetic acid, heating to react at 40 ℃, reacting at 20 ℃ and h, dripping hydrochloric acid solution to adjust the pH of the solution to 6 after the reaction, filtering the solvent, and washing with distilled water to obtain the acrylic ester carboxyl cyclodextrin.
(3) Adding 2g of carboxymethyl chitosan, 3g of acrylic ester carboxyl cyclodextrin and 0.5 of acrylamide of g into distilled water, uniformly stirring, then dropwise adding 0.08 g of ammonium persulfate and 0.038 g of sodium bisulfite, heating to 55 ℃ in nitrogen atmosphere, stirring for reaction 6 h, filtering the solvent after the reaction, and washing with distilled water to obtain the functionalized cyclodextrin grafted chitosan.
(4) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding 10 8 CFU/mL of nitrifying bacteria bacterial suspension, dropwise adding 3% of glutaraldehyde aqueous solution, reacting at room temperature for 8: 8 h, filtering a solvent after the reaction, and washing with distilled water to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Example 3
(1) Adding 3g of ethylenediamine cyclodextrin into tetrahydrofuran, dispersing uniformly, then dripping 7.8 of glycidyl methacrylate of g, heating to react to 80 ℃, reacting 6 h, removing the solvent by rotary evaporation, and washing the product with ethanol to obtain the acrylic ester cyclodextrin.
(2) Adding 3 g of acrylic ester cyclodextrin into 3% sodium hydroxide solution, stirring uniformly, adding 15.2 g of chloroacetic acid, heating to react at 50 ℃, reacting 12 h, dripping hydrochloric acid solution to adjust the pH of the solution to 6 after the reaction, filtering the solvent, and washing with distilled water to obtain the acrylic ester carboxyl cyclodextrin.
(3) Adding 2g of carboxymethyl chitosan, 4.8 of acrylic ester carboxyl cyclodextrin of g and 0.65 of acrylamide of g into distilled water, uniformly stirring, then dropwise adding 0.1 g of ammonium persulfate and 0.048 of sodium bisulfite of g, heating to 70 ℃ in nitrogen atmosphere, stirring for reaction 3 h, filtering a solvent after the reaction, and washing with distilled water to obtain the functionalized cyclodextrin grafted chitosan.
(4) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding 10 5 CFU/mL of nitrifying bacteria bacterial suspension, dropwise adding 3% of glutaraldehyde aqueous solution, reacting at room temperature for 6 h, filtering a solvent after the reaction, and washing with distilled water to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Example 4
(1) Adding 3 g of ethylenediamine cyclodextrin into tetrahydrofuran, dispersing uniformly, then dripping 9 g of glycidyl methacrylate, heating to react to 90 ℃, reacting 6 h, removing the solvent by rotary evaporation, and washing the product with ethanol to obtain the acrylic ester cyclodextrin.
(2) Adding 3 g of acrylic ester cyclodextrin into 3% sodium hydroxide solution, stirring uniformly, adding 18 g of chloroacetic acid, heating to react at 50 ℃, reacting 18h, dripping hydrochloric acid solution to adjust the pH of the solution to 6 after the reaction, filtering the solvent, and washing with distilled water to obtain the acrylic ester carboxyl cyclodextrin.
(3) Adding 2g of carboxymethyl chitosan, 6 g of acrylic ester carboxyl cyclodextrin and 0.8 of acrylamide of g into distilled water, uniformly stirring, then dropwise adding 0.12 g of ammonium persulfate and 0.06 g of sodium bisulfite, heating to 70 ℃ in nitrogen atmosphere, stirring for reaction 3 h, filtering the solvent after the reaction, and washing with distilled water to obtain the functional cyclodextrin grafted chitosan.
(4) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding 10 5 CFU/mL of nitrifying bacteria bacterial suspension, dropwise adding 4% of glutaraldehyde aqueous solution, reacting at room temperature for 8: 8h, filtering a solvent after the reaction, and washing with distilled water to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Comparative example 1
(1) Adding 3 g of ethylenediamine cyclodextrin into tetrahydrofuran, dispersing uniformly, then dripping 4.5 of glycidyl methacrylate of g, heating to react to 70 ℃, reacting 6h, removing the solvent by rotary evaporation, and washing the product with ethanol to obtain the acrylic ester cyclodextrin.
(2) Adding 2g carboxymethyl chitosan, 1.5 g acrylic ester cyclodextrin and 0.3 g acrylamide into distilled water, uniformly stirring, then dropwise adding 0.035 g ammonium persulfate and 0.018 g sodium bisulfite, heating to 70 ℃ in nitrogen atmosphere, stirring for reaction 3 h, filtering the solvent after the reaction, and washing with distilled water to obtain cyclodextrin grafted chitosan.
(3) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding 10 5 CFU/mL of nitrifying bacteria bacterial suspension, dropwise adding 2% of glutaraldehyde aqueous solution, reacting at room temperature for 8: 8 h, filtering a solvent after the reaction, and washing with distilled water to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
Comparative example 2
(1) Adding 2 g of carboxymethyl chitosan and 0.6 of g of acrylamide into distilled water, uniformly stirring, then dropwise adding 0.09 of g of ammonium persulfate and 0.048 of g of sodium bisulfite, heating to 55 ℃ in a nitrogen atmosphere, stirring for reaction 5h, filtering a solvent after the reaction, and washing with distilled water to obtain the polyacrylamide chitosan.
(2) Adding polyacrylamide chitosan into distilled water, stirring and swelling, dropwise adding 10 7 CFU/mL of nitrifying bacteria bacterial suspension, dropwise adding 3% of glutaraldehyde aqueous solution, reacting at room temperature for 8: 8h, filtering a solvent after the reaction, and washing with distilled water to obtain the cross-linked chitosan embedded nitrifying bacteria wastewater treatment agent.
0.2 G of the crosslinked chitosan-embedded nitrifying bacteria wastewater treatment agent is added into a Pb 2+ solution (the concentration is C 0) of 100 mL, the pH of the solution is adjusted to 5, the solution is adsorbed to equilibrium at room temperature, then the concentration C of Pb 2+ in the solution is determined by atomic absorption spectrophotometry, and the removal rate Q is calculated.
Q=（C0-C）/C0×100%。
Claims (5)
1. A cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent is characterized in that: the preparation method of the wastewater treatment agent comprises the following steps:
(1) Adding beta-cyclodextrin into a sodium hydroxide solution, then dropwise adding an acetonitrile solution of p-toluenesulfonyl chloride, and reacting to obtain p-toluenesulfonyl-beta-cyclodextrin; then adding the mixture into ethylenediamine for heating reaction to obtain ethylenediamine-based cyclodextrin;
(2) Adding ethylenediamine-based cyclodextrin into tetrahydrofuran, dispersing uniformly, then dropwise adding glycidyl methacrylate, heating to react to 60-90 ℃, and reacting to 6-18 h to obtain acrylic ester-based cyclodextrin;
(3) Adding acrylic acid ester cyclodextrin into sodium hydroxide solution, stirring uniformly, adding chloroacetic acid, heating to react at 40-60 ℃, reacting at 5-20 h, dropwise adding hydrochloric acid solution after the reaction to adjust the pH of the solution to 6, and obtaining acrylic acid ester carboxyl cyclodextrin;
(4) Adding carboxymethyl chitosan, acrylic ester carboxyl cyclodextrin and acrylamide into distilled water, uniformly stirring, then dropwise adding 0.8-1.5% of ammonium persulfate and 0.4-0.8% of sodium bisulfite, heating to 55-70 ℃ in nitrogen atmosphere, and stirring for reacting 3-6 h to obtain functionalized cyclodextrin grafted chitosan;
(5) Adding the functionalized cyclodextrin grafted chitosan into distilled water, stirring and swelling, then dropwise adding a bacterial suspension of nitrifying bacteria, dropwise adding 2-4% of glutaraldehyde aqueous solution, and reacting at room temperature for 3-8 h to obtain the cyclodextrin crosslinked chitosan embedded nitrifying bacteria wastewater treatment agent.
2. The cyclodextrin crosslinked chitosan-embedded nitrifying bacteria wastewater treatment agent disclosed by claim 1, which is characterized in that: the mass ratio of the ethylenediamine cyclodextrin to the glycidyl methacrylate in the step (2) is 1:0.8-3.
3. The cyclodextrin crosslinked chitosan-embedded nitrifying bacteria wastewater treatment agent disclosed by claim 1, which is characterized in that: the concentration of the sodium hydroxide solution in the step (3) is 1-3%.
4. The cyclodextrin crosslinked chitosan-embedded nitrifying bacteria wastewater treatment agent disclosed by claim 1, which is characterized in that: the mass ratio of the acrylic ester cyclodextrin to the chloroacetic acid in the step (3) is 1:1.5-6.
5. The cyclodextrin crosslinked chitosan-embedded nitrifying bacteria wastewater treatment agent disclosed by claim 1, which is characterized in that: the mass ratio of the carboxymethyl chitosan to the acrylic ester carboxyl cyclodextrin to the acrylamide in the step (4) is 1:0.5-3:0.1-0.4.
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