CN113044961A - Carrier with autotrophic denitrification function and preparation method thereof - Google Patents
Carrier with autotrophic denitrification function and preparation method thereof Download PDFInfo
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- CN113044961A CN113044961A CN202110229672.XA CN202110229672A CN113044961A CN 113044961 A CN113044961 A CN 113044961A CN 202110229672 A CN202110229672 A CN 202110229672A CN 113044961 A CN113044961 A CN 113044961A
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- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000011593 sulfur Substances 0.000 claims abstract description 72
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 72
- 241001509286 Thiobacillus denitrificans Species 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 39
- 238000000855 fermentation Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 230000004151 fermentation Effects 0.000 claims abstract description 32
- 150000003463 sulfur Chemical class 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000001580 bacterial effect Effects 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- 208000005156 Dehydration Diseases 0.000 claims description 22
- 230000018044 dehydration Effects 0.000 claims description 22
- 238000006297 dehydration reaction Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 235000010333 potassium nitrate Nutrition 0.000 claims description 19
- 239000004323 potassium nitrate Substances 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 241000894006 Bacteria Species 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- 241000605118 Thiobacillus Species 0.000 claims description 7
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 235000015097 nutrients Nutrition 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 5
- 229930195725 Mannitol Natural products 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000000594 mannitol Substances 0.000 claims description 5
- 235000010355 mannitol Nutrition 0.000 claims description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 239000003223 protective agent Substances 0.000 claims description 5
- 239000013589 supplement Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000004071 biological effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000008399 tap water Substances 0.000 description 14
- 235000020679 tap water Nutrition 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000010865 sewage Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910021646 siderite Inorganic materials 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 241001052560 Thallis Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000032770 biofilm formation Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- DXFPFMUNUDLNNU-UHFFFAOYSA-L [O-]C([O-])=O.OC(O)=O.S.[Ca+2] Chemical compound [O-]C([O-])=O.OC(O)=O.S.[Ca+2] DXFPFMUNUDLNNU-UHFFFAOYSA-L 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
- 239000008272 agar Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 241000258957 Asteroidea Species 0.000 description 1
- 241001326157 Denitrobacterium Species 0.000 description 1
- 241000907196 Desulfurobacterium Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- 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 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical group [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
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- -1 sulfur-calcium carbonate compound Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/104—Granular carriers
-
- 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
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/026—Treating water for medical or cosmetic purposes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- 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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- Zoology (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biotechnology (AREA)
- Water Supply & Treatment (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Biochemistry (AREA)
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- General Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Medicinal Chemistry (AREA)
- Tropical Medicine & Parasitology (AREA)
- Virology (AREA)
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention provides a carrier with autotrophic denitrification function and a preparation method thereof, and the carrier has high biological activity, high hydrophilicity, high denitrification rate, characteristics of non-inflammability, self-extinguishment after ignition and good safety. A preparation method of a carrier with an autotrophic denitrification function is characterized by comprising the following steps: the method comprises the following steps of 1, preparing a mixture of biologically modified sulfur and thiobacillus denitrificans, mixing a sulfur and a bacterial liquid of the thiobacillus denitrificans, performing anaerobic fermentation, and dehydrating and drying a fermentation liquid to obtain a mixture of the biologically modified sulfur and the thiobacillus denitrificans; 2. preparing a carrier, wherein the mixture in the step S1 and the carbonate are used as main raw materials to prepare the carrier.
Description
Technical Field
The invention belongs to the field of deep purification treatment of sewage (wastewater), and particularly relates to a carrier with an autotrophic denitrification function and a preparation method thereof.
Background
The sewage regeneration and reuse is an effective way for solving the water crisis. At present, urban domestic sewage still contains nitrogen-containing pollutants with certain concentration after secondary treatment. If the nitrogen element in the water body is consumed only by the self-cleaning capability of the environment without deep denitrification treatment, larger pollution load and ecological toxicity are caused to the environment. Therefore, the development of a novel efficient and economical deep denitrification method becomes a hotspot of research in the field of sewage recycling.
The traditional denitrification technology needs to consume a large amount of organic matters, and the secondary effluent of a sewage treatment plant has seriously insufficient carbon source and extremely poor denitrification effect. At present, domestic and foreign researches mainly focus on a denitrification system utilizing sulfur, the sulfur can be utilized as an electron donor under the anoxic or anaerobic condition, energy is obtained through sulfur in a redox state, and nitrate is used as an electron acceptor to be reduced into nitrogen, so that the denitrification process is realized, and the reaction formula is as follows: 55S +20CO2+50NO3 -+38H2O+4NH4 +→4C5H7O2N+25N2+55SO4 2-+64H+。
Because the chemical sulfur has wide sources and low price, the chemical sulfur is widely applied to an autotrophic denitrification system. The carrier or filter material for domestic and overseas autotrophic denitrification also basically takes chemical sulfur as a main electron donor, for example, in patents of 'a material for removing nitrate in water by an autotrophic microbial denitrification method' (CN 105621609B) and 'an autotrophic denitrification biological carrier', and the like, liquid sulfur or chemical sulfur is directly adopted to be melted at high temperature and then mixed with calcium carbonate to be cooled to obtain the composite material. The composite denitrification carrier prepared by the method has the following problems:
1. because the sulfur is adopted as the base material, the calcium carbonate or siderite particles are dispersed in the sulfur base, and the sulfur is continuous; even if the proportion of sulphur in the composite is reduced to below 40%, the composite is still prone to ignition and does not self-extinguish. The blue flame releases pungent and highly toxic sulfur dioxide, which is similar to the danger of sulfur;
2. because the chemical sulfur has extremely low solubility and biological toxicity, the composite material prepared by melting the sulfur at high temperature has low reaction rate in the denitrification process, a large amount of nitrite is remained, and the effluent has certain toxicity;
3. as the high-temperature melting process is adopted, the density of the sulfur, the calcium carbonate and the siderite is higher, so that the specific gravity of the composite material is high, and the bulk density after crushing is usually more than 1100kg/m3Is not beneficial to saving the investment cost of the filter material;
4. because a high-temperature melting process (the temperature is 120-150 ℃), the low-boiling-point sodium thiosulfate and the denitrobacillus which cannot resist high temperature cannot be mixed into the composite material in the processing process. Resulting in the lack of biological activity of the denitrification material prepared by the method.
Foreign scholars find that the byproduct biological sulfur generated after natural gas or industrial waste gas containing hydrogen sulfide is subjected to biological desulfurization has better denitrification reaction activity through research. Biological sulfur core composed of orthogonal S0Formed of rings and orthogonal to S0The rings are covered with a layer of long chain polymer having hydrophilic properties. The special structure of biological sulfur enables chemical sulfur to have larger specific surface area, higher microbial availability, better hydrophilicity and colloidal stability compared with chemical sulfur. Compared with the denitrification process using chemical sulfur as an electron source, the denitrification process using biological sulfur as the electron source has the speed 2-3 times higher, and the concentration of the residual nitrite in the reaction process is low.
However, the biological desulfurization technology is not widely applied at home and abroad, and the byproduct biological sulfur cannot be industrially produced. It cannot be used for preparing composite denitrification carrier in large scale.
Based on the reasons, the inventor utilizes a biological fermentation method to carry out biological modification on a large amount of chemical sulfur or wet desulphurization byproduct sulfur paste powder in China, and the surface property of the sulfur particles is changed by culturing the denitrobacillus to be attached to the fine sulfur particles, so that the hydrophilicity and the biological affinity of the sulfur particles are improved. The biological modified sulfur and calcium carbonate or siderite powder are dispersed in the cement material by using cement as a normal-temperature bonding curing agent to obtain the autotrophic denitrification carrier with high activity.
Disclosure of Invention
The invention provides a carrier with autotrophic denitrification function and a preparation method thereof, and the carrier has high biological activity, high hydrophilicity, high denitrification speed, characteristics of difficult combustion, self-extinguishment after ignition and good safety.
The technical scheme is that the preparation method of the carrier with the autotrophic denitrification function is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
1. preparing a mixture of biologically modified sulfur and thiobacillus denitrificans, mixing the sulfur and a bacterial liquid of the thiobacillus denitrificans, performing anaerobic fermentation, and dehydrating and drying a fermentation liquid to obtain a mixture of biologically modified sulfur and thiobacillus denitrificans;
2. preparing a carrier, wherein the mixture in the step S1 and the carbonate are used as main raw materials to prepare the carrier.
Further, in step S1, the sulfur is industrial sulfur powder or sulfur paste powder produced by wet desulphurization, and the moisture content of the sulfur paste powder produced by wet desulphurization is 6-12%.
Further, in step S1, the Desulfurobacterium denitrificans is ATCC25259, which is purchased from ATCC type culture Collection.
Further, the step S1 is specifically as follows,
(1) preparing the bacterial liquid of the denitrogenated thiobacillus, wherein the concentration of the denitrogenated thiobacillus in the bacterial liquid is higher than 3x108CFU/ml；
(2) Stirring and mixing sulfur passing through a standard sieve of 100 meshes with water to prepare suspension with the sulfur concentration of 5-50%, and mixing the suspension according to the weight percentage of sulfur: the weight ratio of the rhamnolipid to the rhamnolipid is 1000-5000: 1;
(3) adding nutrient components into the suspension, wherein the nutrient components and the addition amount are as follows, potassium nitrate is 0.7-2.1g/L, monopotassium phosphate is 0.5g/L, ammonium chloride is 0.05g/L, magnesium chloride is 0.01g/L, ferrous sulfate is 0.02g/L, and sodium carbonate is 1.0 g/L;
(4) adding the bacterial liquid with the volume of 2-10% of the suspension into the suspension;
(5) keeping the temperature at 32-35 ℃, carrying out anaerobic stirring fermentation, and supplementing potassium nitrate when the concentration of potassium nitrate in the fermentation liquor is lower than 10mg/L during the fermentation, wherein the addition amount of potassium nitrate is 1.4-2.1 g/L; when the pH value of the fermentation liquor is lower than 6.5, sodium carbonate is supplemented, and the pH value is maintained at 7.0-8.5;
(6) after 30-40 batches of potassium nitrate supplement are maintained, the concentration of the thiobacillus denitrificans in the fermentation liquor is higher than 2x108CFU/mL, ending fermentation;
(7) adding a bioflocculant into the fermentation liquor, wherein the addition amount of the bioflocculant is 1.2-1.5g/L,
collecting the precipitated floc, adding 1-3% mannitol as live bacteria dehydration drying protective agent into the floc, and performing primary dehydration drying on the floc by using a vacuum filter or high-speed centrifugation;
(8) and (3) performing secondary dehydration drying on the floc subjected to primary dehydration drying by adopting a low-temperature heat pump drying method, wherein the low temperature is 35-45 ℃, and the water content is reduced to 5-20% after the secondary dehydration drying, thus obtaining the mixture of the biological modified sulfur and the thiobacillus denitrificans.
Further, step S2 is specifically as follows,
(1) weighing the following raw materials, namely, a mixture of 300-450 parts of biologically modified sulfur and thiobacillus denitrificans, 5-15 parts of sodium thiosulfate, 2-5 parts of reduced iron powder, 60-150 parts of carbonate, 100-300 parts of bonding curing agent and 5-15 parts of powdered activated carbon, and uniformly mixing the weighed raw materials in a mixing stirrer by a dry method;
(2) adding 100-300 parts of water into the raw materials mixed by the dry method, and uniformly mixing and stirring to form slurry;
(3) pouring the slurry into a mold, and curing for 2-5 days at 20-35 ℃ and 60-95% humidity to obtain a cured and hardened crude product;
(4) crushing and screening the cured and hardened crude product to obtain particles of 3-30 mm;
(5) and curing the particles in a normal temperature environment for 20-40 days, and fully hardening to obtain a finished product of the carrier.
Further, the bonding curing agent is cement, and the raw material of step S2 further includes 0.5-3 parts of a polycarboxylic acid water reducing agent.
Further, the raw material of step S2 further includes 1-5 parts of nutrient salt, which includes sodium dihydrogen phosphate and magnesium chloride.
A carrier with autotrophic denitrification function is prepared by the method.
The preparation method and the carrier prepared by the method have the following beneficial effects:
(1) because the sulfur particles in the carrier are dispersed by the cement, the safety is high, the carrier can be automatically extinguished after being ignited, and no potential safety hazard exists;
(2) because the carrier contains active thiobacillus denitrificans and sodium thiosulfate, a denitrification ecosystem can be quickly established;
(3) because the sulfur particles in the carrier are wrapped by metabolites of bacteria, the hydrophilicity is enhanced, and the biological toxicity is reduced;
(4) the carrier has high denitrification rate relative to the sulfur-calcium carbonate compound and low concentration of residual nitrite;
(5) because the biological modified sulfur is loose and is not melted, the surface and the interior of the carrier are porous after being hardened, the specific surface area of the carrier is large, the contact area of sulfur particles and bacteria is large, and the reaction is fast;
(6) the bulk density of the carrier after being crushed to 5-12mm particle size is 600-700kg/m3The bulk density is 50-60% lighter than that of the conventional sulfur-calcium carbonate carrier;
(7) because the normal temperature solidification principle of cement is adopted, thalli and biological active substances secreted by the thalli in the mixture can be preserved, and the thalli are prevented from being damaged and losing activity in the high-temperature process.
(8) After the carrier is stored for 2 years, although the number of viable bacteria is reduced to 40 percent of the initial number, the function of the quick start is influenced, other characteristics of the biological modified sulfur and the carrier are not changed, and the later denitrification efficiency is not influenced.
(9) Although the denitrification rate of the biological modified sulfur as the electron source is low, the biological modified sulfur is produced by taking industrial sulfur and sulfur paste powder produced by wet desulphurization as raw materials, and has wide sources.
Drawings
FIG. 1 is a photograph of an object of the present invention.
FIG. 2 shows the effect of the vector of example 1 on the treatment of simulated wastewater.
FIG. 3 shows the effect of the vector of example 2 on the treatment of simulated wastewater.
FIG. 4 shows the effect of the vector of example 3 on the treatment of simulated wastewater.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which, although described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
Description of materials:
industrial sulfur powder: 200-mesh sulfur powder purchased from Linyi national Olympic Ltd
And (3) sulfur paste powder generated by complex iron desulphurization: among them, complex iron desulfurization is one of wet desulfurization methods.
The sulfur paste powder generated by the complex iron desulfurization is a byproduct of the complex iron desulfurization device of the stone drug group.
The main component of the siderite ore powder is ferrous carbonate, which belongs to one kind of carbonate.
Reduced iron powder, available from suzhou starfish powder metallurgy ltd, under the trade name: primary reduced iron powder.
Portland cement, southern Cement, Inc., is sold as Portland cement, model PO 52.5.
Wood powder activated carbon, model 200 of Yuanyi Biotech limited, Jiangxi.
A polycarboxylic acid water reducing agent, Shandong high-strength new material Co., Ltd., GQ-101.
The bioflocculant is a high-efficiency bioflocculant sold by the biological environmental protection science and technology limited of Wihai Hanbang.
Thiobacillus denitrificans, ATCC25259, purchased from ATCC species depositary.
The formula of the culture medium (first-grade culture bottle, seeding tank and fermentation tank) of the thiobacillus denitrificans is as follows: na (Na)2S2O3·5H2O 5 g，KNO3 2 g， KH2PO4 2 g，NaHCO3 1 g，MgCl2 6H2O 0.5 g，FeSO4·7H20.01g of O; the volume is adjusted to 1L by distilled water. Sterilizing at 121 deg.C for 30 min. A slant medium was prepared by adding 15g/L of agar.
Activated sludge: and (4) secondary sedimentation tank sludge of municipal sewage plants in the stannless economical mountainous area.
Example 1
A carrier with an autotrophic denitrification function is prepared by the following method steps: 1. preparing a mixture of biologically modified sulfur and thiobacillus denitrificans, and 2, preparing a carrier.
1. Preparing a mixture of biologically modified sulfur and thiobacillus denitrificans:
(1) sequentially inoculating thiobacillus denitrificans to the inclined plane, the first-stage culture bottle and the seed tank, and fermenting to obtain the strain with the concentration of 5x108CFU/ml of Thiobacillus denitrificans bacterial liquid.
(2) Stirring and mixing 200-mesh industrial sulfur powder with tap water to prepare suspension with the sulfur concentration of 10%; according to the following steps: the rhamnolipid is added into the rhamnolipid in a weight ratio of 2000:1 to promote sulfur to be dispersed into water;
(3) 2.1g/L potassium nitrate, 0.5g/L potassium dihydrogen phosphate, 0.05g/L ammonium chloride, 0.01g/L magnesium chloride, 0.02g/L ferrous sulfate and 1.0g/L sodium carbonate are added into the sulfur suspension;
(4) adding thiobacillus denitrificans liquid with the volume of 5% of the suspension liquid, and uniformly mixing;
(5) the mixed liquid of the sulfur and the denitrogenation thiobacillus liquid is kept warm at 35 ℃, and stirred and fermented in an anaerobic tank. By detecting the content of the nitrate, when the concentration of the nitrate is lower than 10mg/L, 2.1g/L of potassium nitrate is supplemented; when the pH of the fermentation product is lower than 6.5, adjusting the pH by adopting sodium carbonate, and maintaining the pH to be 7.0-8.5;
(6) after 30 batches of potassium nitrate supplement are maintained, the fermentation is ended, and the concentration of the thiobacillus denitrificans in the fermentation product is 5x108CFU/mL；
(7) And performing flocculation precipitation on the fermentation turbid liquid by using a high-efficiency biological flocculant, and performing precipitation concentration on sulfur and thiobacillus denitrificans. The adding amount of the high-efficiency biological flocculant is 1.2g/L, mannitol with the mass fraction of 2% is added into the precipitated floc to be used as a live bacteria dehydration drying protective agent, and then a vacuum filter is adopted for primary dehydration drying;
(8) and (3) performing secondary dehydration drying on the floc subjected to primary dehydration drying by adopting a low-temperature heat pump drying method, keeping the constant temperature of 45 ℃ in the drying process, and drying to obtain a mixture with the water content of 10% and containing 2 hundred million/g of active thiobacillus denitrificans, wherein the mixture is the mixture of biologically modified sulfur and thiobacillus denitrificans.
Instructions for use of the high-efficiency bioflocculant: if high-speed centrifugation (8000 g) is adopted, the equipment investment is too large; if membrane filtration is adopted, because the sulfur paste powder and the microorganisms are tiny (1-2 um), the membrane is easy to block, and the cleaning cost is high. Comprehensively considered, the separation is carried out by adopting a nontoxic biological flocculant.
2. Preparing a carrier:
the raw materials consist of the following components: 450 g of biological modified sulfur, 100 g of siderite powder (325 meshes), 15g of sodium thiosulfate, 2g of reduced iron powder, 150 g of ordinary portland cement (PO 52.5), 6.0 g of wood powder activated carbon (200 meshes), 1.0g of polycarboxylic acid water reducing agent, 1.5g of sodium dihydrogen phosphate, 0.2 g of magnesium chloride and 200 g of tap water.
Mixing the materials except tap water, adding tap water, mixing, stirring to obtain slurry, pouring into a mold, placing the mold in a constant temperature oven at 32 deg.C, curing for 24 hr, removing the mold, and placing in a containerCuring in a constant temperature oven for 3 days, crushing and screening by a crusher to obtain particles of 3-20mm, and standing the particles in an open environment at normal temperature for 28 days to obtain the carrier prepared in the example, as shown in FIG. 1. Measuring the true density of the carrier to be 1.1-1.2g/cm3Bulk density of 600-650kg/m3。
And (3) loading the carrier into a fixed bed reactor, inoculating activated sludge into the reactor, and starting biofilm formation for 7 days. Pumping effluent (the total nitrogen concentration is 23-35 mg/L) of a biochemical secondary sedimentation tank of a certain sewage plant into the reactor by using a peristaltic pump, keeping the hydraulic retention time of sewage in the reactor to be 0.5h, and monitoring the total nitrogen and nitrate nitrogen concentration of the effluent. After long-time continuous operation, the effluent quality is stable. The effect of the treatment with the active carrier is shown in FIG. 2.
Table 1: example 1 Carrier treatment of Total Nitrogen degradation in Secondary sedimentation tank of certain Sewage plant mg/L
As can be seen from the analysis of figure 2 and table 1, the carrier of the invention has the effluent of the secondary sedimentation tank with the total nitrogen concentration of 23-35mg/L of the inlet water after the stabilization after the retention time of 30 minutes is less than 10 mg/L.
Example 2
A carrier with an autotrophic denitrification function is prepared by the following method steps: 1. preparing a mixture of biologically modified sulfur and thiobacillus denitrificans, and 2, preparing a carrier.
1. Preparing a mixture of biologically modified sulfur and thiobacillus denitrificans:
(1) sequentially inoculating thiobacillus denitrificans to the inclined plane, the first-stage culture bottle and the seed tank, and fermenting to obtain the product with the concentration higher than 3x108CFU/ml thiobacillus denitrificans liquid;
(2) stirring and mixing sulfur paste powder generated by 200-mesh complex iron method desulfurization with tap water to prepare suspension with the sulfur concentration of 20%; according to the following steps: the rhamnolipid is added into the rhamnolipid in a weight ratio of 1000:1 to promote sulfur to be dispersed into water;
(3) 2.1g/L potassium nitrate, 0.5g/L potassium dihydrogen phosphate, 0.05g/L ammonium chloride, 0.01g/L magnesium chloride, 0.02g/L ferrous sulfate and 1.0g/L sodium carbonate are added into the sulfur suspension;
(4) adding thiobacillus denitrificans liquid with the volume of 5% of the suspension liquid, and uniformly mixing;
(5) keeping the temperature of the mixed solution at 35 ℃, stirring and fermenting in an anaerobic tank, and supplementing 2.1g/L of potassium nitrate when the concentration of nitrate is lower than 10mg/L by detecting the content of nitrate; when the pH of the fermentation product is lower than 6.5, adjusting the pH by adopting sodium carbonate, and maintaining the pH to be 7.0-8.5;
(6) after 30 batches of potassium nitrate supplement are maintained, the fermentation is ended, and the concentration of the thiobacillus denitrificans in the fermentation product is 5x108CFU/mL；
(7) Carrying out flocculation precipitation on the fermentation turbid liquid by using a high-efficiency biological flocculant, carrying out precipitation concentration on sulfur and thiobacillus denitrificans, adding 1.5g/L of the high-efficiency biological flocculant, adding mannitol with the mass fraction of 2% into a precipitated floc to serve as a live bacteria dehydration drying protective agent, and carrying out primary dehydration drying by using a vacuum filter;
(8) and (3) performing secondary dehydration drying on the floc subjected to primary dehydration drying by adopting a low-temperature heat pump drying method, keeping the constant temperature of 45 ℃ in the drying process, and drying to obtain a mixture with the water content of 8% and containing 2.5 hundred million/g of active thiobacillus denitrificans, wherein the mixture is a mixture of biologically modified sulfur and thiobacillus denitrificans.
2. Preparing a carrier:
the raw materials of the material comprise the following components: 450 g of biological modified sulfur, 100 g of calcium carbonate (200 meshes), 10 g of sodium thiosulfate, 3 g of reduced iron powder, 150 g of ordinary portland cement (PO 62.5), 8.0 g of wood powder activated carbon (200 meshes), 1.0g of polycarboxylic acid water reducing agent, 1.0g of sodium dihydrogen phosphate, 0.2 g of magnesium chloride and 210 g of tap water.
Mixing the materials except tap water, adding tap water, mixing, stirring to obtain slurry, pouring into a mold, placing the mold in a constant temperature oven at 32 deg.C, curing for 24 hr, removing the mold, maintaining in the constant temperature oven for 3d, crushing and sieving to obtain 3-12mm granules, and mixing the granules with waterAfter leaving in an open atmosphere at room temperature for 28 days, the carrier prepared in this example was obtained. Measuring the true density of the carrier to be 1.1-1.2g/cm3Bulk density of 600-700kg/m3。
And (3) loading the carrier into a fixed bed reactor, inoculating activated sludge into the reactor, and starting biofilm formation for 7 days. Pumping the pharmaceutical wastewater (the total nitrogen concentration is 100-. After long-time continuous operation, the effluent quality is stable. The effect of the treatment with the active carrier is shown in FIG. 3.
Table 2: example 2 Carrier treatment of Total Nitrogen degradation in pharmaceutical wastewater mg/L
As can be seen from the analysis of FIG. 3 and Table 2, the carrier of the present invention has a retention time of 4h, and the effluent is less than 30mg/L after the stabilization post-treatment for the pharmaceutical wastewater with the total nitrogen concentration of the inlet water of 100-160 mg/L.
Example 3
A carrier with an autotrophic denitrification function is prepared by the following method steps: 1. preparing a mixture of biologically modified sulfur and thiobacillus denitrificans, and 2, preparing a carrier.
1. Preparing a mixture of biologically modified sulfur and thiobacillus denitrificans:
(1) sequentially inoculating thiobacillus denitrificans to the inclined plane, the first-stage culture bottle and the seed tank, and then obtaining the strain with the concentration of 5x10 through the fermentation tank8CFU/ml thiobacillus denitrificans liquid;
the formula of the slant and seed liquid culture medium is as follows: na (Na)2S2O3·5H2O 5 g ,KNO3 2 g KH2PO4 2 g ,
NaHCO3 1 g ,MgCl2 6H2O 0.5 g FeSO4·7H2O 0.01 g ,
The volume is adjusted to 1L by distilled water. Sterilizing at 121 deg.C for 30 min. A slant medium was prepared by adding 15g/L of agar.
(2) Stirring and mixing industrial sulfur powder of 400 meshes with tap water to prepare suspension with the sulfur concentration of 20%; according to the following steps: the rhamnolipid is added into the rhamnolipid in a weight ratio of 2000:1 to promote sulfur to be dispersed into water;
(3) 2.1g/L potassium nitrate, 0.5g/L potassium dihydrogen phosphate, 0.05g/L ammonium chloride, 0.01g/L magnesium chloride, 0.02g/L ferrous sulfate and 1.0g/L sodium carbonate are added into the sulfur suspension;
(4) adding thiobacillus denitrificans liquid with the volume of 5% of the suspension liquid, and uniformly mixing;
(5) keeping the temperature of the mixed solution at 35 ℃, and stirring and fermenting in an anaerobic tank. By detecting the content of the nitrate, when the concentration of the nitrate is lower than 10mg/L, 2.1g/L of potassium nitrate is supplemented; when the pH of the fermentation product is lower than 6.5, adjusting the pH by adopting sodium carbonate, and maintaining the pH to be 7.0-8.5;
(6) after 30 batches of potassium nitrate supplement are maintained, the fermentation is ended, and the concentration of the thiobacillus denitrificans in the fermentation product is 5x108CFU/mL；
(7) Carrying out flocculation precipitation on the fermentation turbid liquid by using a high-efficiency biological flocculant, carrying out precipitation concentration on sulfur and thiobacillus denitrificans, adding 1.5g/L of the high-efficiency biological flocculant, adding mannitol with the mass fraction of 3% into a precipitated floc to serve as a live bacteria dehydration drying protective agent, and carrying out primary dehydration drying by using a vacuum filter;
(8) and (3) performing secondary dehydration drying on the floc subjected to primary dehydration drying by adopting a low-temperature heat pump drying method, keeping the constant temperature of 45 ℃ in the drying process, and drying to obtain a mixture with the water content of 8% and containing 2.5 hundred million/g of active thiobacillus denitrificans, wherein the mixture is a mixture of biologically modified sulfur and thiobacillus denitrificans.
2. Preparing a carrier:
the raw materials of the material comprise the following components: 300 g of biological modified sulfur, 15g of sodium thiosulfate, 100 g of calcium carbonate (325 meshes), 5g of reduced iron powder, 100 g of ordinary portland cement (PI 52.5), 4.5 g of wood powder activated carbon (200 meshes), 1.0g of polycarboxylic acid water reducing agent, 0.5g of sodium dihydrogen phosphate, 0.1 g of magnesium chloride and 150 g of tap water.
The carrier prepared in the embodiment is obtained by uniformly mixing other materials except tap water, adding tap water, mixing and stirring into a slurry state, pouring into a mold, placing the mold in a constant temperature incubator at 32 ℃, curing for 24 hours, removing the mold, curing in the incubator for 3 days, crushing and screening out particles with the particle size of 3-12mm by a crusher, and placing the particles in a normal-temperature open environment for 28 days. Measuring the true density of the carrier to be 1.1-1.2g/cm3Bulk density of 600-700kg/m3。
And (3) loading the carrier into a fixed bed reactor, inoculating activated sludge into the reactor, and starting biofilm formation for 7 days. Pumping certain photovoltaic production wastewater (the total nitrogen concentration is 400-500 mg/L) into the reactor by using a peristaltic pump, keeping the hydraulic retention time of the sewage in the reactor to be 12h, and monitoring the total nitrogen and nitrate nitrogen concentration of the effluent. After long-time continuous operation, the effluent quality is stable. The effect of the treatment with the active carrier is shown in FIG. 4.
Table 3: example 3 Carrier treatment of Total Nitrogen degradation in certain photovoltaic production wastewater mg/L
As can be seen from the analysis of FIG. 4 and Table 3, the residence time of the carrier of the invention is 12h, and the effluent water after the stabilization post-treatment is lower than 50mg/L for the photovoltaic wastewater with the total nitrogen concentration of the inlet water of 400-500 mg/L.
Example 4
According to the preparation method provided by the patent 'a material (201610204784.9) for removing nitrate in water by autotrophic microbial denitrification', sulfur is adopted: calcium carbonate =1:1, and after heating and melting sulfur at 115 ℃, calcium carbonate powder of 200 meshes is added, and after stirring uniformly, the mixture is cooled and solidified, and is crushed into particles of 1-5mm for later use as a control group 1.
According to the preparation method provided by the patent of 'autotrophic denitrification biological carrier (201821557620.5)', sulfur is adopted: calcium carbonate =4:6, sulfur was melted by heating at 140 ℃, then 160 mesh calcium carbonate powder was added, stirred uniformly and put into a distributor, and the mixture was dropped into cooling water to obtain a 3-8mm sphere as a control group 2.
The vehicle prepared in example 1, example 2 and example 3 of the present invention was subjected to a combustion control experiment with control group 1 and control group 2.
Control test method for judgment of vehicle burning: the time for maintaining combustion, the flame size and the smoke condition of the single particle carrier after the single particle carrier is ignited by a lighter are calculated, and the experimental results are shown in table 4.
Table 4: and (4) combustion control experiment results.
Note: the term "continuously burning until the sulfur is completely burnt out" means that the sulfur in the pellets is completely burnt out, leaving only calcium carbonate powder.
As can be seen from the comparative tests, the preparation method provided by the invention adopts cement as a base material to wrap the sulfur particles, so that the sulfur is separated and can not be continuously combusted, and the sulfur can be automatically extinguished immediately after being ignited. Unlike carriers prepared by other methods, which are constantly burning, fires are easily generated.
The comparative experiment of the start-up period between the control group vector and the vector provided by the invention is as follows.
Artificially prepared simulated wastewater: KNO3 0.72g，NaH2PO4 0.1g，NH4Cl 0.1g，MgCl2 0.05g，FeSO40.05g of tap water 1000 ml.
A2L experimental filter column is adopted, 300ml of sludge in a secondary sedimentation tank is inoculated, the filling amount of a carrier is 1.6L, and water enters from the lower part and flows out from the upper part. The experimental temperature is 25-30 ℃. The hydraulic retention time is 6 h. The results of the experiment are shown in tables 5 and 6.
Table 5: nitrite Nitrogen (NO) in 5 carrier effluent2 --N) case mg/L
Table 6: mg/L of Total Nitrogen (TN) in effluent of 5 carriers
Compared with the conventional carrier prepared by melting the sulfur-calcium carbonate at high temperature, the carrier provided by the invention has the advantages of low nitrite residue, high total nitrogen removal efficiency and quick start in the aspect of sewage treatment effect.
Example 5
The drying method in step (8) of the preparation of biologically modified sulfur in example 1 was changed to drying the fermented mixture in an electric oven at 65 ℃ to obtain a mixture of biologically modified sulfur and Thiobacillus deaminatus, which contained 3X10 of active Thiobacillus deaminatus as measured by plate counting6CUF/g, and then a carrier was prepared according to the method of example 1, and the obtained product was example 5.
Comparative experiments on the start-up period of the control vehicle and the vehicle of the present invention are as follows. Wherein the starting operating conditions are: and (4) after the sludge in the secondary sedimentation tank is inoculated, internal circulation is carried out for 3d, and then water inflow is started.
Artificially prepared simulated wastewater: KNO3 0.72g，NaH2PO4 0.1g，NH4Cl 0.1g，MgCl2 0.05g，FeSO40.05g of tap water 1000 ml.
A2L experimental filter column is adopted, 300ml of sludge in a secondary sedimentation tank is inoculated, the filling amount of a carrier is 1.6L, and water enters from the lower part and flows out from the upper part. The experimental temperature is 25-30 ℃. The hydraulic retention time is 6 h. The results of the experiment are shown in Table 7.
Table 7: mg/L of Total Nitrogen (TN) of 3 carriers effluent
As can be seen from the above comparative experiments, the carrier of example 1, because of containing high concentration of active Thiobacillus denitrificans, starts faster, and the effluent water reaches stability in a very short time; the biologically modified sulfur treated at high temperature contains denitrobacterium inactivated in the thermal drying, which results in slow start-up of example 1; but the modified carrier contains active ingredients and is added with sodium thiosulfate as a quick-acting electron source, so that the carrier is started more quickly than a carrier prepared by a conventional high-temperature melting method, and the removal rate of TN is higher.
Claims (8)
1. A preparation method of a carrier with an autotrophic denitrification function is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, preparing a mixture of biologically modified sulfur and thiobacillus denitrificans, mixing the sulfur and the bacterial liquid of the thiobacillus denitrificans, performing anaerobic fermentation, and dehydrating and drying the fermentation liquid to obtain a mixture of biologically modified sulfur and thiobacillus denitrificans;
s2, preparing a carrier, wherein the mixture obtained in the step S1 and the carbonate are used as main raw materials to prepare the carrier.
2. The method for preparing a vector with autotrophic denitrification function according to claim 1, wherein: in step S1, the sulfur is industrial sulfur powder or sulfur paste powder produced by wet desulphurization.
3. The method for preparing a vector with autotrophic denitrification function according to claim 1, wherein: in step S1, the Thiobacillus denitrificans is ATCC25259, purchased from ATCC species depositary.
4. The method for preparing a vector with autotrophic denitrification function according to claim 1, wherein: the step S1 is specifically described as follows,
(1) preparing the bacterial liquid of the denitrogenated thiobacillus, wherein the concentration of the denitrogenated thiobacillus in the bacterial liquid is higher than 3x108CFU/ml；
(2) Stirring and mixing sulfur passing through a standard sieve of 100 meshes with water to prepare suspension with the sulfur concentration of 5-50%, and mixing the suspension according to the weight percentage of sulfur: the weight ratio of the rhamnolipid to the rhamnolipid is 1000-5000: 1;
(3) adding nutrient components into the suspension, wherein the nutrient components and the addition amount are as follows, potassium nitrate is 0.7-2.1g/L, monopotassium phosphate is 0.5g/L, ammonium chloride is 0.05g/L, magnesium chloride is 0.01g/L, ferrous sulfate is 0.02g/L, and sodium carbonate is 1.0 g/L;
(4) adding the bacterial liquid with the volume of 2-10% of the suspension into the suspension;
(5) keeping the temperature at 32-35 ℃, carrying out anaerobic stirring fermentation, and supplementing potassium nitrate when the concentration of potassium nitrate in the fermentation liquor is lower than 10mg/L during the fermentation, wherein the addition amount of potassium nitrate is 1.4-2.1 g/L; when the pH value of the fermentation liquor is lower than 6.5, sodium carbonate is supplemented, and the pH value is maintained at 7.0-8.5;
(6) after 30-40 batches of potassium nitrate supplement are maintained, the concentration of the thiobacillus denitrificans in the fermentation liquor is higher than 2x108CFU/mL, ending fermentation;
(7) adding a bioflocculant into the fermentation liquor, wherein the addition amount of the bioflocculant is 1.2-1.5g/L, collecting precipitated flocs, adding mannitol with the mass fraction of 1% -3% into the flocs as a live bacteria dehydration drying protective agent, and performing primary dehydration drying on the flocs by adopting a vacuum filter or high-speed centrifugation;
(8) and (3) performing secondary dehydration drying on the floc subjected to primary dehydration drying by adopting a low-temperature heat pump drying method, wherein the low temperature is 35-45 ℃, and the water content is reduced to 5-20% after the secondary dehydration drying, thus obtaining the mixture of the biological modified sulfur and the thiobacillus denitrificans.
5. The method for preparing a vector with autotrophic denitrification function according to claim 1, wherein: the step S2 is specifically as follows,
(1) weighing the following raw materials, namely, a mixture of 300-450 parts of biologically modified sulfur and thiobacillus denitrificans, 5-15 parts of sodium thiosulfate, 2-5 parts of reduced iron powder, 60-150 parts of carbonate, 100-300 parts of bonding curing agent and 5-15 parts of powdered activated carbon, and uniformly mixing the weighed raw materials in a mixing stirrer by a dry method;
(2) adding 100-300 parts of water into the raw materials mixed by the dry method, and uniformly mixing and stirring to form slurry;
(3) pouring the slurry into a mold, and curing for 2-5 days at 20-35 ℃ and 60-95% humidity to obtain a cured and hardened crude product;
(4) crushing and screening the cured and hardened crude product to obtain particles of 3-30 mm;
(5) and curing the particles in a normal temperature environment for 20-40 days, and fully hardening to obtain a finished product of the carrier.
6. The method for preparing a vector with autotrophic denitrification function according to claim 5, wherein: the bonding curing agent is cement, and the raw material of the step S2 further comprises 0.5-3 parts of a polycarboxylic acid water reducing agent.
7. The method for preparing a vector with autotrophic denitrification function according to claim 5, wherein: the raw material of step S2 further includes 1-5 parts of nutrient salts, which include sodium dihydrogen phosphate and magnesium chloride.
8. A carrier with autotrophic denitrification function, which is prepared by the method of any one of claims 1-7.
Priority Applications (1)
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| CN114634246A (en) * | 2022-04-15 | 2022-06-17 | 合肥工业大学 | Method for deep denitrification by utilizing sulfur paste autotrophic nitrogen |
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