CN112619619A - Modified adsorption material for treating wastewater - Google Patents
Modified adsorption material for treating wastewater Download PDFInfo
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- CN112619619A CN112619619A CN202011424278.3A CN202011424278A CN112619619A CN 112619619 A CN112619619 A CN 112619619A CN 202011424278 A CN202011424278 A CN 202011424278A CN 112619619 A CN112619619 A CN 112619619A
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- treating wastewater
- polystyrene resin
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- 239000002351 wastewater Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 28
- 239000011256 inorganic filler Substances 0.000 claims abstract description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 12
- 239000003223 protective agent Substances 0.000 claims abstract description 9
- 239000008394 flocculating agent Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 10
- FHTWQMHOTBIHEP-UHFFFAOYSA-N 2-methylidene-4-phenyl-1,3-dioxolane Chemical compound O1C(=C)OCC1C1=CC=CC=C1 FHTWQMHOTBIHEP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010424 alunite Substances 0.000 claims description 5
- 229910052934 alunite Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims description 5
- 244000063299 Bacillus subtilis Species 0.000 claims description 4
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 241000108664 Nitrobacteria Species 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002612 dispersion medium Substances 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- 241000194108 Bacillus licheniformis Species 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 241000194032 Enterococcus faecalis Species 0.000 claims description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 229930003427 Vitamin E Natural products 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229940032049 enterococcus faecalis Drugs 0.000 claims description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 235000019165 vitamin E Nutrition 0.000 claims description 3
- 239000011709 vitamin E Substances 0.000 claims description 3
- 229940046009 vitamin E Drugs 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 2
- 229930003451 Vitamin B1 Natural products 0.000 claims description 2
- 229930003471 Vitamin B2 Natural products 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229960002477 riboflavin Drugs 0.000 claims description 2
- 229960003495 thiamine Drugs 0.000 claims description 2
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims description 2
- 235000010374 vitamin B1 Nutrition 0.000 claims description 2
- 239000011691 vitamin B1 Substances 0.000 claims description 2
- 235000019164 vitamin B2 Nutrition 0.000 claims description 2
- 239000011716 vitamin B2 Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000011814 protection agent Substances 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 4
- 238000012851 eutrophication Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000009360 aquaculture Methods 0.000 description 9
- 244000144974 aquaculture Species 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000002156 adsorbate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- -1 ferric polysilicate Chemical compound 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Nanotechnology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The scheme relates to a modified adsorption material for treating wastewater, which comprises the following components: 50-60 parts of modified polystyrene resin, 3-6 parts of biological flora, 0.5-1 part of flora protective agent, 10-15 parts of flocculating agent and 20-30 parts of inorganic filler. The invention designs a modified polystyrene resin which has the characteristic of large specific surface area of macroporous resin, has strong adsorption capacity, and meanwhile, the polymer backbone is degradable and is easy to hydrolyze into small molecules in a water body, so that secondary pollution to the environment caused by residual macromolecular polymer is avoided; biological flora is added based on the modified macroporous adsorption resin, the purpose of purifying water quality is achieved by using a small amount of biological flora, and meanwhile, due to the small amount, eutrophication can not be caused to a water body; other additives are matched for use, so that pollutants in the aquatic product wastewater can be better treated, the improvement of the water body environment is promoted, and the natural balance of the water body environment is realized.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a modified adsorbing material for treating wastewater.
Background
The fresh water resources in China are rich, the aquaculture amount is in the front of the world, but most of the aquaculture in China adopts closed water areas such as ponds, warehouses and the like, the self-purification capacity of the water is not as good as that of a living water source, and the eutrophication of the aquaculture water is caused by the application of a large amount of feed; the addition of the bactericide and the disinfectant and the accumulation of animal and plant corpses directly cause the accumulation of a large amount of organic matters, nitrogen and phosphorus in the water body, and the aquaculture wastewater not only causes damage to aquatic products, but also causes great harm to surrounding water areas and ecological environment.
At present, the general sewage treatment process is generally divided into three major categories, namely physical method, chemical method and biological method. With a single method, a good treatment effect is often difficult to achieve, and for aquaculture water, a water treatment agent remains in the water after use and can also cause harm to the health of fishes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the degradable macroporous resin which is used as the adsorption material of the aquatic wastewater, has a good adsorption and catalysis function on pollutants in a water body, and can be degraded into small molecules after being treated for a period of time, so that the secondary pollution to the water body can be avoided.
In order to achieve the purpose, the invention provides the following technical scheme:
a modified adsorption material for treating wastewater comprises the following components: modified polystyrene resin, biological flora, a flora protective agent, a flocculating agent and inorganic filler; wherein the preparation process of the modified polystyrene resin comprises the following steps:
s1: adding azobisisobutyronitrile, styrene and divinylbenzene into a reaction bottle, uniformly mixing, adding toluene, heating to 45 ℃, adding 2-methylene-4-phenyl-1, 3-dioxolane, adding a dispersing agent and a dispersion medium while stirring, heating for reaction for a period of time, naturally cooling, centrifugally separating a product, collecting solids, fully washing with methanol, and drying to obtain polystyrene-ester microspheres;
s2: polystyrene-ester microspheres in CCl4Swelling for 3h, adding chlorosulfonic acid while stirring, reacting for 0.5-1h at 50-60 ℃, washing with ethanol and water in sequence after the reaction is finished, and drying to obtain the modified polystyrene resin.
Further, the reaction condition in the S1 is that the temperature is controlled to be 65-80 ℃, and the reaction time is 8-9 h.
Further, the mass ratio of the styrene, the azobisisobutyronitrile, the 2-methylene-4-phenyl-1, 3-dioxolane, the divinylbenzene and the toluene is 1:0.01: 0.5-1.5: 0.1: 0.1.
Further, the dispersing agent is polyvinylpyrrolidone or polyvinyl alcohol; the dispersion medium was methanol/water in a volume ratio of 80/20.
Further, the biological flora is selected from at least two mixed strains of bacillus subtilis, nitrobacteria, yeast, bacillus licheniformis or enterococcus faecalis.
Further, the flora protecting agent is selected from vitamin C, vitamin B1, vitamin B2, choline chloride, vitamin E or thiourea.
Further, the flocculant is selected from polymeric aluminum oxide, ferric sulfate, ferric polysilicate, aluminum chloride or polymeric aluminum sulfate.
Further, the inorganic filler is selected from at least three compositions of active carbon, diatomite, alunite, calcium hydrogen phosphate, sodium sulfite or magnesium sulfate.
Further, the weight parts of the components are as follows: 50-60 parts of modified polystyrene resin, 3-6 parts of biological flora, 0.5-1 part of flora protective agent, 10-15 parts of flocculating agent and 20-30 parts of inorganic filler.
The invention further provides a preparation method of the modified adsorbing material for treating wastewater, which comprises the following steps:
1) mixing the biological flora and the flora protective agent, crushing by using a micronizer, uniformly stirring, and storing for 10 days in a sealed and dark manner;
2) crushing the flocculating agent and the inorganic filler by using a micro-pulverizer, and uniformly mixing and stirring;
3) and (3) uniformly mixing and stirring the modified polystyrene resin, the step 1) and the step 2) to obtain the modified adsorbing material for treating the wastewater.
The macroporous resin can be prepared by utilizing styrene and divinylbenzene, has certain adsorption property due to the larger specific surface area, and can form van der Waals force with organic substances in a water body, so that the macroporous resin can be used as an adsorbent for sewage treatment. However, the density of benzene rings in the polymer chain is high, so that the adsorption capacity is limited, and the bonds between the polymer chain and adsorbates are easy to fall off; and the polystyrene resin has strong hydrophobicity, so that the polystyrene resin is unevenly dispersed in a water body, and the adsorption effect is weakened.
The invention also uses the cyclic ketene acetal (2-methylene-4-phenyl-1, 3-dioxolane) with benzene ring in the process of preparing the polystyrene macroporous adsorption resin, the cyclic ketene acetal monomer introduces ester group in the main chain of the polymer through the ring-opening polymerization of free radicals, and simultaneously keeps the existence of benzene ring in the side chain, thereby ensuring the adsorption characteristic of the macroporous resin; on one hand, the introduction of the ester group enables the main chain of the polymer to have degradability, and the polymer is easily degraded into small molecules after water treatment; on the other hand, the ester-based chain is inserted into the polymer backbone, so that the spacing between benzene rings on the backbone is effectively lengthened, the electron cloud density at the position is diluted, the steric hindrance caused by the aromatic ring is reduced, more space is made for combining adsorbates with larger volume, and the adsorbates are combined more firmly and are not easy to fall off; with introduction of an ester group in the fragment-COOCH2In CH (Ph), because carbon atoms in CH (Ph) are hybridized in sp3 mode, oxygen atoms in ester groups are closer to benzene rings, lone pair electrons in the oxygen atoms generate an induced electron supply effect on the benzene rings, so that sulfonation reaction at the para positions of the benzene rings is easier to occur, the sulfonation reaction is favorably completed under a milder reaction condition, and sulfonic groups are generated on the surfaces of resin microspheres, so that the hydrophilicity of the resin is effectively increased, the resin microspheres are convenient to disperse in a water body, and the adsorption performance is improved.
The biological flora is attached to the surface of the macroporous resin and can form a large microbial environment with indigenous microorganisms in a water body, thereby achieving the functions of purification and adsorption.
The flora protecting agent can improve the storage stability of the strains, increase the storage time and facilitate transportation.
The flocculating agent and the pollutants in the water body form flocculate, so that the cost is low and the flocculating effect is good.
Compared with the prior art, the invention has the beneficial effects that: the invention designs a modified polystyrene resin which has the characteristic of large specific surface area of macroporous resin, has strong adsorption capacity, and simultaneously the polymer backbone can be degraded and hydrolyzed into micromolecules in water, so that secondary pollution to the environment caused by residual macromolecular polymer is avoided; biological flora is added based on the modified macroporous adsorption resin, the purpose of purifying water quality is achieved by using a small amount of biological flora, and meanwhile, due to the small amount, eutrophication can not be caused to a water body; other additives are matched for use, so that pollutants in aquaculture wastewater can be better treated, the water environment is promoted to be improved, and the natural balance of the water environment is realized.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1: a modified adsorption material for treating wastewater comprises the following components: 50 parts of modified polystyrene resin, 1 part of bacillus subtilis, 2 parts of nitrobacteria, 0.5 part of vitamin C, 10 parts of ferric sulfate and 20 parts of inorganic filler (the mass ratio of activated carbon to diatomite to alunite is 1:1: 1).
Example 2: a modified adsorption material for treating wastewater comprises the following components: 55 parts of modified polystyrene resin, 2 parts of nitrobacteria, 3 parts of yeast, 0.8 part of vitamin E, 12 parts of aluminum chloride and 25 parts of inorganic filler (the mass ratio of alunite, calcium hydrophosphate and sodium sulfite is 2:1: 1).
Example 3: a modified adsorption material for treating wastewater comprises the following components: 60 parts of modified polystyrene resin, 1 part of bacillus subtilis, 2 parts of bacillus licheniformis, 3 parts of enterococcus faecalis, 1 part of thiourea, 15 parts of ferric polysilicate and 30 parts of inorganic filler (the mass ratio of the diatomite, the alunite and the calcium hydrophosphate is 2:2: 1).
Wherein the preparation process of the modified polystyrene resin comprises the following steps:
s1: adding 0.01mol of azobisisobutyronitrile, 1mol of styrene and 0.1mol of divinylbenzene into a reaction bottle, uniformly mixing, adding 0.1mol of toluene, heating to 45 ℃, adding 1.5mol of 2-methylene-4-phenyl-1, 3-dioxolane (the synthesis method is shown in J.Org.Chem.,1978,43(14) and 2773), adding 20ml of polyvinylpyrrolidone and 130ml of methanol/water (the volume ratio is 80/20) while stirring, reacting for 8 hours, naturally cooling, centrifugally separating a product, collecting solids, fully washing and drying the solids by using methanol, and obtaining the polystyrene-ester microspheres;
s2: polystyrene-ester microspheres in CCl4Swelling for 3h, adding 0.2mol of chlorosulfonic acid while stirring, reacting for 1h at 50 ℃, washing with ethanol and water in sequence after the reaction is finished, and drying to obtain the modified polystyrene resin
Example 4: a modified adsorbing material for treating wastewater comprises the same components and using amount as in example 3, and is characterized in that the modified polystyrene resin is
S2 is absent in the preparation process.
Example 5: a modified adsorbing material for treating wastewater comprises the same components and using amount as in example 3, and is characterized in that the modified polystyrene resin is
The preparation process does not add 2-methylene-4-phenyl-1, 3-dioxolane.
Example 6: the components and the using amount of the modified adsorbing material for treating the wastewater are the same as those of example 3, and the difference is that the using amount of the 2-methylene-4-phenyl-1, 3-dioxolane in the preparation of the modified polystyrene resin is 1 mol.
Example 7: the components and the using amount of the modified adsorbing material for treating the wastewater are the same as those of example 3, and the difference is that the using amount of the 2-methylene-4-phenyl-1, 3-dioxolane in the preparation of the modified polystyrene resin is 0.5 mol.
The modified adsorbent materials for treating wastewater of examples 1 to 6 were prepared by the following steps:
1) mixing the biological flora and the flora protective agent, crushing by using a micronizer, uniformly stirring, and storing for 10 days in a sealed and dark manner;
2) crushing the flocculating agent and the inorganic filler by using a micro-pulverizer, and uniformly mixing and stirring;
3) and (3) uniformly mixing and stirring the modified polystyrene resin, the step 1) and the step 2) to obtain the modified adsorbing material for treating the aquaculture wastewater.
The application comprises the following steps: diluting the prepared wastewater adsorbing material with water, and uniformly splashing the wastewater adsorbing material on the surface of a water body to be treated, wherein the water body is sprayed on every 1000m310g of the adsorbent described in examples 1 to 6 was used in aquaculture wastewater, and the treatment was described as application examples 1 to 6.
Detecting COD value and ammonia nitrogen concentration (NH) before and after treatment3-N), Total Phosphorus (TP) and total solids concentration (SS), the removal of each was calculated and reported in table 1.
TABLE 1
| COD value | NH3-N | TP | SS | |
| Application example 1 | 92.5％ | 94.1％ | 94.5％ | 90.2％ |
| Application example 2 | 93.8％ | 95.8％ | 95.1％ | 91.0％ |
| Application example 3 | 95.1％ | 97.2％ | 96.6％ | 91.9％ |
| Application example 4 | 80.1％ | 82.5％ | 82.2％ | 85.3％ |
| Application example 5 | 82.1％ | 81.5％ | 82.0％ | 83.2％ |
| Application example 6 | 88.4％ | 89.3％ | 90.1％ | 88.6％ |
| Application example 7 | 86.9％ | 88.1％ | 88.8％ | 85.3％ |
From the above table, the adsorption material of the present invention has a good treatment effect on aquaculture wastewater, and the treatment effect of application example 4 is poor, because the modified polystyrene resin is not subjected to sulfonation reaction, the resin exhibits strong hydrophobicity, and has poor dispersibility in water, resulting in weak adsorption force; compared with application examples 1-3 and application examples 5-7, the introduction of the ester group can effectively lengthen the distance between the benzene rings on the main chain, reduce steric hindrance, and make more space for combining adsorbates with larger volume, so that the adsorbates are combined more firmly and are not easy to fall off.
The modified polystyrene resins prepared in examples 3 and 5 to 7 were further subjected to degradation test determination, three 10ml portions of wastewater to be treated were taken, 10mg of modified polystyrene resin was added thereto and stirred uniformly, then the mixture was left to stand, ten days later, samples were taken to test the molecular weight of the modified polystyrene resin, and the degradation rates were calculated, the degradation rates of examples 3 and 5 to 7 were 92%, 10%, 80% and 68%, respectively, example 3 was able to degrade into small molecules in water, whereas the molecular weights of the polymers after degradation of examples 6 and 7 were still large, which may cause secondary pollution to water, and example 5 was only a small portion of molecular weight falling off and could not be degraded well.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (9)
1. A modified adsorption material for treating wastewater is characterized by comprising the following components: modified polystyrene resin, biological flora, a flora protective agent, a flocculating agent and inorganic filler; wherein the preparation process of the modified polystyrene resin comprises the following steps:
s1: adding azobisisobutyronitrile, styrene and divinylbenzene into a reaction bottle, uniformly mixing, adding toluene, heating to 45 ℃, adding 2-methylene-4-phenyl-1, 3-dioxolane, adding a dispersing agent and a dispersion medium while stirring, heating for reaction for a period of time, naturally cooling, centrifugally separating a product, collecting solids, fully washing with methanol, and drying to obtain polystyrene-ester microspheres;
s2: polystyrene-ester microspheres in CCl4Swelling for 3h, adding chlorosulfonic acid while stirring, reacting for 0.5-1h at 50-60 ℃, washing with ethanol and water in sequence after the reaction is finished, and drying to obtain the modified polystyrene resin.
2. The modified adsorbent material for treating wastewater according to claim 1, wherein the reaction conditions in S1 are controlled at 65-80 ℃ for 8-9 h.
3. The modified adsorbing material for treating wastewater as claimed in claim 1, wherein the mass ratio of the styrene, the azobisisobutyronitrile, the 2-methylene-4-phenyl-1, 3-dioxolane, the divinylbenzene and the toluene is 1:0.01: 0.5-1.5: 0.1: 0.1.
4. The modified adsorbent material for treating wastewater according to claim 1, wherein the dispersant is polyvinylpyrrolidone or polyvinyl alcohol; the dispersion medium was methanol/water in a volume ratio of 80/20.
5. A modified adsorbent material for the treatment of wastewater as claimed in claim 1, wherein said biological flora is selected from at least two mixed species of bacillus subtilis, nitrobacteria, yeast, bacillus licheniformis or enterococcus faecalis.
6. A modified adsorbent material for the treatment of wastewater as claimed in claim 1, wherein said flora protection agent is selected from the group consisting of vitamin C, vitamin B1, vitamin B2, choline chloride, vitamin E, and thiourea.
7. The modified adsorbent material for treating wastewater of claim 1, wherein the flocculant is selected from the group consisting of polyaluminum oxide, ferric sulfate, polysilicate iron, aluminum chloride, and polyaluminum sulfate.
8. The modified adsorbent material for treating wastewater of claim 1 wherein the inorganic filler is selected from at least three of the group consisting of activated carbon, diatomaceous earth, alunite, dibasic calcium phosphate, sodium sulfite, and magnesium sulfate.
9. The modified adsorbent material for treating wastewater according to claim 1, wherein the components are, by weight: 50-60 parts of modified polystyrene resin, 3-6 parts of biological flora, 0.5-1 part of flora protective agent, 10-15 parts of flocculating agent and 20-30 parts of inorganic filler.
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