CN117904095A - Method for fixing nitrifying bacteria by sodium alginate-polyurethane filler - Google Patents
Method for fixing nitrifying bacteria by sodium alginate-polyurethane filler Download PDFInfo
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- CN117904095A CN117904095A CN202410102178.0A CN202410102178A CN117904095A CN 117904095 A CN117904095 A CN 117904095A CN 202410102178 A CN202410102178 A CN 202410102178A CN 117904095 A CN117904095 A CN 117904095A
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- sodium alginate
- nitrifying bacteria
- polyurethane filler
- nitrifying
- bacteria
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- 230000001546 nitrifying effect Effects 0.000 title claims abstract description 111
- 241000894006 Bacteria Species 0.000 title claims abstract description 103
- 239000000945 filler Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 31
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 30
- 239000011734 sodium Substances 0.000 title claims abstract description 30
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 30
- 239000000661 sodium alginate Substances 0.000 claims abstract description 57
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 57
- 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 abstract description 47
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000000017 hydrogel Substances 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 230000001580 bacterial effect Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002068 microbial inoculum Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000003100 immobilizing effect Effects 0.000 claims 8
- 230000000694 effects Effects 0.000 abstract description 11
- 239000010865 sewage Substances 0.000 abstract description 11
- 238000005273 aeration Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 239000010802 sludge Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 28
- 239000002245 particle Substances 0.000 description 23
- 244000005700 microbiome Species 0.000 description 17
- 230000014759 maintenance of location Effects 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 239000008213 purified water Substances 0.000 description 9
- 239000012085 test solution Substances 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000007836 KH2PO4 Substances 0.000 description 3
- 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 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001141101 Nitrospirales Species 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000605122 Nitrosomonas Species 0.000 description 1
- 241001495394 Nitrosospira Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 231100000719 pollutant Toxicity 0.000 description 1
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 1
- 229960004134 propofol Drugs 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C12N11/093—Polyurethanes
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Molecular Biology (AREA)
- Biological Treatment Of Waste Water (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention discloses a method for fixing nitrifying bacteria by sodium alginate-polyurethane filler, and belongs to the technical field of water treatment. Firstly, mixing sodium alginate with nitrifying bacteria, then adding polyurethane filler into the mixed solution of sodium alginate and nitrifying bacteria, fully and uniformly stirring, and then placing into a calcium chloride solution for crosslinking and fixing. The invention has the advantages that the sodium alginate and the porous polyurethane filler are utilized to directly fix nitrifying bacteria, the defect that nitrifying bacteria are cultured by prolonging the residence time of activated sludge and the residence time of hydraulic power in the traditional sewage biological denitrification process is avoided, and meanwhile, the immobilized nitrifying bacteria carrier has high activity, can directionally improve the nitrifying rate, reduce the tank capacity of an aeration tank, and provides technical support for low-carbon high-efficiency denitrification in the sewage treatment industry.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for fixing nitrifying bacteria by using sodium alginate-polyurethane filler.
Background
Nitrogen overdischarge is one of the key factors causing eutrophication of water. Biological denitrification of sewage mainly depends on nitrification and denitrification of microorganisms, wherein the nitrification is the speed limiting step. This is due to the slow growth rate of nitrifying bacteria in the activated sludge system of the sewage treatment plant, long generation period, and small quantity and small ratio of nitrifying bacteria in the activated sludge. The nitrifying rate of nitrifying bacteria in the sewage treatment plant is lower, so that the nitrifying process needs longer hydraulic retention time to completely remove ammonia nitrogen, and the occupied area of sewage treatment facilities with the denitrification function is larger. Under the condition that urban land resources are very tense, if the nitrifying rate of nitrifying bacteria can be improved, the method has important significance for saving the land resources.
Immobilized microorganism technology relies on physical or chemical means to confine microorganisms to a spatial region. The technology can increase the number of microorganisms in the system, reduce the loss of the microorganisms, and weaken the interference of external factors on the microorganisms. Currently, the most common immobilization method of immobilized microorganism technology is the embedding method. Materials used in the embedding method are divided into two major categories, namely synthetic polymer organic matters and natural polymer organic matters. The polyvinyl alcohol is one of the most common carriers in the synthesis of high molecular organic matters, but the polyvinyl alcohol and the cross-linking agent boric acid of the polyvinyl alcohol have toxic action on microorganisms, so that the activity of the microorganisms can be reduced, and meanwhile, the mass transfer performance of the polyvinyl alcohol as an immobilization material is poor. Sodium alginate is one of the most common carriers in natural polymer organic matters, and compared with polyvinyl alcohol, sodium alginate has the advantages of good mass transfer performance and no toxicity or harm to microorganisms. In addition, the reaction speed of the sodium alginate and the cross-linking agent calcium chloride in the microorganism immobilization process is high, the required time is short, and the use time of the immobilization process can be reduced. But the mechanical property of sodium alginate is also poor and the service life is short.
Therefore, the immobilized microorganism method which has the advantages of excellent mechanical property, long service life, small toxic action on microorganisms, good mass transfer performance, simple preparation process and low cost and can realize efficient nitrification is developed, and has important practical significance for shortening the hydraulic retention time of the nitrification process and saving the occupied area of sewage treatment facilities and equipment.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a method for fixing nitrifying bacteria by sodium alginate-polyurethane filler, which comprises the following steps:
(1) Preparing sodium alginate into sodium alginate hydrogel;
(2) Centrifuging the liquid nitrifying bacteria bacterial agent, removing the supernatant, adding the precipitate into the sodium alginate hydrogel, and uniformly stirring to obtain a nitrifying bacteria hydrogel mixture;
(3) And adding polyurethane filler into the nitrifying bacteria hydrogel mixture, stirring to obtain polyurethane filler containing sodium alginate and nitrifying bacteria mixed solution (the polyurethane filler contains sodium alginate and nitrifying bacteria mixed solution), adding the polyurethane filler into calcium chloride solution for crosslinking and fixing, and cleaning after the crosslinking and fixing are finished.
The method has the advantages of reducing the damage to bacteria in the immobilization process, improving the mechanical property of the bacteria immobilization carrier, fixing nitrifying bacteria with high nitrifying property on polyurethane filler, improving the nitrifying rate directionally, shortening the hydraulic retention time in the sewage denitrification and nitrifying process, and providing technical support for efficient denitrification in the sewage treatment industry.
The liquid nitrifying bacteria bacterial agent can be changed into a powdery nitrifying bacteria bacterial agent, if the powdery nitrifying bacteria bacterial agent is dissolved in purified water and then centrifuged, if the powdery nitrifying bacteria bacterial agent is the liquid bacterial agent, the liquid nitrifying bacteria bacterial agent can be directly centrifuged.
Further, in the step (1), the preparation method of the sodium alginate hydrogel comprises the following steps: adding sodium alginate into water, heating, stirring, fully dissolving, and standing and cooling at room temperature to obtain sodium alginate hydrogel; further, the preparation method of the sodium alginate hydrogel comprises the following steps: adding sodium alginate into a beaker filled with purified water, heating and stirring to obtain sodium alginate solution, and standing and cooling at room temperature to obtain sodium alginate hydrogel.
Further, in the step (1), the mass fraction of the sodium alginate solution is 1%. The preparation method of the sodium alginate hydrogel preferably comprises the following steps: adding sodium alginate into a beaker filled with purified water, heating and stirring for 1h to obtain sodium alginate solution with the mass fraction of 1%, and standing for 1h at room temperature to obtain the sodium alginate hydrogel. The mass fraction of the sodium alginate solution influences the nitrifying rate of the nitrifying bacteria after immobilization, and the mass fraction of the sodium alginate solution is the proper concentration after screening.
Further, in the step (1), the temperature of heating and stirring is 70 ℃ and the rotating speed is 120r/min.
Further, in the step (2), nitrifying bacteria in the liquid nitrifying bacteria microbial inoculum are dominant bacteria, and the relative abundance is 28.39%. The concentration of the mixed liquor suspended solids of the nitrifying bacteria microbial agent is 3.7g/L (the "mixed liquor suspended solids concentration" means the concentration of microorganisms in the microbial agent). Furthermore, the nitromonas and nitrospiral bacteria in the liquid nitrifying bacteria microbial inoculum are dominant bacteria, and the relative abundance is 27.96% and 0.43% respectively.
Further, in the step (2), the mass fraction of the nitrifying bacteria bacterial agent in the nitrifying bacteria hydrogel mixture is 0.37% on a dry weight basis.
Further, in the step (2), the rotational speed at the time of centrifugation is 6000r/min, preferably 10min.
Further, in the step (3), the specification of the polyurethane filler was 1X 1cm and the pore density was 20ppi.
Further, in the step (3), the time of crosslinking and fixing is 2 hours, and the cleaning is that the pure water is used for flushing for 3 times after the crosslinking and fixing is finished.
Further, in the step (3), the mass fraction of the calcium chloride solution is 2%.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) The immobilized material sodium alginate used in the invention is natural polymer organic matters, is nontoxic and harmless to microorganisms in the immobilization process, has good mass transfer performance, and is beneficial to improving the treatment effect of the microorganisms on pollutants. In addition, the reaction speed of the sodium alginate and the crosslinking agent calcium chloride is high, so that the immobilization preparation process is simple and quick;
(2) The polyurethane filler used in the invention provides excellent mechanical support for sodium alginate, can prolong the service life of the sodium alginate, and can be stably used for more than 60 days when sodium alginate-polyurethane filler fixed nitrifying bacteria particles are added into a reactor;
(3) The fixed microorganisms have a large quantity of nitrifying bacteria, the ratio of the nitrifying bacteria to the sodium alginate-polyurethane filler is high, the nitrifying rate of the sodium alginate-polyurethane filler fixed nitrifying bacteria can reach 9.32 mg/(g MLSS.h), the sodium alginate-polyurethane filler fixed nitrifying bacteria particles are added into the reactor, the starting time of the reactor is short, and ammonia nitrogen can be completely oxidized and removed under the condition of shorter hydraulic retention time.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a diagram of the sodium alginate-polyurethane filler immobilized nitrifying bacteria of example 1;
FIG. 2 is a graph showing the effluent of the reactor of application example 1 with ammonia nitrogen concentration of 30 mg/L;
FIG. 3 is a graph showing the effluent of the reactor of application example 1 with an ammonia nitrogen concentration of 50 mg/L;
FIG. 4 is a graph showing the effluent of the reactor of application example 1 with ammonia nitrogen concentration of 100 mg/L;
FIG. 5 shows the effect of polyvinyl alcohol-sodium alginate immobilized nitrifying bacteria on ammonia nitrogen in comparative example 1;
FIG. 6 shows the morphology change of the polyvinyl alcohol-sodium alginate immobilized nitrifying bacteria particles in comparative example 1.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The liquid nitrifying bacteria preparation in the embodiment of the invention is purchased from Shanghai Propofol biotechnology Co., ltd, wherein the relative abundance of nitromonas (Nitrosomonas) and nitrospiral (Nitrosospira) are 27.96% and 0.43% respectively, and the suspension solid concentration of the mixed liquid of the nitrifying bacteria preparation is 3.7g/L.
Example 1
(1) Adding 20g of sodium alginate into 2L of purified water, heating and stirring at 70 ℃ and 120r/min for 1h, and then standing and cooling for 1h to obtain sodium alginate hydrogel;
(2) Taking 2L of liquid nitrifying bacteria agent, centrifuging (the rotating speed is 6000 r/min) for 10min, removing supernatant, pouring sediment into the sodium alginate hydrogel, and uniformly stirring to obtain nitrifying bacteria hydrogel mixture, wherein the mass fraction of the nitrifying bacteria agent in the nitrifying bacteria hydrogel mixture is 0.37% based on dry weight;
(3) Adding polyurethane filler (with the specification of 1 multiplied by 1cm and the pore density of 20 ppi) into the nitrifying bacteria hydrogel mixture, continuously stirring to enable nitrifying bacteria hydrogel to fully permeate into the polyurethane filler, adding the polyurethane filler (containing sodium alginate and nitrifying bacteria mixed solution in the polyurethane filler) into 10L of calcium chloride solution with the mass fraction of 2%, crosslinking and fixing for 2 hours, and washing 3 times with purified water after the crosslinking is finished to obtain sodium alginate-polyurethane filler fixed nitrifying bacteria particles with the specification of 1 multiplied by 1cm, as shown in figure 1.
Example 2
(1) Adding 1g of sodium alginate into a 100mL beaker filled with purified water, heating and stirring for 1h at 70 ℃, keeping the rotating speed at 120r/min, and standing for 1h at room temperature to obtain sodium alginate hydrogel;
(2) Taking 100mL of nitrifying bacteria bacterial agent, centrifuging (the rotating speed is 6000 r/min) for 10min, discarding supernatant, pouring sediment into the sodium alginate hydrogel, and uniformly stirring to obtain a nitrifying bacteria hydrogel mixture, wherein the mass fraction of the nitrifying bacteria bacterial agent in the nitrifying bacteria hydrogel mixture is 0.37% based on dry weight;
(3) Adding polyurethane filler (with the specification of 1 multiplied by 1cm and the pore density of 20 ppi) into the nitrifying bacteria hydrogel mixture, continuously stirring to enable nitrifying bacteria hydrogel to fully permeate into the polyurethane filler, then adding the polyurethane filler (containing sodium alginate and nitrifying bacteria mixed solution in the polyurethane filler) into 500mL of calcium chloride solution with the mass fraction of 2%, carrying out crosslinking and fixing for 2 hours, and washing 3 times with purified water after the crosslinking is finished to obtain sodium alginate-polyurethane filler fixed nitrifying bacteria particles with the specification of 1 multiplied by 1 cm.
And (3) placing the sodium alginate-polyurethane filler fixed nitrifying bacteria particles prepared in the step (3) into 300mL of prepared test solution (each substance and substance concentration in the test solution are :NH4Cl:382mg/L,MgSO4·7H2O:4mg/L,KH2PO4:10mg/L,FeSO4·7H2O:4mg/L,MnCl2·4H2O:0.2mg/L,CuSO4·5H2O:0.2mg/L) mL, dropwise adding saturated sodium bicarbonate solution into the test solution, regulating the pH to 7-8, maintaining the dissolved oxygen concentration in the solution to 4mg/L, placing the test solution into a constant-temperature shaking table with the rotating speed of 200rpm and the temperature of 25 ℃, taking a water sample once before the shaking table, timing to be 0h, taking the water sample once every 0.5h, fully and uniformly mixing the test solution every time, continuously sampling for 6 times, wherein the sampling amount is respectively 0.5h, 1h, 1.5h, 2h, 2.5h and 3h, filtering the test solution with a 0.45um filter membrane immediately after sampling, sealing and reserving filtrate for measuring ammonia nitrogen, nitrite nitrogen and nitrate in the filtrate, regulating the pH of the solution in a conical flask to 7-8 with the saturated sodium carbonate solution after each sampling, placing the test solution into the constant-temperature shaking table, and continuously reacting the filtrate under the condition of 4 ℃ before the measurement.
And (3) drawing by taking the sampling time t (h) as an abscissa and taking the ammonia nitrogen mass concentration p (mg/L) of residual ammonia nitrogen in the test solution as an ordinate (calculated by N), and fitting data points in the drawing (p=r.t+b) to obtain the absolute value r of the slope of the straight line, wherein the unit is mg NH 4 + -N/(L.h). The nitrifying rate P of the nitrifying bacteria microbial inoculum is expressed as mg NH 4 + -N/(g MLSS.h), and is calculated according to the following formula:
Wherein: the concentration of the M-nitrifying bacteria agent is mg/L, and M=3761 mg/L;
V 1 -volume of fixed nitrifying bacteria inoculum in mL, V 1 = 100mL;
V 2 -test solution volume in mL, V 2 = 300mL;
r-sample determination the absolute value of the slope of the experimental fit line is given in mg NH 4 + -N/(L.h).
The nitrifying rate of the sodium alginate-polyurethane filler immobilized nitrifying bacteria obtained by the calculation method can reach 9.32 mg/(gMLSS.h), and the result shows that the sodium alginate-polyurethane filler immobilized nitrifying bacteria has good nitrifying performance.
Application example 1 Effect of treating simulated wastewater
The sodium alginate-polyurethane filler fixed nitrifying bacteria particles obtained in example 1 were fed into a reactor, the filling ratio (volume ratio of immobilized particles to water inlet) was set to 40%, the diameter of the reactor was 160mm, the height was 320mm (height to diameter ratio was 2), the effective volume was 6L, and the reactor material was organic glass.
The reactor is provided with a 30L water inlet barrel, water distribution components in the water inlet barrel are NH + 4-N、KH2PO4 (nitrogen-phosphorus ratio is 5), caCl 2(111mg/L)、MgSO4(15mg/L)、FeSO4·7H2 O (11.1 mg/L) and NaCl (50 mg/L), hydraulic retention time is regulated by a timer, aeration is carried out by an aeration pump and an aeration head, and the concentration of dissolved oxygen in the reactor is controlled by a gas flowmeter.
The reactor is operated under the conditions that the ammonia nitrogen concentration of the inlet water is 30mg/L, 50mg/L and 100mg/L, the temperature is set to 25 ℃, the pH is controlled to 7-8, the dissolved oxygen is controlled to 4-5 mg/L, and the change condition of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in the outlet water is monitored every day.
As can be seen from fig. 2, the ammonia nitrogen removal rate of the reactor can reach 100% on the 1 st day of start-up, which indicates that the reactor has good operation effect, can realize quick start-up, and can completely remove ammonia nitrogen when HRT is 2 hours for simulated wastewater with inlet ammonia nitrogen concentration of 30 mg/L; as can be seen from FIG. 3, for the simulated wastewater with the influent ammonia nitrogen concentration of 50mg/L, the ammonia nitrogen removal rate fluctuates between 90% and 100% when the HRT is 2 hours; as can be seen from fig. 4, for the simulated wastewater with the ammonia nitrogen concentration of 100mg/L in the influent water, the ammonia nitrogen removal effect can be enhanced by extending HRT, and when HRT is 6h, the ammonia nitrogen removal rate can reach more than 80%.
In conclusion, the reactor built by fixing nitrifying bacteria particles based on the sodium alginate-polyurethane filler has the advantages of short starting time, short required hydraulic retention time, stable and efficient ammonia nitrogen removal effect. In addition, the sodium alginate-polyurethane filler fixed nitrifying bacteria particles not only still maintain high-efficiency nitrifying performance after being used for 60 days, but also have no condition of particle breakage, and the service life of the particles is long.
Application example 2 effect of treatment on real domestic sewage
The sodium alginate-polyurethane filler fixed nitrifying bacteria particles obtained in example 1 were fed into a reactor, the filling ratio (volume ratio of immobilized particles to water inlet) was set to 40%, the diameter of the reactor was 160mm, the height was 320mm (height to diameter ratio was 2), the effective volume was 6L, and the reactor material was organic glass.
The reactor is provided with a 30L water inlet barrel, the hydraulic retention time is regulated by a timer, aeration is carried out by an aeration pump and an aeration head, and the concentration of dissolved oxygen in the reactor is controlled by a flowmeter.
The temperature of the reactor is set to 25 ℃, the dissolved oxygen is controlled to be 4-5 mg/L, and the change conditions of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in the effluent are monitored every day.
The reactor runs stably under the conditions that the hydraulic retention time is 4h and the fluctuation of the concentration of the ammonia nitrogen in the inlet water is large, and the removal rate of the ammonia nitrogen can reach 80%. This shows that the sodium alginate-polyurethane filler fixed nitrifying bacteria particles also have high-efficiency treatment capacity on ammonia nitrogen in the actual domestic sewage.
Comparative example 1 (no polyurethane filler as support)
Adding 200g of polyvinyl alcohol into a beaker filled with 2L of purified water, soaking for 24 hours, putting the beaker into a constant-temperature water bath kettle, heating (70 ℃) for 2 hours to obtain polyvinyl alcohol hydrogel, adding 16g of sodium alginate into the polyvinyl alcohol hydrogel, heating and stirring for 1 hour at 70 ℃, rotating at 120r/min, and standing for 1 hour to obtain polyvinyl alcohol-sodium alginate hydrogel;
Taking 2L of nitrifying bacteria bacterial agent, centrifuging for 10min, taking out the supernatant, pouring the precipitate into the polyvinyl alcohol-sodium alginate hydrogel, and uniformly stirring to obtain nitrifying bacteria hydrogel mixture;
Dropwise adding the nitrifying bacteria hydrogel mixture into 20L of cross-linking agent (the cross-linking agent consists of 4% of boric acid by mass and 2% of calcium chloride by mass), cross-linking and fixing for 16 hours, and washing 3 times with purified water after cross-linking is finished to obtain polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles;
Polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles are added into a reactor, the filling ratio (the volume ratio of the immobilized particles to the inlet water) is set to be 40%, the diameter of the reactor is 160mm, the height is 320mm (the ratio of the height to the diameter is 2), the effective volume is 6L, and the reactor is made of organic glass.
The reactor is provided with a 30L water inlet barrel, water distribution components in the water inlet barrel are NH + 4-N、KH2PO4 (nitrogen-phosphorus ratio is 5), caCl 2(111mg/L)、MgSO4(15mg/L)、FeSO4·7H2 O (11.1 mg/L) and NaCl (50 mg/L), hydraulic retention time is regulated by a timer, aeration is carried out by an aeration pump and an aeration head, and the concentration of dissolved oxygen in the reactor is controlled by a flowmeter.
The temperature is set to 25 ℃, the pH is controlled to 7-8, the dissolved oxygen is controlled to 4-5 mg/L, the hydraulic retention time is 4h, and the change conditions of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in the effluent are monitored every day.
As can be seen from FIG. 5, the ammonia nitrogen concentration of the inlet water is 50mg/L, and the ammonia nitrogen removal rate of the reactor built based on the polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles is about 90% under the condition that the hydraulic retention time is 4 hours. However, as can be seen from fig. 6, as the use time of the polyvinyl alcohol-sodium alginate immobilized nitrifying bacteria particles increases, the polyvinyl alcohol-sodium alginate immobilized nitrifying bacteria particles become soft and a dissolution phenomenon occurs.
Compared with polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles, the reactor built based on sodium alginate-polyurethane filler fixed nitrifying bacteria particles has better ammonia nitrogen removal effect and longer service life under the same hydraulic retention time.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. The method for fixing nitrifying bacteria by using sodium alginate-polyurethane filler is characterized by comprising the following steps of:
(1) Preparing sodium alginate into sodium alginate hydrogel;
(2) Centrifuging the liquid nitrifying bacteria bacterial agent, removing the supernatant, adding the precipitate into the sodium alginate hydrogel, and uniformly stirring to obtain a nitrifying bacteria hydrogel mixture;
(3) And adding the polyurethane filler into the nitrifying bacteria hydrogel mixture, stirring to obtain the polyurethane filler containing the sodium alginate and nitrifying bacteria mixed solution, crosslinking and fixing the polyurethane filler by using a calcium chloride solution, and cleaning after the crosslinking and fixing are finished.
2. The method for immobilizing nitrifying bacteria by using sodium alginate-polyurethane filler according to claim 1, wherein in the step (1), the preparation method of the sodium alginate hydrogel is as follows: adding sodium alginate into water, heating and stirring, and standing and cooling at room temperature to obtain sodium alginate hydrogel.
3. The method for immobilizing nitrifying bacteria by sodium alginate-polyurethane filler according to claim 2, wherein in the step (1), the mass fraction of the sodium alginate solution is 1%.
4. The method for immobilizing nitrifying bacteria by sodium alginate-polyurethane filler according to claim 2, wherein in the step (1), the temperature of heating and stirring is 70℃and the rotation speed is 120r/min.
5. The method for immobilizing nitrifying bacteria by using sodium alginate-polyurethane filler according to claim 1, wherein in the step (2), nitrifying bacteria in the liquid nitrifying bacteria microbial inoculum are dominant bacteria, and the relative abundance is 28.39%.
6. The method for immobilizing nitrifying bacteria by using sodium alginate-polyurethane filler according to claim 5, wherein the nitrifying monad and the nitrifying spiral bacteria in the liquid nitrifying bacterial agent are dominant bacteria, and the relative abundance is 27.96% and 0.43% respectively.
7. The method for immobilizing nitrifying bacteria by using the sodium alginate-polyurethane filler according to claim 1, wherein in the step (2), the mass fraction of the nitrifying bacteria bacterial agent in the nitrifying bacteria hydrogel mixture is 0.37% on a dry weight basis.
8. The method for immobilizing nitrifying bacteria using sodium alginate-polyurethane filler according to claim 1, wherein in the step (2), the rotational speed at the time of centrifugation is 6000r/min.
9. The method for immobilizing nitrifying bacteria using sodium alginate-polyurethane filler according to claim 1, wherein in the step (3), the polyurethane filler has a specification of 1X 1cm and a pore density of 20ppi.
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