CN116854260B - Sustained-release sewage treatment agent and preparation method thereof - Google Patents
Sustained-release sewage treatment agent and preparation method thereof Download PDFInfo
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- CN116854260B CN116854260B CN202310937868.3A CN202310937868A CN116854260B CN 116854260 B CN116854260 B CN 116854260B CN 202310937868 A CN202310937868 A CN 202310937868A CN 116854260 B CN116854260 B CN 116854260B
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- 239000010865 sewage Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000013268 sustained release Methods 0.000 title description 3
- 239000012730 sustained-release form Substances 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000004005 microsphere Substances 0.000 claims abstract description 36
- 239000002562 thickening agent Substances 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 239000008394 flocculating agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 60
- 239000000178 monomer Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- 229920002401 polyacrylamide Polymers 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000159 gelatin Polymers 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004642 Polyimide Substances 0.000 claims description 20
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 229920001721 polyimide Polymers 0.000 claims description 20
- 108010010803 Gelatin Proteins 0.000 claims description 19
- 229920002907 Guar gum Polymers 0.000 claims description 19
- 239000008273 gelatin Substances 0.000 claims description 19
- 235000019322 gelatine Nutrition 0.000 claims description 19
- 235000011852 gelatine desserts Nutrition 0.000 claims description 19
- 235000010417 guar gum Nutrition 0.000 claims description 19
- 239000000665 guar gum Substances 0.000 claims description 19
- 229960002154 guar gum Drugs 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 239000002280 amphoteric surfactant Substances 0.000 claims description 15
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 10
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical group CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 10
- 229920000053 polysorbate 80 Polymers 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 229940057995 liquid paraffin Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000008274 jelly Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical group CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 3
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 23
- 150000002500 ions Chemical class 0.000 abstract description 16
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 28
- 229920001223 polyethylene glycol Polymers 0.000 description 28
- 241000894006 Bacteria Species 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 12
- 230000001546 nitrifying effect Effects 0.000 description 12
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 8
- 239000005543 nano-size silicon particle Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 244000063299 Bacillus subtilis Species 0.000 description 7
- 235000014469 Bacillus subtilis Nutrition 0.000 description 7
- 239000012213 gelatinous substance Substances 0.000 description 6
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical group CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 241000589755 Pseudomonas mendocina Species 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000009519 fu-yuan Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
Abstract
The invention relates to the technical field of sewage treatment, in particular to a slow-release sewage treatment agent and a preparation method thereof, wherein the sewage treatment agent comprises the following raw materials in parts by weight: 40-50 parts of slow release microspheres, 4-6 parts of thickening agent, 8-10 parts of surfactant, 20-30 parts of flocculating agent, 5-10 parts of metal oxide and 3-5 parts of dispersing agent. The sewage treatment agent not only can cooperatively treat high ammonia nitrogen, COD, heavy metal ions and some micromolecular harmful substances in sewage, has excellent sewage purification effect, but also has a good slow release function, and achieves the effect of long-acting utilization.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a slow-release sewage treatment agent and a preparation method thereof.
Background
Along with the vigorous development of economy, the productivity is continuously accelerated, the sewage discharge amount is also rapidly increased, and the sewage can cause secondary pollution to the environment if being improperly treated, thereby further threatening the ecological environment and human health. Ammonia nitrogen and COD in sewage can cause water quality deterioration, so that water body unbalance is caused, the survival of animals and plants in the water body is influenced, meanwhile, heavy metal ions and compounds thereof in the sewage can be enriched in fish and other aquatic organisms, and serious harm is caused to human beings and surrounding ecological environment through the circulation of drinking water and food chains.
At present, the method for sewage treatment mainly comprises a chemical method and a biological method, wherein the chemical method is to add medicines into a water body to achieve the effect of water purification, but due to complex pollutant types of sewage, the existing water treatment agents are difficult to cooperatively treat various pollutants such as ammonia nitrogen, COD and heavy metal ions, and the effect of sewage purification is poor; for biological methods, a certain microbial agent is added into a water body for multiple times to realize the purification effect, but microorganisms directly added into the water body exist in a free mode, so that the microorganisms are seriously lost and cannot be applied in the water body for a long time, and the purification effect on sewage is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a slow-release sewage treatment agent and a preparation method thereof, and the sewage treatment agent not only can remove ammonia nitrogen in sewage, reduce COD content and purify heavy metals, but also has a good slow-release function, can slowly release strains in a water body, and achieves the effect of long-acting utilization.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The invention provides a slow-release sewage treatment agent, which comprises the following raw materials in parts by weight: 40-50 parts of slow release microspheres, 4-6 parts of thickening agent, 8-10 parts of surfactant, 20-30 parts of flocculating agent, 5-10 parts of metal oxide and 3-5 parts of dispersing agent.
In some embodiments, the preparation of the sustained release microsphere comprises the steps of:
(1) Dissolving diamine monomer and grafting monomer in N, N-dimethylformamide to obtain phase A, dispersing nonionic surfactant in liquid paraffin to obtain phase B, mixing the phase A and the phase B under stirring to form a nonaqueous emulsion system, adding dianhydride monomer to react for 4-6 hours to obtain polymer, adding a mixture of acetic anhydride and pyridine to perform chemical imidization to obtain precipitate, washing and drying the precipitate, performing thermal imidization to obtain modified polyimide polymer, and performing heat treatment on the modified polyimide polymer at 190 ℃ for 1 hour to obtain a modified polyimide porous carrier;
(2) Adding the modified polyimide porous carrier prepared in the step (1) into a strain solution, soaking for 2-3h, taking out, and drying to obtain microspheres loaded with strains;
(3) And (3) adding the strain-loaded microspheres obtained in the step (2) into a slow-release film solution, uniformly mixing, and drying to obtain the slow-release microspheres.
The molar ratio of the diamine monomer to the dianhydride monomer is 1:1.07, wherein the diamine monomer is 4,4' -diaminodiphenyl ether, the dianhydride monomer is pyromellitic dianhydride, the addition amount of the grafting monomer is 30wt% of the dianhydride monomer, the nonionic surfactant comprises span 85 and tween 80, and the weight ratio of the span 85 to the tween 80 is 1.8: the addition amount of the mixture of the acetic anhydride and the pyridine is 12% of the volume of the N, N-dimethylformamide, and the volume ratio of the acetic anhydride to the pyridine in the mixture of the acetic anhydride and the pyridine is 2:1.
The grafting monomer is obtained by the following steps: polyethylene glycol, 3, 5-diaminobenzoic acid, a catalyst and an entrainer are added into a reactor to react under a protective atmosphere, and crude products are obtained and then extracted and distilled under reduced pressure to obtain grafted monomers.
The molar ratio of the polyethylene glycol to the 3, 5-diaminobenzoic acid is 1:1.32, the average molecular weight of the polyethylene glycol is 600, the catalyst is p-toluenesulfonic acid, the dosage of the catalyst is 4.8wt% of the polyethylene glycol, the entrainer is toluene, and the addition of the entrainer is 125 wt% of the polyethylene glycol.
The source of the polyethylene glycol is not particularly limited and can be purchased commercially, including but not limited to, polyethylene glycol from Shanghai, chemical technology, inc.
The strain solution comprises the mixture of nitrifying bacteria, denitrifying bacteria and bacillus subtilis, and the ratio of the viable bacteria to the bacterial strain is 1:1:1.25, wherein the nitrifying bacteria are nitrifying bacteria, the denitrifying bacteria are Pseudomonas mendocina, and the living bacterial amount of the strain solution is 10 10 CFU/g.
The slow-release film solution comprises the following components in percentage by mass: 8% of sodium alginate, 8% of gelatin, 5% of polyvinyl alcohol, 1.1% of methyl-pentapolyethylene glycol-succinimidyl acrylate, 1% of dihydroxypropyl PABA ethyl ester and the balance of water.
The slow release film solution is prepared by the following steps: mixing sodium alginate and water, dissolving in water bath at 50deg.C, adding gelatin, heating to 85deg.C to dissolve, adding polyvinyl alcohol under stirring to dissolve, adding methyl-pentapolyethylene glycol-succinimidyl acrylate and dihydroxypropyl PABA ethyl ester, and mixing uniformly to obtain the slow-release membrane solution.
The CAS number of methyl-pentapolyethylene glycol-succinimidyl acrylate is 1449390-12-8, the CAS number of dihydroxypropyl PABA ethyl ester is 58882-17-0, the polymerization degree of polyvinyl alcohol is 1799, the alcoholysis degree is 98-98%, and the average molecular weight is 44.05.
The source of the polyvinyl alcohol is not particularly limited and can be purchased commercially, including but not limited to, polyvinyl alcohol from Shanghai Hengfi Biotechnology Co., ltd, and the gelatin is industrial gelatin, including but not limited to, commercial gelatin from Shanghai county Fuyuan gelatin Co., ltd.
In order to reduce ammonia nitrogen and COD content in sewage, researchers in the field at present mainly add microbial agents into water, but the method can lead microorganisms to exist in a free form, so that the microorganisms are seriously lost and cannot be applied in the water for a long time, and thus the purification effect on sewage is limited.
In some embodiments, the thickener comprises at least one of xanthan gum, guar gum, gelatin, polyacrylamide.
Preferably, the thickener is a mixture of guar gum and polyacrylamide in a weight ratio of (0.3-0.7): 1, preferably 0.5:1.
The source of the guar is not particularly limited and may be purchased commercially, including but not limited to, guar from the chemical industry company of the river sea, any hilly city.
In some embodiments, the polyacrylamide is an anionic polyacrylamide.
Preferably, the molecular weight of the anionic polyacrylamide is 1500-3000.
The source of the anionic polyacrylamide is not particularly limited and can be purchased commercially, including but not limited to anionic polyacrylamide available from Henan Yanglin environmental protection technology Co., ltd, model DEFS and molecular weight 2000.
In some embodiments, the surfactant comprises an amphoteric surfactant and an anionic surfactant in a weight ratio of 1 (1-1.5).
In some embodiments, the amphoteric surfactant is cocamidopropyl betaine and the anionic surfactant is sodium dodecyl sulfate.
The cocoamidopropyl betaine has a CAS number of 61789-40-0 and sodium dodecyl sulfate has a CAS number of 151-21-3.
In some embodiments, the flocculant comprises at least one of aluminum sulfate, aluminum chloride, and polyaluminum chloride.
Preferably, the flocculant is a combination of aluminum sulfate and polyaluminum chloride in a weight ratio of (0.5-1): 1.
The slow release microsphere of the application has better effect on reducing ammonia nitrogen concentration and COD content, but has no obvious effect on the treatment of heavy metal ions, and the applicant finds that after a great deal of researches, the slow release microsphere is combined with a certain amount of specific surfactant, thickener and flocculant to prepare a water treatment agent, especially the surfactant is cocamidopropyl betaine and sodium dodecyl sulfate with the weight ratio of 1 (1-1.5), the thickener is a mixture of guar gum and polyacrylamide with the weight ratio of 0.3-0.7) 1, the synergistic treatment can be carried out on high ammonia nitrogen, COD, heavy metal ions and some small molecular harmful substances in the sewage, the excellent sewage purifying effect is realized, and the applicant considers that the possible reasons are that firstly guar gum and anionic polyacrylamide with a specific proportion can form flocculation glue, meanwhile, the amphoteric surfactant cocamidopropyl betaine is adsorbed on a molecular chain through self charge static electricity, and the anionic surfactant sodium dodecyl sulfate can promote the formation of the flocculation glue of guar gum, secondly the polyacrylamide and the oleamide can be associated with the oleamide propyl guar gum to form a three-dimensional structure, and the three-dimensional suspended particles can be combined with the alumina chloride to form a three-dimensional suspended particle with high-dimensional absorption effect, and the three-dimensional suspended particle can be reduced, the three-dimensional suspended particle can be combined with the space of the ammonia nitrogen can be formed, and the three-dimensional suspended particle can have high absorption effect can be formed, and the bridging effect ensures that suspended particles are connected and are easy to settle, thereby enhancing the sewage purification effect.
In some embodiments, the metal oxide comprises at least one of silica, titania, zinc oxide, antimony dioxide.
Preferably, the metal oxide is nano silicon dioxide, and the average particle size of the nano silicon dioxide is 15-30nm.
More preferably, the nanosilica has an average particle size of 20nm.
The source of the nano-silica is not particularly limited and can be purchased commercially, including but not limited to the nano-silica available from Yu mu (Ningbo) New Material Co., ltd., model YM-SiO2-20.
In some embodiments, the dispersant is methylpentanol or fatty alcohol polyoxyethylene ether.
Preferably, the dispersant is methylpentanol.
The second aspect of the invention provides a preparation method of a slow-release sewage treatment agent, which comprises the following steps: mixing a surfactant and a flocculating agent at 50-60 ℃, sequentially adding a metal oxide, a dispersing agent and a thickening agent under the stirring condition, cooling to below 30 ℃, adding slow-release microspheres, continuously stirring to obtain a semi-jelly, and drying and crushing the semi-jelly to obtain the slow-release sewage treatment agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the slow-release microsphere is prepared by adopting a special porous carrier to load the strain and then coating a layer of degradable slow-release film, and the pore structure of the porous carrier and the pores formed by the degradation of the slow-release film component in water are matched with each other so that the strain in the microsphere is slowly released, thus the long-acting purification effect on sewage is realized;
(2) The invention prepares the water treatment agent by combining and adding specific surfactants, thickening agents and flocculating agents into the slow-release microspheres, particularly the cocoamidopropyl betaine and sodium dodecyl sulfate with the weight ratio of 1 (1-1.5) and the mixture of guar gum and polyacrylamide with the weight ratio of 1 (0.3-0.7) are adopted as the surfactants, so that the synergistic treatment can be carried out on high ammonia nitrogen, COD, heavy metal ions and some small-molecular harmful substances in sewage, and the sewage purification effect is excellent.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The slow-release sewage treatment agent comprises the following raw materials in parts by weight: 45 parts of slow release microspheres, 5 parts of thickener, 9 parts of surfactant, 25 parts of flocculant, 7 parts of metal oxide and 4 parts of dispersing agent.
The preparation of the slow release microsphere comprises the following steps:
(1) Dissolving diamine monomer and grafting monomer in N, N-dimethylformamide to obtain phase A, dispersing nonionic surfactant in liquid paraffin to obtain phase B, mixing the phase A and the phase B under stirring to form a nonaqueous emulsion system, adding dianhydride monomer to react for 4-6 hours to obtain polymer, adding a mixture of acetic anhydride and pyridine to perform chemical imidization to obtain precipitate, washing and drying the precipitate, performing thermal imidization to obtain modified polyimide polymer, and performing heat treatment on the modified polyimide polymer at 190 ℃ for 1 hour to obtain a modified polyimide porous carrier;
(2) Adding the modified polyimide porous carrier prepared in the step (1) into a strain solution, soaking for 2-3h, taking out, and drying to obtain microspheres loaded with strains;
(3) And (3) adding the strain-loaded microspheres obtained in the step (2) into a slow-release film solution, uniformly mixing, and drying to obtain the slow-release microspheres.
The molar ratio of diamine monomer to dianhydride monomer is 1:1.07, wherein the diamine monomer is 4,4' -diaminodiphenyl ether, the dianhydride monomer is pyromellitic dianhydride, the addition amount of the grafting monomer is 30wt% of the dianhydride monomer, the nonionic surfactant comprises span 85 and tween 80, and the weight ratio of the span 85 to the tween 80 is 1.8:1, the addition amount of the mixture of the acetic anhydride and the pyridine is 12 percent of the volume of the N, N-dimethylformamide, and the volume ratio of the acetic anhydride to the pyridine in the mixture of the acetic anhydride and the pyridine is 2:1.
The grafting monomer is obtained by the following steps: polyethylene glycol, 3, 5-diaminobenzoic acid, a catalyst and an entrainer are added into a reactor to react under a protective atmosphere, and crude products are obtained and then extracted and distilled under reduced pressure to obtain grafted monomers.
The molar ratio of polyethylene glycol to 3, 5-diaminobenzoic acid is 1:1.32, the average molecular weight of the polyethylene glycol is 600, the catalyst is p-toluenesulfonic acid, the dosage of the catalyst is 4.8wt% of the polyethylene glycol, the entrainer is toluene, and the addition of the entrainer is 125 wt% of the polyethylene glycol.
The source of the polyethylene glycol is not particularly limited and can be purchased commercially, including but not limited to, polyethylene glycol from Shanghai, chemical technology, inc.
The strain solution comprises the mixture of nitrifying bacteria, denitrifying bacteria and bacillus subtilis, and the ratio of the viable bacteria to the bacillus subtilis is 1:1:1.25, nitrifying bacteria are nitrifying bacteria, denitrifying bacteria are Pseudomonas mendocina, and the living bacterial amount of the bacterial strain solution is 10 10 CFU/g.
The slow-release film solution comprises the following components in percentage by mass: 8% of sodium alginate, 8% of gelatin, 5% of polyvinyl alcohol, 1.1% of methyl-pentapolyethylene glycol-succinimidyl acrylate, 1% of dihydroxypropyl PABA ethyl ester and the balance of water.
The slow release film solution is obtained by the following steps: mixing sodium alginate and water, dissolving in water bath at 50deg.C, adding gelatin, heating to 85deg.C to dissolve, adding polyvinyl alcohol under stirring to dissolve, adding methyl-pentapolyethylene glycol-succinimidyl acrylate and dihydroxypropyl PABA ethyl ester, and mixing uniformly to obtain the slow-release membrane solution.
The CAS number of methyl-pentapolyethylene glycol-succinimidyl acrylate is 1449390-12-8, the CAS number of dihydroxypropyl PABA ethyl ester is 58882-17-0, the polymerization degree of polyvinyl alcohol is 1799, the alcoholysis degree is 98-98%, and the average molecular weight is 44.05.
Polyvinyl alcohol was purchased from Shanghai Heng Fizea Biotech Co., ltd. Gelatin was an industrial gelatin, and was purchased from Shangshui county Fuyuan gelatin Co., ltd.
The thickener is a mixture of guar gum and polyacrylamide, and the weight ratio of the guar gum to the polyacrylamide is 0.5:1.
Guar gum is purchased from Jianghai chemical industry Co., ltd, and polyacrylamide is anionic polyacrylamide, and is purchased from Henan Yanglin environmental protection technology Co., ltd, and the model is DEFS, and the molecular weight is 2000.
The surfactant comprises an amphoteric surfactant and an anionic surfactant, and the weight ratio of the amphoteric surfactant to the anionic surfactant is 1:1.25, wherein the amphoteric surfactant is cocamidopropyl betaine, and the anionic surfactant is sodium dodecyl sulfate.
The flocculant is a combination of aluminum sulfate and polyaluminum chloride, and the weight ratio of the aluminum sulfate to the polyaluminum chloride is 0.75:1.
The metal oxide is nano silicon dioxide with the average grain diameter of 20nm, and the nano silicon dioxide is purchased from Yumu (Ningbo) new material Co., ltd, and the model is YM-SiO2-20.
The dispersing agent is methyl amyl alcohol.
The preparation method of the slow-release sewage treatment agent comprises the following steps: mixing a surfactant and a flocculating agent at 55 ℃, sequentially adding a metal oxide, a dispersing agent and a thickening agent under the stirring condition, cooling to below 30 ℃, adding slow-release microspheres, continuously stirring to obtain a semi-gelatinous substance, and drying and crushing the semi-gelatinous substance to obtain the slow-release sewage treatment agent.
Example 2
The slow-release sewage treatment agent comprises the following raw materials in parts by weight: 40 parts of slow release microspheres, 4 parts of thickener, 8 parts of surfactant, 20 parts of flocculant, 5 parts of metal oxide and 3 parts of dispersing agent.
The preparation of the slow release microsphere comprises the following steps:
(1) Dissolving diamine monomer and grafting monomer in N, N-dimethylformamide to obtain phase A, dispersing nonionic surfactant in liquid paraffin to obtain phase B, mixing the phase A and the phase B under stirring to form a nonaqueous emulsion system, adding dianhydride monomer to react for 4-6 hours to obtain polymer, adding a mixture of acetic anhydride and pyridine to perform chemical imidization to obtain precipitate, washing and drying the precipitate, performing thermal imidization to obtain modified polyimide polymer, and performing heat treatment on the modified polyimide polymer at 190 ℃ for 1 hour to obtain a modified polyimide porous carrier;
(2) Adding the modified polyimide porous carrier prepared in the step (1) into a strain solution, soaking for 2-3h, taking out, and drying to obtain microspheres loaded with strains;
(3) And (3) adding the strain-loaded microspheres obtained in the step (2) into a slow-release film solution, uniformly mixing, and drying to obtain the slow-release microspheres.
The molar ratio of diamine monomer to dianhydride monomer is 1:1.07, wherein the diamine monomer is 4,4' -diaminodiphenyl ether, the dianhydride monomer is pyromellitic dianhydride, the addition amount of the grafting monomer is 30wt% of the dianhydride monomer, the nonionic surfactant comprises span 85 and tween 80, and the weight ratio of the span 85 to the tween 80 is 1.8:1, the addition amount of the mixture of the acetic anhydride and the pyridine is 12 percent of the volume of the N, N-dimethylformamide, and the volume ratio of the acetic anhydride to the pyridine in the mixture of the acetic anhydride and the pyridine is 2:1.
The grafting monomer is obtained by the following steps: polyethylene glycol, 3, 5-diaminobenzoic acid, a catalyst and an entrainer are added into a reactor to react under a protective atmosphere, and crude products are obtained and then extracted and distilled under reduced pressure to obtain grafted monomers.
The molar ratio of polyethylene glycol to 3, 5-diaminobenzoic acid is 1:1.32, the average molecular weight of the polyethylene glycol is 600, the catalyst is p-toluenesulfonic acid, the dosage of the catalyst is 4.8wt% of the polyethylene glycol, the entrainer is toluene, and the addition of the entrainer is 125 wt% of the polyethylene glycol.
The source of the polyethylene glycol is not particularly limited and can be purchased commercially, including but not limited to, polyethylene glycol from Shanghai, chemical technology, inc.
The strain solution comprises the mixture of nitrifying bacteria, denitrifying bacteria and bacillus subtilis, and the ratio of the viable bacteria to the bacillus subtilis is 1:1:1.25, nitrifying bacteria are nitrifying bacteria, denitrifying bacteria are Pseudomonas mendocina, and the living bacterial amount of the bacterial strain solution is 10 10 CFU/g.
The slow-release film solution comprises the following components in percentage by mass: 8% of sodium alginate, 8% of gelatin, 5% of polyvinyl alcohol, 1.1% of methyl-pentapolyethylene glycol-succinimidyl acrylate, 1% of dihydroxypropyl PABA ethyl ester and the balance of water.
The slow release film solution is obtained by the following steps: mixing sodium alginate and water, dissolving in water bath at 50deg.C, adding gelatin, heating to 85deg.C to dissolve, adding polyvinyl alcohol under stirring to dissolve, adding methyl-pentapolyethylene glycol-succinimidyl acrylate and dihydroxypropyl PABA ethyl ester, and mixing uniformly to obtain the slow-release membrane solution.
The CAS number of methyl-pentapolyethylene glycol-succinimidyl acrylate is 1449390-12-8, the CAS number of dihydroxypropyl PABA ethyl ester is 58882-17-0, the polymerization degree of polyvinyl alcohol is 1799, the alcoholysis degree is 98-98%, and the average molecular weight is 44.05.
Polyvinyl alcohol was purchased from Shanghai Heng Fizea Biotech Co., ltd. Gelatin was an industrial gelatin, and was purchased from Shangshui county Fuyuan gelatin Co., ltd.
The thickener is a mixture of guar gum and polyacrylamide, and the weight ratio of the guar gum to the polyacrylamide is 0.3:1.
Guar gum is purchased from Jianghai chemical industry Co., ltd, and polyacrylamide is anionic polyacrylamide, and is purchased from Henan Yanglin environmental protection technology Co., ltd, and the model is DEFS, and the molecular weight is 2000.
The surfactant comprises an amphoteric surfactant and an anionic surfactant, and the weight ratio of the amphoteric surfactant to the anionic surfactant is 1:1, wherein the amphoteric surfactant is cocamidopropyl betaine, and the anionic surfactant is sodium dodecyl sulfate.
The flocculant is a combination of aluminum sulfate and polyaluminum chloride, and the weight ratio of the aluminum sulfate to the polyaluminum chloride is 0.5:1.
The metal oxide is nano silicon dioxide with the average grain diameter of 20nm, and the nano silicon dioxide is purchased from Yumu (Ningbo) new material Co., ltd, and the model is YM-SiO2-20.
The dispersing agent is methyl amyl alcohol.
The preparation method of the slow-release sewage treatment agent comprises the following steps: mixing a surfactant and a flocculating agent at 55 ℃, sequentially adding a metal oxide, a dispersing agent and a thickening agent under the stirring condition, cooling to below 30 ℃, adding slow-release microspheres, continuously stirring to obtain a semi-gelatinous substance, and drying and crushing the semi-gelatinous substance to obtain the slow-release sewage treatment agent.
Example 3
The slow-release sewage treatment agent comprises the following raw materials in parts by weight: 50 parts of slow release microspheres, 6 parts of thickener, 10 parts of surfactant, 30 parts of flocculant, 10 parts of metal oxide and 5 parts of dispersing agent.
The preparation of the slow release microsphere comprises the following steps:
(1) Dissolving diamine monomer and grafting monomer in N, N-dimethylformamide to obtain phase A, dispersing nonionic surfactant in liquid paraffin to obtain phase B, mixing the phase A and the phase B under stirring to form a nonaqueous emulsion system, adding dianhydride monomer to react for 4-6 hours to obtain polymer, adding a mixture of acetic anhydride and pyridine to perform chemical imidization to obtain precipitate, washing and drying the precipitate, performing thermal imidization to obtain modified polyimide polymer, and performing heat treatment on the modified polyimide polymer at 190 ℃ for 1 hour to obtain a modified polyimide porous carrier;
(2) Adding the modified polyimide porous carrier prepared in the step (1) into a strain solution, soaking for 2-3h, taking out, and drying to obtain microspheres loaded with strains;
(3) And (3) adding the strain-loaded microspheres obtained in the step (2) into a slow-release film solution, uniformly mixing, and drying to obtain the slow-release microspheres.
The molar ratio of diamine monomer to dianhydride monomer is 1:1.07, wherein the diamine monomer is 4,4' -diaminodiphenyl ether, the dianhydride monomer is pyromellitic dianhydride, the addition amount of the grafting monomer is 30wt% of the dianhydride monomer, the nonionic surfactant comprises span 85 and tween 80, and the weight ratio of the span 85 to the tween 80 is 1.8:1, the addition amount of the mixture of the acetic anhydride and the pyridine is 12 percent of the volume of the N, N-dimethylformamide, and the volume ratio of the acetic anhydride to the pyridine in the mixture of the acetic anhydride and the pyridine is 2:1.
The grafting monomer is obtained by the following steps: polyethylene glycol, 3, 5-diaminobenzoic acid, a catalyst and an entrainer are added into a reactor to react under a protective atmosphere, and crude products are obtained and then extracted and distilled under reduced pressure to obtain grafted monomers.
The molar ratio of polyethylene glycol to 3, 5-diaminobenzoic acid is 1:1.32, the average molecular weight of the polyethylene glycol is 600, the catalyst is p-toluenesulfonic acid, the dosage of the catalyst is 4.8wt% of the polyethylene glycol, the entrainer is toluene, and the addition of the entrainer is 125 wt% of the polyethylene glycol.
The source of the polyethylene glycol is not particularly limited and can be purchased commercially, including but not limited to, polyethylene glycol from Shanghai, chemical technology, inc.
The strain solution comprises the mixture of nitrifying bacteria, denitrifying bacteria and bacillus subtilis, and the ratio of the viable bacteria to the bacillus subtilis is 1:1:1.25, nitrifying bacteria are nitrifying bacteria, denitrifying bacteria are Pseudomonas mendocina, and the living bacterial amount of the bacterial strain solution is 10 10 CFU/g.
The slow-release film solution comprises the following components in percentage by mass: 8% of sodium alginate, 8% of gelatin, 5% of polyvinyl alcohol, 1.1% of methyl-pentapolyethylene glycol-succinimidyl acrylate, 1% of dihydroxypropyl PABA ethyl ester and the balance of water.
The slow release film solution is obtained by the following steps: mixing sodium alginate and water, dissolving in water bath at 50deg.C, adding gelatin, heating to 85deg.C to dissolve, adding polyvinyl alcohol under stirring to dissolve, adding methyl-pentapolyethylene glycol-succinimidyl acrylate and dihydroxypropyl PABA ethyl ester, and mixing uniformly to obtain the slow-release membrane solution.
The CAS number of methyl-pentapolyethylene glycol-succinimidyl acrylate is 1449390-12-8, the CAS number of dihydroxypropyl PABA ethyl ester is 58882-17-0, the polymerization degree of polyvinyl alcohol is 1799, the alcoholysis degree is 98-98%, and the average molecular weight is 44.05.
Polyvinyl alcohol was purchased from Shanghai Heng Fizea Biotech Co., ltd. Gelatin was an industrial gelatin, and was purchased from Shangshui county Fuyuan gelatin Co., ltd.
The thickener is a mixture of guar gum and polyacrylamide, and the weight ratio of the guar gum to the polyacrylamide is 0.3:1.
Guar gum is purchased from Jianghai chemical industry Co., ltd, and polyacrylamide is anionic polyacrylamide, and is purchased from Henan Yanglin environmental protection technology Co., ltd, and the model is DEFS, and the molecular weight is 2000.
The surfactant comprises an amphoteric surfactant and an anionic surfactant, and the weight ratio of the amphoteric surfactant to the anionic surfactant is 1:1, wherein the amphoteric surfactant is cocamidopropyl betaine, and the anionic surfactant is sodium dodecyl sulfate.
The flocculant is a combination of aluminum sulfate and polyaluminum chloride, and the weight ratio of the aluminum sulfate to the polyaluminum chloride is 0.5:1.
The metal oxide is nano silicon dioxide with the average grain diameter of 20nm, and the nano silicon dioxide is purchased from Yumu (Ningbo) new material Co., ltd, and the model is YM-SiO2-20.
The dispersing agent is methyl amyl alcohol.
The preparation method of the slow-release sewage treatment agent comprises the following steps: mixing a surfactant and a flocculating agent at 55 ℃, sequentially adding a metal oxide, a dispersing agent and a thickening agent under the stirring condition, cooling to below 30 ℃, adding slow-release microspheres, continuously stirring to obtain a semi-gelatinous substance, and drying and crushing the semi-gelatinous substance to obtain the slow-release sewage treatment agent.
Example 4
The embodiment provides a slow-release sewage treatment agent and a preparation method thereof, and the specific implementation mode is the same as the embodiment 1, except that guar gum is not included in the thickener.
Example 5
The present example provides a slow-release sewage treatment agent and a preparation method thereof, and a specific embodiment is the same as example 1, except that the thickener does not include anionic polyacrylamide.
Example 6
The present example provides a slow-release sewage treatment agent and a preparation method thereof, and a specific embodiment is the same as example 1, except that the surfactant does not include sodium dodecyl sulfate.
Evaluation of Performance
1. Sewage purification effect
The initial concentration of ammonia nitrogen in wastewater of a certain factory is 300mg/L, the initial concentration of COD is 1000mg/L, and the concentration of heavy metal ions is respectively as follows: cu 2+30mg/L,Cr6+85mg/L,Zn2+40mg/L,Ni2+ mg/L, adjusting the pH of the wastewater to be neutral, and then taking 6 parts of the wastewater with the same amount, and respectively adding the water treatment agents of examples 1-6 with the addition amount of 20g/L.
Sampling and measuring ammonia nitrogen concentration and COD concentration after 24h and 3 days, respectively measuring the concentration of each heavy metal ion after 24h by an atomic absorption spectrophotometer, and calculating the ion adsorption rate, wherein the ion adsorption rate has the following calculation formula: ion adsorption ratio (%) = (initial ion concentration-ion concentration after treatment)/initial ion concentration×100%.
The test results are shown in Table 1.
TABLE 1
As can be seen from the data in table 1, the water treatment agents of examples 1 to 3 are excellent in reducing ammonia nitrogen and COD concentration and heavy metal ion adsorption effect, and according to the data, the reduction of ammonia nitrogen concentration and COD concentration is more obvious with the extension of treatment time, and the water treatment agent is proved to have better slow release performance; in examples 4 and 5, the removal effect on ammonia nitrogen and COD is slightly poor due to the change of the components of the thickener, and the adsorption effect on various heavy metal ions is obviously deteriorated to different degrees; example 6 has a slightly inferior ammonia nitrogen and COD removal effect due to the change of the components of the surfactant, and also has a remarkably inferior adsorption effect on various heavy metal ions.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (5)
1. The slow-release sewage treatment agent is characterized by comprising the following raw materials in parts by weight: 40-50 parts of slow release microspheres, 4-6 parts of thickening agent, 8-10 parts of surfactant, 20-30 parts of flocculating agent, 5-10 parts of metal oxide and 3-5 parts of dispersing agent;
the preparation of the slow release microsphere comprises the following steps:
(1) Dissolving diamine monomer and grafting monomer in N, N-dimethylformamide to obtain a phase A, dispersing nonionic surfactant in liquid paraffin to obtain a phase B, mixing the phase A and the phase B under stirring to form a nonaqueous emulsion system, adding dianhydride monomer to react for 4-6 hours to obtain a polymer, adding a mixture of acetic anhydride and pyridine to perform chemical imidization to obtain a precipitate, washing and drying the precipitate, performing thermal imidization to obtain a modified polyimide polymer, and performing heat treatment on the modified polyimide polymer to obtain a modified polyimide porous carrier;
(2) Adding the modified polyimide porous carrier prepared in the step (1) into a strain solution, soaking for 2-3h, taking out, and drying to obtain microspheres loaded with strains;
(3) Adding the strain-loaded microspheres obtained in the step (2) into a slow-release film solution, uniformly mixing, and drying to obtain slow-release microspheres;
The molar ratio of the diamine monomer to the dianhydride monomer is 1:1.07, wherein the diamine monomer is 4,4' -diaminodiphenyl ether, the dianhydride monomer is pyromellitic dianhydride, the addition amount of the grafting monomer is 30wt% of the dianhydride monomer, the nonionic surfactant comprises span 85 and tween 80, and the weight ratio of the span 85 to the tween 80 is 1.8:1, the addition amount of the mixture of acetic anhydride and pyridine is 12% of the volume of N, N-dimethylformamide, and the volume ratio of the acetic anhydride to the pyridine in the mixture of the acetic anhydride and the pyridine is 2:1;
the slow-release film solution comprises the following components in percentage by mass: 8% of sodium alginate, 8% of gelatin, 5% of polyvinyl alcohol, 1.1% of methyl-pentapolyethylene glycol-succinimidyl acrylate, 1% of dihydroxypropyl PABA ethyl ester and the balance of water;
The thickener is a mixture of guar gum and polyacrylamide, and the weight ratio of the guar gum to the polyacrylamide is (0.3-0.7) 1;
The surfactant comprises an amphoteric surfactant and an anionic surfactant, and the weight ratio of the amphoteric surfactant to the anionic surfactant is 1 (1-1.5);
the amphoteric surfactant is cocamidopropyl betaine, and the anionic surfactant is sodium dodecyl sulfate;
the flocculant comprises at least one of aluminum sulfate, aluminum chloride and polyaluminum chloride.
2. The slow-release sewage treatment agent according to claim 1, wherein the polyacrylamide is anionic polyacrylamide.
3. The slow release type sewage treatment agent according to claim 1, wherein the metal oxide comprises at least one of silica, titanium dioxide, zinc oxide and antimony dioxide.
4. The slow-release sewage treatment agent according to claim 1, wherein the dispersing agent is methylpentanol or fatty alcohol polyoxyethylene ether.
5. A method for preparing the slow-release sewage treatment agent according to any one of claims 1 to 4, comprising the steps of: mixing a surfactant and a flocculating agent at 50-60 ℃, sequentially adding a metal oxide, a dispersing agent and a thickening agent under the stirring condition, cooling to below 30 ℃, adding slow-release microspheres, continuously stirring to obtain a semi-jelly, and drying and crushing the semi-jelly to obtain the slow-release sewage treatment agent.
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