CN116813079A - Biological composite filler for generating polysulfide to realize deep denitrification and preparation method thereof - Google Patents
Biological composite filler for generating polysulfide to realize deep denitrification and preparation method thereof Download PDFInfo
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- CN116813079A CN116813079A CN202310792714.XA CN202310792714A CN116813079A CN 116813079 A CN116813079 A CN 116813079A CN 202310792714 A CN202310792714 A CN 202310792714A CN 116813079 A CN116813079 A CN 116813079A
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- sulfur
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- polysulfide
- composite filler
- biological composite
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- 239000000945 filler Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 27
- 150000008117 polysulfides Polymers 0.000 title claims abstract description 27
- 239000005077 polysulfide Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 63
- 239000011593 sulfur Substances 0.000 claims abstract description 63
- 241000894006 Bacteria Species 0.000 claims abstract description 19
- 235000018417 cysteine Nutrition 0.000 claims abstract description 17
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 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 19
- 235000010413 sodium alginate Nutrition 0.000 claims description 19
- 239000000661 sodium alginate Substances 0.000 claims description 19
- 229940005550 sodium alginate Drugs 0.000 claims description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000007909 melt granulation Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 230000001651 autotrophic effect Effects 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 11
- 239000010865 sewage Substances 0.000 abstract description 9
- 244000005700 microbiome Species 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 abstract description 2
- 230000001404 mediated effect Effects 0.000 abstract description 2
- 150000008116 organic polysulfides Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011573 trace mineral Substances 0.000 description 6
- 235000013619 trace mineral Nutrition 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000035755 proliferation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 229920006248 expandable polystyrene Polymers 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IOKBJSAKTZEMBR-UHFFFAOYSA-N 2-chloro-4-fluoro-3-methylbenzonitrile Chemical compound CC1=C(F)C=CC(C#N)=C1Cl IOKBJSAKTZEMBR-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 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
- C02F3/28—Anaerobic digestion processes
-
- 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
-
- 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 discloses a preparation method of biological composite filler for generating polysulfide to realize deep denitrification, which belongs to the technical field of sewage biological treatment. The absorption and utilization of sulfur autotrophic bacteria to elemental sulfur are mediated by extracellular substances, under the condition of elemental sulfur, the substances containing sulfhydryl structures are highly expressed and differentially expressed, and activate the elemental sulfur, so that sulfur is biologically modified to generate polysulfide which is used as a soluble intermediate for bacterial utilization. The biological composite filler prepared by the invention has the advantages that the formation of organic polysulfide is promoted by adding a small amount of cysteine, the solubility of sulfur in sewage is improved, the formation of sulfur source and EPS absorbed by sulfur oxidizing bacteria is facilitated, the domestication time of microorganisms is shortened, and the denitrification capability is improved.
Description
Technical Field
The invention belongs to the field of sewage denitrification treatment, and particularly relates to a biological composite filler for generating polysulfide to realize deep denitrification and a preparation method thereof.
Background
Elemental sulfur is often used in the field of sewage treatment due to its low cost, availability, non-toxicity and innocuity. Deep denitrification of nutrient-deficient nitrogen-containing sewage such as drinking water, groundwater, secondary effluent from municipal sewage plants, and the like by using elemental sulfur as an inorganic electron donor is a hot spot of research in recent years. Compared with the heterotrophic denitrification process using an organic carbon source as an electron donor, the elemental sulfur autotrophic denitrification process (Sulfur Autotrophic Denitrification, SADN) has the advantages of low sludge yield and low running cost. But the low solubility of elemental sulfur results in poor bioavailability thereof, thus limiting the rate of SADN and affecting the wide range of applications of the process.
At present, many researches are devoted to exploring how to improve electron slave S 0 Transfer rate to sulfur oxide denitrifying bacteria for nitrate reduction to increase SADN rate, polysulfide (S n 2- ) Is produced by chemical reaction of elemental sulfur and sulfide under neutral to alkaline condition (formula 1), and is used as a transfer carrier of soluble zero-valent sulfur in water, its bioavailability is far higher than that of S 0 ；S n 2- Once generated, the catalyst can be rapidly utilized by sulfur oxidation denitrifying bacteria to realize rapid reduction of nitrate (formula 2), thus S n 2- Can be used as sulfur oxidation denitrifying bacteria and S 0 And the electron transfer rate between the two is accelerated by the electron conduction medium.
However, polysulfide chemical valenceThe dosage is very expensive and difficult to preserve for a long time, and is not suitable for direct addition in the sewage treatment process. S is promoted by using sulfide (such as sodium sulfide, sodium hydrosulfide, etc.) as precursor n 2- Naturally occurring, but sulfide is a safety risk for transportation, use and storage.
Organic carbon source is added into a sulfur autotrophic reactor, and the conversion of elemental sulfur or sulfate into S can be realized through heterotrophic sulfur reducing bacteria n 2- Is to increase the denitrification rate. However, this approach has the difficulty that the amount of organic carbon is difficult to control accurately, and excessive amount can lead to the proliferation of heterotrophic bacteria in large quantity, occupy the ecological niche of sulfur autotrophic bacteria, and destroy the balance of the reactor; in the process of sulfur autotrophic bacteria proliferation, more or less organic matters are generated, and a small amount of non-corresponding organic matters cannot promote the reactor, but can cause higher COD of effluent. In the prior researches and practices, trace COD is always detected in the effluent of all sulfur autotrophic reaction tanks without an additional organic carbon source, which is generally considered to be an endogenous organic substance generated when sulfur autotrophic bacteria proliferate cells, and the additional high-quality organic carbon sources such as sodium acetate, ethanol and the like are mainly absorbed and utilized by heterotrophic bacteria to perform heterotrophic denitrification or heterotrophic sulfur reduction activities, so that only few sulfur autotrophic bacteria can absorb and utilize the organic carbon sources.
Disclosure of Invention
The invention provides a biological composite filler for generating polysulfide to realize deep denitrification and a preparation method thereof, and the prepared biological composite filler can shorten the domestication time of a sulfur autotrophic reactor, improve the bioavailability of sulfur simple substances and realize efficient and deep denitrification.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the biological composite filler for generating polysulfide to realize deep denitrification comprises the following steps:
s1: mixing polyvinyl acetate with glycerol to obtain a mixture A;
s2: mixing and stirring sulfur and calcium carbonate, adding the mixture into the mixture A after uniformly mixing, and carrying out first mixing to obtain a mixture B;
s3: mixing cysteine, microelements and sodium alginate water solution for the second time, and dissolving to obtain a mixture C;
s4: and (3) adding the mixture B and the mixture C obtained in the step (S2) and sodium dodecyl benzene sulfonate into a container for third mixing, adding a foaming agent, fully stirring and uniformly mixing to obtain a mixture, and carrying out heating melting, feeding, injection molding and granulating to obtain the required filler.
In the above steps, the mass ratio of the polyvinyl acetate to the glycerol in the step S1 is (15 to 20): (30-35);
s2, stirring the sulfur and the calcium carbonate until the gray yellow color is uniform, wherein the sulfur and the calcium carbonate are powdery; the mass ratio of the sulfur to the calcium carbonate is (20-40): (15-20); the mass ratio of the sulfur to the mixture A is (20-40): (3-6);
the mass ratio of the sulfur to the cysteine is (20-40): (0.5-2); the mass fraction of the sodium alginate aqueous solution is 2-5wt%; the mass ratio of the sulfur to the sodium alginate solution is (20-40): (1-3); the composition of the trace elements (g L-1 based on sodium alginate solution): disodium ethylenediamine tetraacetate (EDTA-Na) 5, ferrous sulfate (FeSO) 4 ) 5, disodium edetate (EDTA-Na) 15, boric acid (H) 3 BO 4 ) 0.0014 manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O) 0.99, copper sulfate pentahydrate (CuSO) 4 ·5H 2 O) 0.25, zinc sulfate heptahydrate (ZnSO) 4 ·7H 2 O) 0.43 Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) 0.19 sodium selenate decahydrate (NaSeO) 4 ·10H 2 O) 0.21, sodium molybdate dihydrate (NaMoO) 4 ·2H 2 O)0.22；
The second mixing mode in the step S3 is heating and stirring, the temperature is 45-55 ℃ and the time is 10-20 min;
the mass ratio of the sulfur to the sodium dodecyl benzene sulfonate is (20-40): (4-7);
the mass ratio of the sulfur to the foaming agent is (20-40): (5-8); the foaming agent is sodium bicarbonate solution, and the mass fraction of the sodium bicarbonate solution is 0.5-2 wt%;
s4, carrying out the melting granulation under the conditions of protective atmosphere and stirring; the temperature of the melting granulation is 240-280 ℃, the stirring rotation speed is 120-150 rpm, and the specific time is based on the mass of the raw materials; the vacuum feeding can be one of an electric vacuum feeding machine or a pneumatic vacuum feeding machine.
The particle size of the biological composite filler for realizing deep denitrification by the polysulfide prepared by the preparation method is 8-15 mm.
The beneficial effects are that: the invention provides a biological composite filler for generating polysulfide to realize deep denitrification and a preparation method thereof, and compared with the prior art, the biological composite filler has the following advantages:
the biological composite filler for generating polysulfide to realize deep denitrification provided by the invention takes sulfur and limestone as matrixes, cysteine is added to be uniformly mixed, trace elements are supplemented, and the biological composite filler for generating polysulfide to realize deep denitrification is finally formed through bonding and foaming treatment. Sodium alginate is used as a natural anionic polysaccharide, is nontoxic, has better biocompatibility, can effectively protect microorganisms from harmful environmental media, and is an ideal material for fixing microorganism cells. The sodium dodecyl benzene sulfonate is used as a solid surfactant, so that the hydrophilicity of the surface of the filler is improved, the enrichment degree of microorganisms is increased, the activity of the microorganisms is greatly improved, the utilization rate of sulfur sources, carbon sources and nutrient substances is greatly increased, and the denitrification effect of the microorganisms on nitrogen-containing pollutants can be improved. The absorption and utilization of sulfur autotrophic bacteria to elemental sulfur are mediated by extracellular substances, under the condition of elemental sulfur, the substances containing sulfhydryl structures are highly expressed and differentially expressed, the substances activate the elemental sulfur, biologically modify the sulfur to generate polysulfide which is used as a soluble intermediate, and change the chemical form of the existence of the sulfur, and the hydrophobicity is converted into hydrophilicity so as to facilitate the bacterial utilization. The biological composite filler prepared by the invention activates the elemental sulfur by adding a small amount of cysteine, so that the elemental sulfur is changed into a soluble polysulfide form to enter cells, S n 2- Once generated, the mixed solution can be rapidly utilized by sulfur oxidation denitrifying bacteria to realize rapid reduction of nitrate and a small amount of cysteineThe amino acid is used as a primer for activating elemental sulfur by the sulfur autotrophic denitrifying bacteria to enable the elemental sulfur to be easier to absorb, so that the formation of organic polysulfide is promoted, the solubility of sulfur in sewage is improved, the proliferation and growth of microorganisms are promoted by combining microelements, the formation of sulfur source and EPS (expandable polystyrene) is facilitated for sulfur oxidizing bacteria, the domestication time of the microorganisms is shortened, the denitrification capability is improved, no chemicals such as organic matters, sulfides and the like are required to be additionally added, and the biological treatment unit is simple, the operation cost is low, the denitrification effect is good, the system performance is stable, and the denitrification rate is high.
Drawings
FIG. 1 is a graph showing the effluent effect of the reactor in example 1 of the present invention;
FIG. 2 is a graph showing the effluent effect of the reactor in example 2 of the present invention;
FIG. 3 is a graph showing the effluent effect of the reactor in example 3 of the present invention.
Detailed Description
The invention is described in detail below with reference to the attached drawings and the specific embodiments:
the preparation method of the biological composite filler for generating polysulfide to realize deep denitrification comprises the following steps:
mixing polyvinyl acetate with glycerol to obtain a mixture A; the mass ratio of the polyvinyl acetate to the glycerol is preferably (15-20): (30 to 35), more preferably 20:30;
mixing and stirring sulfur and calcium carbonate, uniformly distributing, adding the mixture into the mixture A, and carrying out first mixing to obtain a mixture B, wherein the sulfur and the calcium carbonate are powdery, and the mass ratio of the sulfur to the calcium carbonate is (20-40): (15 to 20), more preferably 30:20, a step of; the mass ratio of the sulfur to the mixture A is (20-40): (3-6), more preferably 30:5, the sulfur can be used as a sulfur source by sulfur autotrophic denitrifying bacteria to form sulfur autotrophic denitrification; the calcium carbonate is a buffering agent, resists the influence of external adverse pH, and the mixture A is used as an adhesive of sulfur and calcium carbonate, so that toughness, strength and plasticity can be provided for the filler; the first mixing mode is preferably stirring, and the rotating speed of stirring is preferably 10000-20000 rpm, more preferably 15000rpm, and the time is preferably 0.5-1 h, more preferably 0.75h;
mixing cysteine, microelements and sodium alginate water solution for the second time, and dissolving to obtain a mixture C; the mass fraction of the sodium alginate aqueous solution is preferably 2-5 wt%, more preferably 4wt%, and the sodium alginate aqueous solution can be self-made solution or purchased product, and the mass ratio of the sulfur to the cysteine is preferably (20-40): (0.5 to 2), more preferably 30:1, the mass ratio of the sulfur to the sodium alginate solution is (20-40): (1-3), more preferably 30:2; the cysteine and the trace elements are added into the sodium alginate solution, the mixing is not required, the second mixing mode is heating and stirring, the stirring rotating speed is preferably 200-600 rpm, more preferably 300rpm, the time is preferably 20-50 min, more preferably 40min, the temperature is preferably 45-55 ℃, and more preferably 50 ℃;
adding the mixture B, the mixture C and sodium dodecyl benzene sulfonate into a container for third mixing, adding a foaming agent, fully stirring and uniformly mixing to obtain a mixture, and carrying out heating melting, vacuum feeding and injection molding granulation to obtain a required filler; the second mixing is preferably that the mixture B and the mixture C are primarily mixed, and then the obtained primary mixed material is remixed with sodium dodecyl benzene sulfonate, the primary mixing is preferably stirring, the stirring speed is preferably 8000-15000 rpm, more preferably 12000rpm, the time is preferably 40-60 min, more preferably 50min, and the remixing mode is preferably the same as the primary mixing and is not repeated. In the invention, the mass ratio of the sulfur to the sodium dodecyl benzene sulfonate is (20-40): (4-7), wherein the mass ratio of the sulfur to the foaming agent is (20-40): (5-8), more preferably 30:6 to 7; the foaming agent is sodium bicarbonate solution, the mass fraction is preferably 0.5-2 wt%, more preferably 1-2 wt%, and the foaming agent is added uniformly during the third mixing; the melt granulation is carried out under the conditions of protective atmosphere and stirring, the temperature of the melt granulation is preferably 240-280 ℃, more preferably 270 ℃, and the rotating speed of the stirring is 120-150 rpm. The specific operation steps of the granulation are not particularly limited, and the granular materials with the granularity of 8-15 mm can be obtained; in an embodiment of the present invention, the apparatus used for granulation is preferably a granulator, and specifically, the composite material obtained after heat treatment is conveyed to granulation for granulation. The biological composite filler has larger mechanical strength, smaller particle size and larger specific surface area preferably through granulation.
Example 1
The mass ratio of polyvinyl acetate to glycerol is 20:30 preparing a mixture A, weighing 35 parts of sulfur, 15 parts of calcium carbonate and 5 parts of the mixture A by mass part, and stirring for 1h under the condition that the rotating speed is 15000rpm until the mixture A is uniformly mixed to obtain a mixture B; weighing 2 parts of cysteine and 3 parts of sodium alginate solution in parts by weight, adding cysteine and trace elements into the 4wt% sodium alginate solution, and heating and stirring for 50min at the temperature of 45-55 ℃ at the rotating speed of 300rpm to obtain a mixture C; weighing 7 parts by mass of sodium dodecyl benzene sulfonate, adding sodium dodecyl benzene sulfonate after primary mixing of the mixture B and the mixture C, stirring for 50min at the rotating speed of 12000rpm, weighing 5 parts by mass of 1wt% sodium bicarbonate solution, and uniformly adding in the stirring process to obtain a filler raw material; and (3) conveying the raw materials into an injection molding machine through a vacuum feeding machine, carrying out filling production under the conditions of protective atmosphere and stirring, maintaining the temperature of 240-280 ℃, and cooling to obtain the biological composite filling.
Example 2
The mass ratio of polyvinyl acetate to glycerol is 20:30, preparing a mixture A, weighing 30 parts of sulfur, 20 parts of calcium carbonate and 5 parts of the mixture A in parts by weight, and stirring for 0.75h under the condition that the rotating speed is 15000rpm until the mixture A is uniformly mixed to obtain a mixture B; weighing 1 part of cysteine and 2 parts of sodium alginate solution in parts by weight, adding cysteine and trace elements into the 4wt% sodium alginate solution, and heating and stirring for 40min at the rotating speed of 300rpm and the temperature of 45-55 ℃ to obtain a mixture C; weighing 5 parts by mass of sodium dodecyl benzene sulfonate, adding sodium dodecyl benzene sulfonate after primary mixing of the mixture B and the mixture C, stirring for 50min at the rotating speed of 12000rpm, and uniformly adding 3 parts by mass of 2wt% sodium bicarbonate solution in the stirring process to obtain a filler raw material; and (3) conveying the raw materials into an injection molding machine through a vacuum feeding machine, carrying out filling production under the conditions of protective atmosphere and stirring, maintaining the temperature of 240-280 ℃, and cooling to obtain the biological composite filling.
Example 3
The mass ratio of polyvinyl acetate to glycerol is 20:30 preparing a mixture A, weighing 25 parts of sulfur, 25 parts of calcium carbonate and 3 parts of the mixture A in parts by weight, and stirring for 0.5h under the condition that the rotating speed is 15000rpm until the mixture A is uniformly mixed to obtain a mixture B; weighing 0.5 part of cysteine and 1 part of sodium alginate solution in parts by weight, adding cysteine and trace elements into the 4wt% sodium alginate solution, and heating and stirring for 45min at the temperature of 45-55 ℃ at the rotating speed of 300rpm to obtain a mixture C; weighing 4 parts by mass of sodium dodecyl benzene sulfonate, adding sodium dodecyl benzene sulfonate after primary mixing of the mixture B and the mixture C, stirring for 50min at the rotating speed of 12000rpm, weighing 5 parts by mass of 0.5wt% sodium bicarbonate solution, and uniformly adding in the stirring process to obtain a filler raw material; and (3) conveying the raw materials into an injection molding machine through a vacuum feeding machine, carrying out filling production under the conditions of protective atmosphere and stirring, maintaining the temperature of 240-280 ℃, and cooling to obtain the biological composite filling.
Respectively filling the biological composite filler particles prepared in the examples 1-3 into a fixed bed biological column reactor, inoculating and enriching a nitrate-dependent sulfur autotrophic denitrifying bacteria solution and anaerobic sludge for culture, and performing film formation; after film formation is completed, introducing simulated nitrogenous wastewater into the reactor by utilizing a peristaltic pump, wherein the simulated nitrogenous wastewater is prepared from sodium nitrate and tap water, and the nitrate nitrogen concentration in the simulated nitrogenous wastewater is 40mg/L; the reactor is operated for a period of time respectively in a first stage (0-30 d), a second stage (30-60 d) and a third stage (60-90 d), the hydraulic retention time of each stage is respectively 9h, 6h and 3h, and the water outlet condition is observed. The reactor corresponding to the biological composite filler particles prepared in example 1 is denoted as a reactor E1, the reactor corresponding to the biological composite filler particles prepared in example 2 is denoted as a reactor E2, and the reactor corresponding to the biological composite filler particles prepared in example 3 is denoted as a reactor E3, and the results are shown in FIGS. 1 to 3, respectively. As can be seen from FIGS. 1 to 3, the effluent effect of the reactor E2 is excellent, the average removal rate of nitrate nitrogen reaches 91.7% in the stage III, and the removal rate of other reactors is basically about 88%, which proves that the biological composite filler particles provided by the invention can realize excellent denitrification effect in the aspect of sewage treatment and have higher practical use value.
The foregoing is merely a preferred embodiment of the present invention and will assist those skilled in the art in further understanding the present invention, but is not intended to limit the present invention in any way. It should be noted that several variations and modifications could be made by those skilled in the art without departing from the spirit of the invention, which would fall within the protection of the invention.
Claims (10)
1. The preparation method of the biological composite filler for generating polysulfide to realize deep denitrification is characterized by comprising the following steps of:
s1: mixing polyvinyl acetate with glycerol to obtain a mixture A;
s2: mixing and stirring sulfur and calcium carbonate, adding the mixture into the mixture A after uniformly mixing, and carrying out first mixing to obtain a mixture B;
s3: mixing cysteine, microelements and sodium alginate water solution for the second time, and dissolving to obtain a mixture C;
s4: adding the mixture B, the mixture C and sodium dodecyl benzene sulfonate into a container for third mixing, adding a foaming agent, fully stirring and uniformly mixing to obtain a mixture, and carrying out heating melting, feeding, injection molding and granulating to obtain the required filler.
2. The preparation method of the biological composite filler for generating polysulfide to realize deep denitrification according to claim 1, wherein the mass ratio of polyvinyl acetate to glycerol in S1 is (15-20): (30-35).
3. The preparation method of the biological composite filler for generating polysulfide to realize deep denitrification according to claim 1, wherein the mass ratio of sulfur to calcium carbonate is (20-40): (15-20); the mass ratio of the sulfur to the mixture A is (20-40): (3-6).
4. The method for preparing the biological composite filler for generating polysulfide to realize deep denitrification according to claim 1 or 3, wherein the mass ratio of sulfur to cysteine in S3 is (20-40): (0.5-2); the mass ratio of the sulfur to the sodium alginate solution is (20-40): (1-3).
5. The preparation method of the biological composite filler for generating polysulfide to realize deep denitrification, which is characterized by comprising the following steps of 2-5wt% of sodium alginate aqueous solution.
6. The method for preparing the biological composite filler for generating polysulfide to realize deep denitrification according to claim 4, wherein the second mixing mode in S3 is heating and stirring, the temperature is 45-55 ℃, and the time is 10-20 min.
7. The method for preparing the biological composite filler for generating polysulfide to realize deep denitrification according to claim 1 or 3, wherein the mass ratio of sulfur to sodium dodecyl benzene sulfonate in S4 is (20-40): (4-7); the mass ratio of the sulfur to the foaming agent is (20-40): (5-8).
8. The preparation method of the biological composite filler for generating polysulfide to realize deep denitrification according to claim 7, wherein the foaming agent is sodium bicarbonate solution, and the mass fraction of the sodium bicarbonate solution is 0.5-2wt%.
9. The method for producing a biological composite filler for deep denitrification by polysulfide formation according to claim 1, wherein the melt granulation in S4 is performed under a protective atmosphere and under stirring; the temperature is 240-280 ℃, and the stirring speed is 120-150 rpm.
10. The biological composite filler for generating polysulfide to realize deep denitrification, which is prepared by the method of any one of claims 1 to 9, is characterized in that the particle size of the filler is 8 to 15mm; the cysteine in the filler can change elemental sulfur into soluble polysulfide, and the polysulfide is utilized by sulfur oxidation denitrifying bacteria after being produced, so that nitrate reduction is realized.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117550714A (en) * | 2023-12-21 | 2024-02-13 | 广东卓信环境科技股份有限公司 | Sulfur autotrophic denitrification filler |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117550714A (en) * | 2023-12-21 | 2024-02-13 | 广东卓信环境科技股份有限公司 | Sulfur autotrophic denitrification filler |
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