WO2016041403A2 - 一种用于去除水中戊唑醇复式反应器及其系统和方法 - Google Patents
一种用于去除水中戊唑醇复式反应器及其系统和方法 Download PDFInfo
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- WO2016041403A2 WO2016041403A2 PCT/CN2015/083877 CN2015083877W WO2016041403A2 WO 2016041403 A2 WO2016041403 A2 WO 2016041403A2 CN 2015083877 W CN2015083877 W CN 2015083877W WO 2016041403 A2 WO2016041403 A2 WO 2016041403A2
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- water
- resin
- reactor
- tebuconazole
- backwash
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 215
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000005839 Tebuconazole Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 113
- 229920005989 resin Polymers 0.000 claims abstract description 113
- 238000001179 sorption measurement Methods 0.000 claims abstract description 49
- 244000005700 microbiome Species 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000005273 aeration Methods 0.000 claims description 31
- 235000015097 nutrients Nutrition 0.000 claims description 20
- 230000000813 microbial effect Effects 0.000 claims description 17
- 238000011001 backwashing Methods 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 241000894006 Bacteria Species 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003698 anagen phase Effects 0.000 claims description 7
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 7
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 7
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 7
- 239000001888 Peptone Substances 0.000 claims description 6
- 108010080698 Peptones Proteins 0.000 claims description 6
- 235000015278 beef Nutrition 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 230000004060 metabolic process Effects 0.000 claims description 6
- 238000009629 microbiological culture Methods 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 235000019319 peptone Nutrition 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 241000736131 Sphingomonas Species 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229920005553 polystyrene-acrylate Polymers 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 230000001580 bacterial effect Effects 0.000 claims 2
- LQDARGUHUSPFNL-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(COC(F)(F)C(F)F)CN1C=NC=N1 LQDARGUHUSPFNL-UHFFFAOYSA-N 0.000 claims 1
- 239000005840 Tetraconazole Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 235000016709 nutrition Nutrition 0.000 claims 1
- 230000035764 nutrition Effects 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 9
- 238000006065 biodegradation reaction Methods 0.000 abstract description 8
- 238000003795 desorption Methods 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract 1
- 239000010914 pesticide waste Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000000575 pesticide Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 15
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 11
- 241001135759 Sphingomonas sp. Species 0.000 description 10
- 239000002609 medium Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- XYVMOLOUBJBNBF-UHFFFAOYSA-N 3h-1,3-oxazol-2-one Chemical compound OC1=NC=CO1 XYVMOLOUBJBNBF-UHFFFAOYSA-N 0.000 description 5
- 239000006143 cell culture medium Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910000397 disodium phosphate Inorganic materials 0.000 description 5
- 235000019800 disodium phosphate Nutrition 0.000 description 5
- 241000228245 Aspergillus niger Species 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 241000221785 Erysiphales Species 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003987 organophosphate pesticide Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 108020004465 16S ribosomal RNA Proteins 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 210000003495 flagella Anatomy 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- URKOMYMAXPYINW-UHFFFAOYSA-N quetiapine Chemical compound C1CN(CCOCCO)CCN1C1=NC2=CC=CC=C2SC2=CC=CC=C12 URKOMYMAXPYINW-UHFFFAOYSA-N 0.000 description 1
- 229960004431 quetiapine Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
- C02F3/06—Aerobic processes using submerged filters
-
- 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
- C02F3/341—Consortia of bacteria
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- 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
- C02F2209/40—Liquid flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- 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
- C02F3/108—Immobilising gels, polymers or the like
-
- 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
Definitions
- the invention discloses a system and a method for removing tebuconazole in water, more specifically a tebuconazole double reactor for removing water and a system and method thereof, namely a microorganism-loaded resin and a double reactor An integrated system and method for removing tebuconazole from water.
- the pollution of pesticides on soil and water bodies is becoming more and more serious.
- pesticides applied to crops have a dose of less than 0.3% effective for pests, and 99.7% of the remaining pesticides remain on the surface of crops and in the soil and water in the natural environment, eventually entering the river with rainfall and irrigation water.
- Lakes and groundwater pose potential health hazards to humans and other aquatic organisms.
- Tebuconazole preparation is widely used as an important pesticide in the world, and can effectively control various rust, powdery mildew, net blotch, root rot, scab and smut of cereal crops, on fruit trees.
- the first type is based on biochemical methods, using microbes to destroy the structure of tebuconazole, turning it into a small molecule that is less toxic or more susceptible to degradation.
- biodegradation is an economical treatment technology, it has The following defects limit its treatment and application of tebuconazole wastewater: (1) weak resistance to water quality fluctuations, can not withstand high pollution load impact in wastewater; (2) the process of microbial degradation of tebuconazole is slow, usually 3-5 Days are slower than traditional adsorption and chemical oxidation methods.
- the second type is based on the adsorption method, which separates tebuconazole from the water body without changing its chemical structure.
- the adsorption method is the most commonly used and highly efficient treatment method in laboratory or industrial production, this is the case.
- the biggest drawback of the physical treatment method is that the adsorbed material after adsorption needs to be desorbed and regenerated, so the resulting desorption liquid needs to be effectively disposed, otherwise it will cause secondary pollution.
- the adsorption method mainly focuses on the adsorption of tebuconazole by activated carbon, and the use of resin adsorption technology to remove tebuconazole in wastewater has not been reported.
- the third type is the oxidation of tebuconazole with chemical agents.
- this method has been reported by a patent (a method for treating organophosphorus pesticide wastewater by using immobilized microorganisms, publication number: CN103102015A).
- this method needs to be used during use. Adding multiple agents, complicated operation and high running cost are not an efficient and economical method. Especially for the removal of low concentration tebuconazole, water quality deterioration and biological toxicity may occur due to the addition of excess chemicals. increase.
- the present invention provides a system and method for removing tebuconazole in water by using a novel duplex reactor and a microorganism-loaded resin, and adopting a novel microorganism-loaded adsorption resin as a double reactor. Adsorbing the filler, rapidly adsorbing and removing tebuconazole in the water, and simultaneously degrading the adsorbed tebuconazole through the microorganism supported on the resin to realize in-situ regeneration of the adsorbent resin.
- the treatment methods for pesticide wastewater mainly include oxidation method, biodegradation method and adsorption method, while the method for removing tebuconazole is rare, and only the oxidation method is reported.
- the method described in the comparative patent has the following disadvantages in removing tebuconazole from water: Aspergillus niger can only degrade organophosphorus pesticides and cannot degrade tebuconazole in water; activated carbon is mainly microporous structure, which has not only small adsorption capacity but low adsorption rate. Moreover, after the strain is attached, the micropores are clogged, and it is difficult to exert the adsorption effect, and can only be used as a carrier of the strain; no supporting reactor and treatment system are provided, and the activated carbon is difficult to separate in water, which is difficult to be practically applied.
- Pesticide wastewater treatment technology based on adsorption as the core (Comparative Patent 3 name: A deep treatment method for pesticide industrial wastewater, publication number: CN101746930 A): Production wastewater and magnetic properties of quetiapine pesticides after aerobic biochemical treatment The resin is continuously dynamically adsorbed, and the upper-flow suspended bed magnetic resin contact reactor is used as an adsorption reactor, and water is continuously fed in and out to adsorb and remove pollutants in water.
- the method described in the comparative patent has the following disadvantages: the magnetic resin mainly removes contaminants by ion exchange, and tebuconazole is not ionic in water, so it cannot be removed by ion exchange; the magnetic resin needs to be regenerated with brine after adsorbing pollutants. Secondary pollution occurs during the disposal of the regenerant.
- the invention utilizes the multi-layer resin in the double reactor to adsorb and remove tebuconazole in water, and then degrades the tebuconazole adsorbed on the resin through the microorganisms loaded on the resin, and the resin is regenerated in situ, thereby achieving continuous advancement. Water outlet operation mode.
- a resin adsorbent material using a high molecular polymer as a microbial carrier can not only load microorganisms, but also adsorb tebuconazole in water, and has a large adsorption capacity and a high adsorption rate;
- the complex structure and multi-layer adsorption materials of the new complex reactor effectively increase the contact time of adsorbent materials, microorganisms and pollutants, and improve the adsorption removal rate and biodegradation rate of tebuconazole in water;
- the multi-layer honeycomb polymer support frame in the reactor effectively reduces the swelling and accumulation pressure between the adsorbent materials, avoids the breakage and loss of the adsorbent material, and at the same time, the reduction of the height of the single-layer adsorbent material layer also effectively avoids the knotting. And blockage;
- a double reactor consisting of a reactor shell, a reactor inner casing, an inlet pipe, a water distributor, an outlet pipe, an aeration pipe, an aeration head, an exhaust pipe, a gas collecting reflection cone, and a honeycomb It is composed of a support frame, a resin loaded with microorganisms, a backwash water inlet pipe, and a backwash water outlet pipe.
- the inlet pipe of the double reactor is connected to the reactor casing at the top of the reactor; the exhaust pipe is connected to the inner casing of the reactor near the conical gas collecting hood; the outlet pipe is in the upper part of the reactor, and the lower part of the conical collecting hood Connected to the inner shell of the reactor; the honeycomb support is placed in the inner shell of the reactor, filled with resin carrying microorganisms; the water distributor is at the bottom of the inner shell of the reactor; and the backwash water outlet pipe is in each layer of the honeycomb support frame Above, connected to the inner casing of the reactor; the backwash water inlet pipe is connected to the outer casing at the bottom of the porous water distribution plate of the reactor; the aeration pipe is connected to the aeration head, and the position of the aeration head is directly above the water distribution plate of the reactor .
- a system for removing tebuconazole from water by using a microorganism-loaded resin and a double reactor which comprises an additional nutrient solution storage tank, an influent water sample adjustment tank, a backwash water collection tank, a double reactor, a backwash water storage tank, Filter, flow meter, water pump, aeration pump.
- the storage tank of the additional nutrient solution is connected with the water inlet regulating tank, and the double reactor is respectively connected with the water inlet adjusting tank, the backwash water storage tank, the backwash water outlet collecting tank and the aeration pump.
- a method for removing tebuconazole in water by using a novel adsorption-microbial degradation composite reactor the steps of which include:
- Step 1 Prepare a microbial adsorption resin:
- Sphingomonas sp. Sphingomonas sp.
- Sphingomonas sp. was first isolated from the soil.
- Japanese scholar Yabuuchi et al. first proposed Sphingomonas. Takeuchi was equal to 1993.
- Sphingomonas is a subclass of 4 variant bacteria.
- the strains of this genus are Gram-negative bacteria, no spores, unilaterally producing polar flagella, mostly yellow. Obligate aerobic and capable of producing catalase.) Colonies are inoculated into liquid beef peptone medium in the dark, at a temperature of 28 ° C;
- Resin-loaded microorganism the collected cells are inoculated into a mineral liquid medium, and the resin is added and shake cultured for 3-5 days to obtain a microbial-loaded adsorption resin;
- the microorganism-loaded adsorption resin is washed with deionized water and filled into the honeycomb support of the double reactor.
- the strain used was Sphingomonas sp.
- the resin used was an adsorption resin of a polystyrene or polyacrylate skeleton.
- Adjusting the influent flow rate and the flow rate of the additional nutrient solution controlling the water sample COD Cr in the influent water regulating tank to be no less than 20 mg/L, and the water sample enters the double reactor through the inlet pipe to open the aeration pump;
- the applied nutrient solution is methanol One of ethanol, glucose, and sodium acetate solutions.
- Step 3 Adsorption-microbial degradation of tebuconazole:
- the water sample passes through the resin of the multi-layer loaded microorganism, the tebuconazole is adsorbed and removed by the resin, and the adsorbed water is discharged from the outlet pipe, and the microorganisms attached to the resin utilize the external nutrient solution and the pentane in the water.
- oxazolol degrades the tebuconazole adsorbed on the resin, and the water sample has a hydraulic retention time of not less than 30 minutes in the double reactor.
- Step 4 Backwashing: After 7-10 days of operation, some of the bacteria will die and fall off due to the metabolism of the microorganisms attached to the resin. Close the pump, valve and outlet valve of the inlet pipe, open the backwash water inlet pipe and backwash.
- the valve of the water outlet pipe has a backwashing time of not less than 2 minutes, the backwash water enters the backwash water outlet tank, and is discharged into the sewage treatment plant for treatment; the valves of the backwash water inlet pipe and the backwash water outlet pipe are closed, Open the pump, valve and outlet valve of the inlet line and continue operation.
- the complex reactor integrates various functions such as water inflow, water distribution, aeration, exhaust, adsorption, biodegradation and backwashing, and can be continuously operated, and has the advantages of high processing efficiency and small floor space;
- the multi-layer honeycomb support frame and screen can not only reduce the increase of the stacking pressure caused by the excessively high resin layer, but also the large pressure breakage and loss caused by the swelling of the resin layer water; it can also avoid the formation of the entire layer of resin. Increased water resistance can reduce head loss and save power consumption;
- Resin loaded with Sphingomonas sp. strain can effectively adsorb tebuconazole in water, has large adsorption capacity and high adsorption rate, and does not change water quality while removing tebuconazole in water;
- Figure 1 is a schematic view showing the structure of the double reactor in the embodiment of the present invention (labeled: 1-reactor outer casing; 2-reactor inner shell; 3-reactor drain pipe; 4-backwash water outlet pipe; 5-aeration head; - water distributor; 7-inlet pipe; 8-exhaust pipe; 9-gas collecting reflector; 10-cell support frame; 11-loaded microbial resin; 12-aeration pipe; 13-backwash water Water pipe).
- FIG. 2 is a schematic structural view (support frame, inner screen) of the honeycomb support frame in the double reactor of the present invention
- the left frame is the support frame wall
- the right picture is the screen at the bottom and the top of the support frame to prevent the resin from being flowed by water. Washed away.
- Figure 3 is a schematic view of the overall structure of the system of the present invention (labeled: 14 - additional nutrient solution storage tank; 15 - water inlet conditioning tank; 16 - backwash water outlet tank; 17 - duplex reactor; 18 - backwash water Storage tank; 19-filter; 20-flow meter; 21-water pump; 22-aeration pump).
- FIG. 4 is a flow chart of a method of the present invention.
- FIG. 3 The overall structure of the treatment pilot system is shown in FIG. 3, including: an additional nutrient solution storage tank 14, an influent water regulating tank 15, a backwash water collecting tank 16, a double reactor 17, a backwash water tank 18, a filter 19, The flow meter 20, the water pump 21, and the aeration pump 22.
- the additional nutrient solution storage tank 14 is connected to the influent water regulating tank 15, and the double reactor 17 is respectively combined with the influent water regulating tank (15), the backwash water storage tank 18, the backwash water outlet tank 16 and the aeration pump (22).
- a water pump 21, a filter 19, and a flow meter 20 are disposed between the duplex reactor 17 and the water inlet regulating tank (15).
- the structure of the duplex reactor 17 used is as shown in FIG. 1 and includes: a reactor shell 1, a reactor inner shell 2, an inlet pipe 7, a water distributor 6, an outlet pipe 3, an aeration pipe 12, an aeration head 5, and an exhaust gas.
- the tube 8, the gas collecting reflection cone 9, the honeycomb support frame 10, the microorganism-loaded resin 11, the backwash water inlet pipe 13, and the backwash water outlet pipe 4 are composed.
- the inlet pipe 7 of the double reactor is connected to the reactor casing 1 at the top of the reactor; the exhaust pipe 8 is connected to the reactor inner casing 2 near the tapered gas collecting hood; the outlet pipe 3 is at the upper part of the reactor, and the cone The lower part of the collecting hood is connected to the inner casing 2 of the reactor; the honeycomb supporting frame (10) is shown in Fig.
- the water distributor 6 is reacting The bottom of the inner casing 2; the backwash water outlet pipe 4 is connected to the reactor inner casing 2 on each layer of the honeycomb support frame 10; the backwash water inlet pipe 13 is in the reactor water distributor 6 (porous water distribution plate) The bottom is connected to the outer casing 1; the aeration pipe 12 is connected to the aeration head 5, and the position of the aeration head 5 is directly above the reactor water distributor 6.
- Step 1 Prepare a microbial adsorption resin:
- Microbial culture First, the colony of Sphingomonas sp. in the plate is inoculated into liquid beef peptone medium in the dark, at a temperature of 28 degrees Celsius;
- Resin-loaded microorganism the collected cells are inoculated into a mineral liquid medium, and the polystyrene adsorption resin is added, followed by shaking culture for 3 days to obtain a microbial-loaded adsorption resin;
- the microorganism-loaded adsorption resin is washed with deionized water and filled into a honeycomb support frame of the double reactor.
- Step 2 Influent water: adjust the influent flow rate and the flow rate of the additional nutrient solution (methanol solution), and control the water sample COD Cr in the influent water regulating tank to be 25 ⁇ 5 mg/L, wherein the tebuconazole concentration is 4.0 ⁇ 0.5 mg/L. .
- the water sample enters the double reactor through the inlet pipe and opens the aeration pump.
- Step 3 Adsorption-microbial degradation of tebuconazole:
- the water sample passes through the resin of the multi-layer loaded microorganism, the tebuconazole is adsorbed and removed by the resin, and the adsorbed water is discharged from the outlet pipe, and the microorganisms attached to the resin utilize the external nutrient solution and the pentane in the water.
- oxazolol degrades the tebuconazole adsorbed on the resin, and the water sample has a hydraulic retention time of 30 minutes in the duplex reactor.
- the effluent COD Cr is less than or equal to 15 mg/L, and the concentration of tebuconazole in the water is 0.1 mg/L or less.
- Step 4 Backwashing: After 7 days of operation, some of the bacteria will die and fall off due to the metabolism of the microorganisms attached to the resin. Close the pumps, valves and outlet valves of the water inlet pipe, and open the backwash water inlet pipe and backwash water. The valve of the water pipe, the backwashing time is 2 minutes, the backwash water enters the backwash water outlet tank, and is discharged into the sewage treatment plant for treatment. Close the valves of the backwash water inlet pipe and the backwash water outlet pipe, open the pump, valve and outlet pipe valves of the inlet pipe and continue to operate.
- the processing system used was the same as in Example 1.
- Step 1 Prepare a microbial adsorption resin:
- Microbial culture First, the colony of Sphingomonas sp. in the plate is inoculated into liquid beef peptone medium in the dark, at a temperature of 28 degrees Celsius;
- Resin-loaded microorganism the collected cells are inoculated into a mineral liquid medium, and the polyacrylate adsorption resin is added, followed by shaking culture for 4 days to obtain a microbial-loaded adsorption resin;
- the microorganism-loaded adsorption resin is washed with deionized water and filled into the honeycomb support of the double reactor.
- Step 2 Influent water: adjust the influent flow rate and the flow rate of the additional nutrient solution (glucose solution), and control the water sample COD Cr in the influent water regulating tank to be 40 ⁇ 5 mg/L, wherein the tebuconazole concentration is 10.0 ⁇ 0.5 mg/L. .
- the water sample enters the double reactor through the inlet pipe and opens the aeration pump.
- Step 3 Adsorption-microbial degradation of tebuconazole:
- the water sample passes through the resin of the multi-layer loaded microorganism, the tebuconazole is adsorbed and removed by the resin, and the adsorbed water is discharged from the outlet pipe, and the microorganisms attached to the resin utilize the external nutrient solution and the pentane in the water.
- oxazolol degrades the tebuconazole adsorbed on the resin, and the water sample has a hydraulic retention time of 50 minutes in the duplex reactor.
- the effluent COD Cr is less than or equal to 20 mg/L, and the concentration of tebuconazole in the water is 0.2 mg/L or less.
- Step 4 Backwashing: After 8 days of operation, some of the bacteria will die and fall off due to the metabolism of the microorganisms attached to the resin. Close the pump, valve and outlet valve of the water inlet pipe, open the backwash water inlet pipe and backwash water. The valve of the water pipe, the backwashing time is 3 minutes, the backwash water enters the backwash water outlet tank, and is discharged into the sewage treatment plant for treatment. Close the valves of the backwash water inlet pipe and the backwash water outlet pipe, open the pump, valve and outlet pipe valves of the inlet pipe and continue to operate.
- Effluent COD Cr (mg/L) 17 15 11 19 15 17 20 15 Concentration of tebuconazole (mg/L) 0.15 0.17 0.10 0.19 0.20 0.11 0.14 0.16
- the processing system used was the same as in Example 1.
- Step 1 Prepare a microbial adsorption resin:
- Microbial culture First, the colony of Sphingomonas sp. in the plate is inoculated into liquid beef peptone medium in the dark, at a temperature of 28 degrees Celsius;
- Resin-loaded microorganism the collected cells are inoculated into a mineral liquid medium, and the polystyrene adsorption resin is added, followed by shaking culture for 5 days to obtain a microbial-loaded adsorption resin;
- the microorganism-loaded adsorption resin is washed with deionized water and filled into the honeycomb support of the double reactor.
- Step 2 Influent water: adjust the influent flow rate and the flow rate of the additional nutrient solution (sodium acetate solution), and control the water sample COD Cr in the influent water regulating tank to be 60 ⁇ 5 mg/L, wherein the tebuconazole concentration is 20.0 ⁇ 0.5 mg/ L.
- the water sample enters the double reactor through the inlet pipe and opens the aeration pump.
- Step 3 Adsorption-microbial degradation of tebuconazole:
- the water sample passes through the resin of the multi-layer loaded microorganism, the tebuconazole is adsorbed and removed by the resin, and the adsorbed water is discharged from the outlet pipe, and the microorganisms attached to the resin utilize the external nutrient solution and the pentane in the water.
- oxazolol degrades the tebuconazole adsorbed on the resin, and the water sample has a hydraulic retention time of 80 minutes in the duplex reactor.
- the effluent COD Cr is less than or equal to 25 mg/L, and the concentration of tebuconazole in the water is 0.30 mg/L or less.
- Step 4 Backwashing: After 10 days of operation, some of the bacteria will die and fall off due to the metabolism of the microorganisms attached to the resin. Close the pump, valve and outlet valve of the inlet pipe, open the backwash water inlet pipe and backwash water. The valve of the water pipe, the backwashing time is 5 minutes, the backwash water enters the backwash water outlet tank, and is discharged into the sewage treatment plant for treatment. Close the valves of the backwash water inlet pipe and the backwash water outlet pipe, open the pump, valve and outlet pipe valves of the inlet pipe and continue to operate.
- the processing system used was the same as in Example 1.
- Step 1 Prepare a microbial adsorption resin:
- Microbial culture First, the colony of Sphingomonas sp. in the plate is inoculated into liquid beef peptone medium in the dark, at a temperature of 28 degrees Celsius;
- Resin-loaded microorganism the collected cells are inoculated into a mineral liquid medium, and the polyacrylate adsorption resin is added, followed by shaking culture for 3 days to obtain a microbial-loaded adsorption resin;
- the microorganism-loaded adsorption resin is washed with deionized water and filled into the honeycomb support of the double reactor.
- Step 2 Influent water: adjust the influent flow rate and the flow rate of the external nutrient solution (ethanol solution), and control the water sample COD Cr in the influent water regulating tank to be 80 ⁇ 5 mg/L, wherein the tebuconazole concentration is 25.0 ⁇ 0.5 mg/L. .
- the water sample enters the double reactor through the inlet pipe and opens the aeration pump.
- Step 3 Adsorption-microbial degradation of tebuconazole:
- the water sample passes through the resin of the multi-layer loaded microorganism, the tebuconazole is adsorbed and removed by the resin, and the adsorbed water is discharged from the outlet pipe, and the microorganisms attached to the resin utilize the external nutrient solution and the pentane in the water.
- oxazolol degrades the tebuconazole adsorbed on the resin, and the water sample has a hydraulic retention time of 80 minutes in the duplex reactor.
- the effluent COD Cr is less than 25 mg/L, and the concentration of tebuconazole in the water is less than or equal to 0.5 mg/L.
- Step 4 Backwashing: After 9 days of operation, some of the bacteria will die and fall off due to the metabolism of the microorganisms attached to the resin. Close the pump, valve and outlet valve of the water inlet pipe, open the backwash water inlet pipe and backwash water. The valve of the water pipe, the backwashing time is 4 minutes, the backwash water enters the backwash water outlet tank, and is discharged into the sewage treatment plant for treatment. Close the valves of the backwash water inlet pipe and the backwash water outlet pipe, open the pump, valve and outlet pipe valves of the inlet pipe and continue to operate.
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Abstract
本发明公开了一种用于去除水中戊唑醇复式反应器及其系统和方法,属于水处理领域。含戊唑醇的水样经进水口进入复式反应器夹层,后经布水器进入复式反应器内层,水中戊唑醇被内层负载微生物的树脂吸附去除,吸附出水中戊唑醇浓度低于国家农药废水排放标准限值。负载在树脂上的微生物以水中有机碳为碳源,降解吸附在树脂上的戊唑醇。该系统与方法不仅打破了传统微生物降解法抗水质波动性差、降解时间长的不足,同时也解决了树脂吸附法中吸附饱和树脂的原位再生问题,有效克服树脂脱附再生过程中产生的脱附液容易造成二次污染的难题。
Description
本发明公开了一种去除水中戊唑醇的系统与方法,更具体地说是一种用于去除水中戊唑醇复式反应器及其系统和方法,即一种负载微生物的树脂与复式反应器相集成的去除水中戊唑醇的系统与方法。
农药在控制农作物病虫害、提高农作物产量方面发挥着极其重要的作用,然而伴随着农业生产对农药的依赖性日益增加,农药对土壤、水体的污染也愈来愈严重。通常实施在农作物上的农药仅有不足0.3%的剂量有效作用于害虫,剩余99.7%的农药则残留在农作物表面与自然环境中的土壤、水体中,最终随着降雨和灌溉水进入到河流、湖泊以及地下水中,对人类和其他水生物造成潜在的健康危害。戊唑醇制剂作为一种重要的农药在世界上得到广泛应用,可有效地防治禾谷类作物的多种锈病、白粉病、网斑病、根腐病、赤霉病和黑穗病,果树上的叶斑病、锈病、白粉病和黑星病等多种真菌性病害。目前已经在50多个国家的65种农作物上获得登记,而由此带来的环境问题也日益显现。虽然戊唑醇在环境中残留浓度不高,但其对环境的危害和潜在风险不容忽视,很多学者对戊唑醇废水治理进行了研究。目前,文献报道的对戊唑醇的去除方法主要有三类:
第一类是以生化法为主,利用微生物将戊唑醇的结构破坏,使其转变为毒性更低或更易于降解的小分子,虽然生物降解法是一种经济的处理技术,但是它有如下缺陷限制了其对戊唑醇废水的治理与应用:(1)抗水质波动能力弱,承受不了废水中高污染负荷冲击;(2)微生物降解戊唑醇的过程较为缓慢,通常要3-5天,比传统的吸附、化学氧化法慢。虽然有文献报道筛选和培养降解戊唑醇的菌种(吴红萍等,戊唑醇农药降解菌的筛选及其降解效能初探,农药,2013年2月10),但该文献并没有鉴定是何种菌种,也没有实际应用该菌种降解水中戊唑醇,并开发出相应的成套技术和系统。因此,国内应用生物降解技术去除水中的戊唑醇的研究尚未见报道。
第二类则是以吸附法为主,将戊唑醇从水体中分离出来,不改变其化学结构,虽然吸附法是在实验室或者工业生产中最常用和效率比较高的处理方法,但是这
种物理处理方法最大的缺陷是吸附后的吸附材料需要脱附再生,因此产生的脱附液需要有效处置,否则会造成二次污。目前吸附法研究主要集中在用活性炭吸附戊唑醇,而采用树脂吸附技术去除废水中戊唑醇的研究尚未见报道。
第三类则是用化学药剂氧化戊唑醇,目前这个方法已经有专利报道(一种利用固定化微生物治理有机磷农药废水的方法,公开号:CN103102015A),然而这种方法在使用过程中需要投加多种药剂,操作复杂,运行成本也较高,不是一种高效经济的方法,特别是对于低浓度戊唑醇的去除过程中,由于过量药剂的添加,有可能造成水质恶化和生物毒性增加。
因此如何集上述方法的优点,克服各自的不足,在此基础上开发高效去除水中戊唑醇处理系统和方法有着重要的应用价值。
发明内容
1.要解决的技术问题
针对现有水中戊唑醇去除方法中的不足,本发明提供一种利用新型复式反应器与负载微生物的树脂去除水中戊唑醇的系统和方法,采用新型负载微生物的吸附树脂作为复式反应器的吸附填料,快速吸附去除水中戊唑醇,同时通过负载在树脂上的微生物降解被吸附的戊唑醇,实现吸附树脂的原位再生。
现有公开专利中针对农药废水的治理方法主要有氧化法、生物降解法和吸附法,而针对戊唑醇去除方法很少,仅报道了氧化法。上述方法虽然有自身的优势并已经应用在农药废水的治理,但在实际应用过程中依然存在一些不足,需要改进和提高:
(1)对比现有基于氧化为核心的技术(对比专利1名称:戊唑醇农药废水处理工艺CN 102923919 A):采用芬顿氧化、二氧化氯氧化、铁碳-混凝集成工艺氧化降解戊唑醇。然而对比专利所述方法在去除水中戊唑醇时存在以下不足:
处理过程中需要调节pH值,消耗大量酸碱;Fenton氧化过程和铁碳-混凝沉淀过程会产生大量泥渣和沉淀物,此类物质是危险固废,需要进行安全处置,费用较高;该方法通常用于高浓废水的处理,然而对于低浓度尾水中的戊唑醇难以去除,也不经济;处置过程中大量化学药剂的投加,严重改变了水体的水质条件,不利于水生态系统的平衡和保护;
(2)对比现有基于生物降解为核心的农药废水治理技术(对比专利2名称:一
种利用固定化微生物治理有机磷农药废水的方法,公开号:CN103102015A):驯化的真菌黑曲霉吸附到直径为5-8mml的活性炭上,然后将制得含有饱和黑曲霉的活性炭投入到废水之中,降解有机磷农药。然而对比专利所述方法在去除水中戊唑醇时存在以下不足:黑曲霉菌仅能降解有机磷农药,无法降解水中戊唑醇;活性炭主要为微孔结构,不仅吸附容量小、吸附速率低,且菌种附着后导致其微孔堵塞,难以发挥吸附作用,仅能作为菌种的载体;没有提供配套的反应器和处理系统,活性炭投加在水中不易进行分离,难以实际应用。
(3)基于吸附为核心的农药废水治理技术(对比专利3名称:一种农药工业废水深度处理方法,公开号:CN101746930 A):经好氧生化处理后的喹硫磷农药的生产废水与磁性树脂连续动态吸附,用上流式悬浮床磁性树脂接触反应器做为吸附反应器,连续进出水,吸附去除水中污染物。然而对比专利所述方法存在以下不足:磁性树脂主要通过离子交换作用去除污染物,而戊唑醇在水中并非离子态,因此无法通过离子交换作用去除;磁性树脂吸附污染物后需用盐水再生,再生液处置过程中会产生二次污染。
2.技术方案
本发明利用复式反应器中的多层树脂吸附去除水中的戊唑醇,然后通过负载在树脂上的菌种微生物降解吸附在树脂上的戊唑醇,树脂得到原位再生,从而可以实现连续进水出水运行模式。
相比较已有文献报道和公开的专利技术与方法,本发明的创新点如下:
(1)采用高分子聚合物的树脂吸附材料作为微生物载体,不仅能够负载微生物,还可以吸附水中戊唑醇,且吸附容量大、吸附速率高;
(2)通过负载在树脂上的鞘氨醇单胞菌(Sphingomonas sp.)菌种,对吸附在树脂上的戊唑醇有很好的降解作用,吸附后的树脂无需外加脱附液脱附再生。在去除水中戊唑醇的同时不会改变水质,也不会产生额外的脱附液和废渣;
(3)新型复式反应器的复式结构和多层吸附材料,有效增加吸附材料、微生物与污染物接触时间,提高对水中戊唑醇的吸附去除率与生物降解率;
(4)反应器内多层蜂窝状聚合物支撑架,有效减少吸附材料间的溶胀与堆积压力,避免吸附材料的破碎和流失,同时单层吸附材料层高的减小也有效的避免了板结和堵塞现象;
一种复式反应器,由下述部件构成:反应器外壳、反应器内壳、进水管、布水器、出水管、曝气管、曝气头、排气管、集气反射锥体、蜂窝状支撑架、负载微生物的树脂、反冲洗水进水管、反冲洗水出水管组成。其中,复式反应器的进水管在反应器顶部,与反应器外壳相连;排气管在锥形集气罩附近,与反应器内壳相连;出水管在反应器上部、锥形集气罩下部,与反应器内壳相连;蜂窝状支撑架在反应器内壳内,里面填充有负载微生物的树脂;布水器在反应器内壳底部;反冲洗水出水管在每层蜂窝状支撑架的上面,与反应器内壳相连;反冲洗水进水管在反应器的多孔布水板底部,与外壳相连;曝气管连接曝气头,曝气头的位置在反应器布水板的正上方。
一种利用负载微生物的树脂与复式反应器去除水中戊唑醇的系统,其由外加营养溶液储备槽、进水水样调节槽、反冲洗水收集槽、复式反应器、反冲洗水储备槽、过滤器、流量计、水泵、曝气泵组成。其中,外加营养溶液存储槽与进水调节槽相连,复式反应器分别与进水调节槽、反冲洗水存储槽、反冲洗水出水收集槽、曝气泵相连。
一种利用新型吸附-微生物降解复合反应器去除水中戊唑醇的方法,其步骤包括:
步骤1、制备负载微生物的吸附树脂:
a.微生物培养:首先将平板中的鞘氨醇单胞菌(Sphingomonas sp.,土壤中分离得到,1990年日本学者Yabuuchi等首次提出鞘氨醇单胞菌属。Takeuchi等于1993年对此作了修正。根据16S rRNA序列比较,鞘氨醇单胞菌属于变形细菌的4亚类。该属的菌株均为革兰氏阴性菌,无孢子,以单侧生极性鞭毛运动,多呈黄色,专性需氧且能产生过氧化氢酶。)菌落接种到液体牛肉蛋白胨培养基中避光培养,温度28摄氏度;
b.菌体收集:将处于对数生长期的菌体培养液离心分离(离心时间20分钟,转速5000G),分离得到的菌体用磷酸氢二钠与磷酸二氢钾配制的缓冲液(pH=7.3)清洗;
c.树脂负载微生物:将收集的菌体接种到矿物质液体培养基中,加入树脂后进行振荡培养3-5天,得到负载微生物的吸附树脂;
d.填充树脂:将负载微生物的吸附树脂用去离子水清洗,填充到复式反应器的蜂窝状支撑架里。
所用菌种为鞘氨醇单胞菌(Sphingomonas sp.),所用树脂为聚苯乙烯、聚丙烯酸酯类骨架的吸附树脂。
步骤2、进水:
调节进水流量和外加营养溶液流量,控制进水调节槽中的水样CODCr不低于20mg/L,水样通过进水管进入复式反应器,打开曝气泵;所用的外加营养溶液为甲醇、乙醇、葡萄糖、乙酸钠溶液中的一种。
步骤3、吸附-微生物降解戊唑醇:水样经过多层负载微生物的树脂,戊唑醇被树脂吸附去除,吸附出水由出水管排出,同时树脂上附载的微生物利用水中的外加营养溶液和戊唑醇作为碳源,将吸附在树脂上的戊唑醇降解,水样在复式反应器中水力停留时间不低于30分钟。
步骤4.反冲洗:运行7-10天后,由于树脂上附载微生物的代谢会导致部分菌体死亡和脱落,关闭进水管路的泵、阀门和出水管阀门,打开反冲洗水进水管和反冲洗水出水管的阀门,反冲洗时间不低于2分钟,反冲洗水进入到反冲洗水出水收集槽,而后排入污水处理厂处理;关闭反冲洗水进水管和反冲洗水出水管的阀门,打开进水管路的泵、阀门和出水管阀门,继续运行。
3、有益效果
(1)复式反应器集进水、布水、曝气、排气、吸附、生物降解、反冲洗等多种功能于一体,可以连续运行,具有处理效率高、占地面积小的优点;
(2)多层蜂窝状支撑架和筛网不仅可以减小树脂层过高导致堆积压力增大,以及树脂层水中溶胀而产生的巨大压力破碎流失;还可以避免整层树脂相互板结导致的过水阻力增加,因此能够减少水头损失,节省动力消耗;
(3)负载鞘氨醇单胞菌(Sphingomonas sp.)菌种的树脂,可有效吸附水中戊唑醇,吸附容量大、吸附速率高,在去除水中戊唑醇的同时不改变水质;
(4)吸附后的树脂无需转移,也不需要用脱附剂脱附再生,而是利用树脂上负载的鞘氨醇单胞菌(Sphingomonas sp.)菌种降解树脂上吸附的戊唑醇,实现了树脂的原位再生,且不产生脱附液。
图1实施例中复式反应器结构示意图(图中标注:1-反应器外壳;2-反应器内壳;3-反应器排水管;4-反冲洗水出水管;5-曝气头;6-布水器;7-进水管;8-排气管;9-集气反射锥体;10-蜂窝状支撑架;11-负载微生物的树脂;12-曝气管;13-反冲洗水进水管)。
图2为本发明中复式反应器内蜂窝状支撑架的结构示意图(支撑架、内部筛网),左图为支撑架壁,右图为支撑架底部和顶部部的筛网,防止树脂被水流冲走。图3为本发明的系统总体结构示意图(图中标注:14-外加营养液储备槽;15-进水调节槽;16-反冲洗水出水收集槽;17-复式反应器;18-反冲洗水储槽;19-过滤器;20-流量计;21-水泵;22-曝气泵)。
图4为本发明的方法流程图。
以下通过实施例进一步说明本发明。
实施例1:
处理中试系统总体结构如图3所示,包括:外加营养溶液储备槽14、进水调节槽15、反冲洗水收集槽16、复式反应器17、反冲洗水储槽18、过滤器19、流量计20、水泵21、曝气泵22。其中,外加营养溶液存储槽14与进水调节槽15相连,复式反应器17分别与进水调节槽(15)、反冲洗水储槽18、反冲洗水出水收集槽16和曝气泵(22)相连;复式反应器17与进水调节槽(15)之间设置有水泵21、过滤器19和流量计20。
所用复式反应器17结构如图1所示,包括:反应器外壳1、反应器内壳2、进水管7、布水器6、出水管3、曝气管12、曝气头5、排气管8、集气反射锥体9、蜂窝状支撑架10、负载微生物的树脂11、反冲洗水进水管13、反冲洗水出水管4组成。其中,复式反应器的进水管7在反应器顶部,与反应器外壳1相连;排气管8在锥形集气罩附近,与反应器内壳2相连;出水管3在反应器上部、锥形集气罩下部,与反应器内壳2相连;蜂窝状支撑架(10)如图2所示,在反应器内壳2内,里面填充有负载微生物的树脂11;布水器6在反应器内壳2底部;反冲洗水出水管4在每层蜂窝状支撑架10的上面,与反应器内壳2相连;反冲洗水进水管13在反应器的布水器6(多孔布水板)底部,与外壳1相连;曝气管12连接曝气头5,曝气头5的位置在反应器布水器6的正上方。
水中戊唑醇的去除方法流程如图4所示,其步骤具体如下:
步骤1、制备负载微生物的吸附树脂:
a.微生物培养:首先将平板中的鞘氨醇单胞菌(Sphingomonas sp.,)菌落接种到液体牛肉蛋白胨培养基中避光培养,温度28摄氏度;
b.菌体收集:将处于对数生长期的菌体培养液离心分离(离心时间20分钟,转速5000G),分离得到的菌体用磷酸氢二钠与磷酸二氢钾配制的缓冲液(pH=7.3)清洗;
c.树脂负载微生物:将收集的菌体接种到矿物质液体培养基中,加入聚苯乙烯吸附树脂后进行振荡培养3天,得到负载微生物的吸附树脂;
d.填充树脂:将负载微生物的吸附树脂用去离子水清洗,填充到复式反应器的蜂窝状支撑架内。
步骤2、进水:调节进水流量和外加营养溶液(甲醇溶液)流量,控制进水调节槽中的水样CODCr为25±5mg/L,其中戊唑醇浓度为4.0±0.5mg/L。水样通过进水管进入复式反应器,打开曝气泵。
步骤3、吸附-微生物降解戊唑醇:水样经过多层负载微生物的树脂,戊唑醇被树脂吸附去除,吸附出水由出水管排出,同时树脂上附载的微生物利用水中的外加营养溶液和戊唑醇作为碳源,将吸附在树脂上的戊唑醇降解,水样在复式反应器中水力停留时间30分钟。出水CODCr小于等于15mg/L,水中戊唑醇浓度小于等于0.1mg/L。
步骤4.反冲洗:运行7天后,由于树脂上附载微生物的代谢会导致部分菌体死亡和脱落,关闭进水管路的泵、阀门和出水管阀门,打开反冲洗水进水管和反冲洗水出水管的阀门,反冲洗时间2分钟,反冲洗水进入到反冲洗水出水收集槽,而后排入污水处理厂处理。关闭反冲洗水进水管和反冲洗水出水管的阀门,打开进水管路的泵、阀门和出水管阀门,继续运行。
实施例1的运行效果
运行时间(天) | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
进水CODCr(mg/L) | 25 | 28 | 27 | 23 | 29 | 21 | 27 |
进水戊唑醇浓度(mg/L) | 3.7 | 3.9 | 4.2 | 3.7 | 4.4 | 4.5 | 4.3 |
出水CODCr(mg/L) | 8 | 12 | 11 | 9 | 15 | 14 | 13 |
出水戊唑醇浓度(mg/L) | 0.05 | 0.07 | 0.08 | 0.09 | 0.07 | 0.08 | 0.10 |
实施例2:
所用处理系统同实施例1。
步骤1、制备负载微生物的吸附树脂:
a.微生物培养:首先将平板中的鞘氨醇单胞菌(Sphingomonas sp.)菌落接种到液体牛肉蛋白胨培养基中避光培养,温度28摄氏度;
b.菌体收集:将处于对数生长期的菌体培养液离心分离(离心时间20分钟,转速5000G),分离得到的菌体用磷酸氢二钠与磷酸二氢钾配制的缓冲液(pH=7.3)清洗;
c.树脂负载微生物:将收集的菌体接种到矿物质液体培养基中,加入聚丙烯酸酯吸附树脂后进行振荡培养4天,得到负载微生物的吸附树脂;
d.填充树脂:将负载微生物的吸附树脂用去离子水清洗,填充到复式反应器的蜂窝状支撑架里。
步骤2、进水:调节进水流量和外加营养溶液(葡萄糖溶液)流量,控制进水调节槽中的水样CODCr为40±5mg/L,其中戊唑醇浓度为10.0±0.5mg/L。水样通过进水管进入复式反应器,打开曝气泵。
步骤3、吸附-微生物降解戊唑醇:水样经过多层负载微生物的树脂,戊唑醇被树脂吸附去除,吸附出水由出水管排出,同时树脂上附载的微生物利用水中的外加营养溶液和戊唑醇作为碳源,将吸附在树脂上的戊唑醇降解,水样在复式反应器中水力停留时间50分钟。出水CODCr小于等于20mg/L,水中戊唑醇浓度小于等于0.2mg/L。
步骤4.反冲洗:运行8天后,由于树脂上附载微生物的代谢会导致部分菌体死亡和脱落,关闭进水管路的泵、阀门和出水管阀门,打开反冲洗水进水管和反冲洗水出水管的阀门,反冲洗时间3分钟,反冲洗水进入到反冲洗水出水收集槽,而后排入污水处理厂处理。关闭反冲洗水进水管和反冲洗水出水管的阀门,打开进水管路的泵、阀门和出水管阀门,继续运行。
实施例2的运行效果
运行时间(天) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
进水CODCr(mg/L) | 45 | 38 | 37 | 43 | 39 | 41 | 44 | 42 |
进水戊唑醇浓度(mg/L) | 9.7 | 9.9 | 10.2 | 9.8 | 10.4 | 10.5 | 10..3 | 10.1 |
出水CODCr(mg/L) | 17 | 15 | 11 | 19 | 15 | 17 | 20 | 15 |
出水戊唑醇浓度(mg/L) | 0.15 | 0.17 | 0.10 | 0.19 | 0.20 | 0.11 | 0.14 | 0.16 |
实施例3
所用处理系统同实施例1。
步骤1、制备负载微生物的吸附树脂:
a.微生物培养:首先将平板中的鞘氨醇单胞菌(Sphingomonas sp.)菌落接种到液体牛肉蛋白胨培养基中避光培养,温度28摄氏度;
b.菌体收集:将处于对数生长期的菌体培养液离心分离(离心时间20分钟,转速5000G),分离得到的菌体用磷酸氢二钠与磷酸二氢钾配制的缓冲液(pH=7.3)清洗;
c.树脂负载微生物:将收集的菌体接种到矿物质液体培养基中,加入聚苯乙烯吸附树脂后进行振荡培养5天,得到负载微生物的吸附树脂;
d.填充树脂:将负载微生物的吸附树脂用去离子水清洗,填充到复式反应器的蜂窝状支撑架里。
步骤2、进水:调节进水流量和外加营养溶液(乙酸钠溶液)流量,控制进水调节槽中的水样CODCr为60±5mg/L,其中戊唑醇浓度为20.0±0.5mg/L。水样通过进水管进入复式反应器,打开曝气泵。
步骤3、吸附-微生物降解戊唑醇:水样经过多层负载微生物的树脂,戊唑醇被树脂吸附去除,吸附出水由出水管排出,同时树脂上附载的微生物利用水中的外加营养溶液和戊唑醇作为碳源,将吸附在树脂上的戊唑醇降解,水样在复式反应器中水力停留时间80分钟。出水CODCr小于等于25mg/L,水中戊唑醇浓度小于等于0.30mg/L。
步骤4.反冲洗:运行10天后,由于树脂上附载微生物的代谢会导致部分菌体死亡和脱落,关闭进水管路的泵、阀门和出水管阀门,打开反冲洗水进水管和反冲洗水出水管的阀门,反冲洗时间5分钟,反冲洗水进入到反冲洗水出水收集槽,而后排入污水处理厂处理。关闭反冲洗水进水管和反冲洗水出水管的阀门,打开进水管路的泵、阀门和出水管阀门,继续运行。
实施例3的运行效果
实施例4
所用处理系统同实施例1。
步骤1、制备负载微生物的吸附树脂:
a.微生物培养:首先将平板中的鞘氨醇单胞菌(Sphingomonas sp.)菌落接种到液体牛肉蛋白胨培养基中避光培养,温度28摄氏度;
b.菌体收集:将处于对数生长期的菌体培养液离心分离(离心时间20分钟,转速5000G),分离得到的菌体用磷酸氢二钠与磷酸二氢钾配制的缓冲液(pH=7.3)清洗;
c.树脂负载微生物:将收集的菌体接种到矿物质液体培养基中,加入聚丙烯酸酯吸附树脂后进行振荡培养3天,得到负载微生物的吸附树脂;
d.填充树脂:将负载微生物的吸附树脂用去离子水清洗,填充到复式反应器的蜂窝状支撑架里。
步骤2、进水:调节进水流量和外加营养溶液(乙醇溶液)流量,控制进水调节槽中的水样CODCr为80±5mg/L,其中戊唑醇浓度为25.0±0.5mg/L。水样通过进水管进入复式反应器,打开曝气泵。
步骤3、吸附-微生物降解戊唑醇:水样经过多层负载微生物的树脂,戊唑醇被树脂吸附去除,吸附出水由出水管排出,同时树脂上附载的微生物利用水中的外加营养溶液和戊唑醇作为碳源,将吸附在树脂上的戊唑醇降解,水样在复式反应器中水力停留时间80分钟。出水CODCr小于25mg/L,水中戊唑醇浓度小于等于0.5mg/L。
步骤4.反冲洗:运行9天后,由于树脂上附载微生物的代谢会导致部分菌体死亡和脱落,关闭进水管路的泵、阀门和出水管阀门,打开反冲洗水进水管和反冲洗水出水管的阀门,反冲洗时间4分钟,反冲洗水进入到反冲洗水出水收集槽,而后排入污水处理厂处理。关闭反冲洗水进水管和反冲洗水出水管的阀门,打开进水管路的泵、阀门和出水管阀门,继续运行。
实施例4的运行效果
Claims (9)
- 一种用于去除水中戊唑醇复式反应器,其由特征在于,复式反应器由下述部件构成:反应器外壳(1)、反应器内壳(2)、进水管(7)、布水器(6)、出水管(3)、曝气管(12)、曝气头(5)、排气管(8)、集气反射锥体(9)、蜂窝状支撑架(10)、负载微生物的树脂(11)、反冲洗水进水管(13)、反冲洗水出水管(4)组成;其中,复式反应器的进水管(7)在反应器顶部,与反应器外壳(1)相连;排气管(8)在锥形集气罩附近,与反应器内壳(2)相连;出水管(3)在反应器上部、锥形集气罩下部,与反应器内壳(2)相连;蜂窝状支撑架(10)在反应器内壳(2)内,里面填充有负载微生物的树脂(11);布水器(6)在反应器内壳(2)底部;反冲洗水出水管(4)在每层蜂窝状支撑架(10)的上面,与反应器内壳(2)相连;反冲洗水进水管(13)在反应器布水器(6)底部,与外壳相连;曝气管(12)连接曝气头(5),曝气头(5)的位置在反应器布水器(6)的正上方。
- 根据权利要求1所述的复式反应器,其特征在于,所述的树脂(11)为聚苯乙烯、聚丙烯酸酯类骨架的吸附树脂。
- 根据权利要求1或2所述的复式反应器,其特征在于,所述的树脂(11)上负载微生物为鞘氨醇单胞菌属菌种。
- 一种用于去除水中戊唑醇复式反应器的系统,其由权利要求1-3任意一项所述的复式反应器(17)、外加营养溶液储备槽(14)、进水水样调节槽(15)、反冲洗水收集槽(16)、反冲洗水储备槽(18)、过滤器(19)、流量计(20)、水泵(21)和曝气泵(22)组成,其中,外加营养溶液存储槽(14)与进水调节槽(15)相连,复式反应器(17)分别与进水调节槽(15)、反冲洗水存储槽(18)、反冲洗水出水收集槽(16)、曝气泵(22)相连。
- 根据权利要求4所述的用于去除水中戊唑醇复式反应器用于去除水中戊唑醇方法方法,其步骤包括:步骤1、制备负载微生物的吸附树脂:a.微生物培养:首先将平板中的鞘氨醇单胞菌菌落接种到液体牛肉蛋白胨培养基中避光培养,温度28摄氏度;b.菌体收集:将处于对数生长期的菌体培养液离心分离,分离得到的菌体用磷酸氢二钠与磷酸二氢钾配制的缓冲液清洗;c.树脂负载微生物:将收集的菌体接种到矿物质液体培养基中,加入树脂后进行振荡培养3-5天,得到负载微生物的吸附树脂;d.填充树脂:将负载微生物的吸附树脂用去离子水清洗,填充到复式反应器的蜂窝状支撑架里;步骤2、进水:调节进水流量和外加营养溶液流量,控制进水调节槽中的水样CODCr不低于20mg/L,水样通过进水管进入复式反应器,打开曝气泵;步骤3、吸附-微生物降解戊唑醇:水样经过多层负载微生物的树脂,戊唑醇被树脂吸附去除,吸附出水由出水管排出,同时树脂上附载的微生物利用水中的外加营养和戊唑醇作为碳源,将其生物降解,水样在复式反应器中水力停留时间不低于30分钟;步骤4、反冲洗:运行7-10天后,由于树脂上附载微生物的代谢会导致部分菌体死亡和脱落,关闭进水管路的泵、阀门和出水管阀门,打开反冲洗水进水管和反冲洗水出水管的阀门,反冲洗时间不低于2分钟,反冲洗水进入到反冲洗水出水收集槽,而后排入污水处理厂处理;关闭反冲洗水进水管和反冲洗水出水管的阀门,打开进水管路的泵、阀门和出水管阀门,继续运行。
- 据权利要求4所述的方法,其特征是:所述步骤1的反应过程中所用树脂为聚苯乙烯、聚丙烯酸酯类骨架的吸附树脂。
- 根据权利要求4所述的方法,其特征是:步骤2中的外加营养溶液为甲醇、乙醇、葡萄糖或乙酸钠溶液中的一种。
- 根据权利要求4所述的方法,其特征是:所述将处于对数生长期的菌体培养液离心分离,其离心时间20分钟,转速5000G。
- 根据权利要求4所述的方法,其特征是:所述磷酸氢二钠与磷酸二氢钾配制的缓冲液的pH=7.3。
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