CN113697945A - Biomembrane reactor for deep purification of sewage and operation method thereof - Google Patents
Biomembrane reactor for deep purification of sewage and operation method thereof Download PDFInfo
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- CN113697945A CN113697945A CN202010808085.1A CN202010808085A CN113697945A CN 113697945 A CN113697945 A CN 113697945A CN 202010808085 A CN202010808085 A CN 202010808085A CN 113697945 A CN113697945 A CN 113697945A
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- water
- water inlet
- backwashing
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000010865 sewage Substances 0.000 title claims abstract description 29
- 238000000746 purification Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 209
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000011001 backwashing Methods 0.000 claims abstract description 69
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 45
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 37
- 239000003153 chemical reaction reagent Substances 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003860 storage Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000002351 wastewater Substances 0.000 claims description 22
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 20
- 239000004927 clay Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 230000002708 enhancing effect Effects 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- -1 aluminum ions Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 8
- 239000008213 purified water Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000010842 industrial wastewater Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000012258 culturing Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims 4
- 238000009826 distribution Methods 0.000 abstract description 58
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 20
- 239000011574 phosphorus Substances 0.000 abstract description 20
- 230000001988 toxicity Effects 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 230000004060 metabolic process Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 46
- 239000011449 brick Substances 0.000 description 31
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 16
- 238000005192 partition Methods 0.000 description 16
- 239000001632 sodium acetate Substances 0.000 description 16
- 235000017281 sodium acetate Nutrition 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000011010 flushing procedure Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 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 5
- 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 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000001651 autotrophic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010841 municipal wastewater Substances 0.000 description 3
- 229910000951 Aluminide Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 231100000820 toxicity test Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YBCXDOQKQWMGBF-UHFFFAOYSA-N 9,10-dioxoanthracene-2,6-disulfonic acid;sodium Chemical compound [Na].[Na].OS(=O)(=O)C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 YBCXDOQKQWMGBF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 241000512250 phototrophic bacterium Species 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010918 textile wastewater Substances 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
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2866—Particular arrangements for anaerobic reactors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
-
- 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
- C02F2209/005—Processes using a programmable logic controller [PLC]
-
- 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
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- 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
- C02F2209/14—NH3-N
-
- 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
- C02F2209/15—N03-N
-
- 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
- C02F2303/14—Maintenance of water treatment installations
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a biomembrane reactor for deep purification of sewage and an operation method thereof, wherein the biomembrane reactor is provided with a back flush component, a water inlet area, a cobble layer, a haydite layer and a functional filter material layer from the bottom to the top; the outer side of the top of the biomembrane reactor is provided with an overflow weir, a water inlet pool and a water outlet pool. The operation method overcomes the defect of higher cost caused by an external carbon source by adopting sulfur autotrophic-heterotrophic denitrification, and improves the metabolism rate of microorganisms by adding a trace amount of quinone redox mediator substances, thereby improving the denitrification efficiency; the removal of total phosphorus and trace organic pollutants is synchronously promoted by adopting the functional filter material layer, and the toxicity of the effluent is reduced. The invention obviously improves the removal of total nitrogen, total phosphorus and biological toxicity in the sewage, and enhances the recycling safety of the treated sewage. In addition, the water distribution uniformity of the backwashing component of the invention reaches more than 90%, and the backwashing energy consumption is reduced by 30-40%.
Description
Technical Field
The invention belongs to the technical field of biomembrane sewage treatment, and particularly relates to a biomembrane reactor for deep sewage purification and an operation method thereof.
Background
With the continuous improvement of the discharge standard of sewage treatment, the removal of pollutants such as total nitrogen, total phosphorus and the like in sewage poses a great challenge to sewage treatment plants, and with the gradual attention of new pollutants and other substances in sewage, the reduction of the biological toxicity of effluent in the advanced sewage treatment and safe reuse becomes one of the research hotspots of sewage treatment.
The traditional activated sludge process is difficult to reach the increasingly strict sewage discharge standard, and the denitrification filter tank process in the biomembrane method gradually becomes an application hotspot because of the advantages of simple operation, small occupied area, low cost, deep denitrification and the like. The method of sulfur autotrophic-heterotrophic denitrification and the like is gradually applied to the denitrification filter tank process because of the advantages of lower cost relative to the method of adding a carbon source and the like, but compared with the traditional heterotrophic denitrification, the denitrification rate is slower, and when the operating environment temperature is lower, the denitrification process in the denitrification filter tank is also inhibited, so that the denitrification efficiency is greatly reduced, and how to effectively improve the denitrification rate is one of the main problems in the application. Generally, the way of improving the denitrification rate of the denitrification filter tank mainly comprises the steps of improving a carrier, improving the design of a nitrification device, adding a biological enhancer, improving the operation temperature and the like, for example, the invention patent of China, namely 'multipoint enhanced denitrification and denitrification biological filter tank' (publication number CN208200506U), achieves the purposes of reducing the water head loss in unit time and improving the efficiency of the denitrification filter tank by arranging a plurality of water inlet and carbon source adding pumps to distribute water and add medicines, but causes the problems of increased equipment cost, increased operation difficulty and the like; chinese invention patent "a preparation method and application of ecological matrix particles for river water body enhanced nitrogen removal" (publication No. CN106365305B) adopts high-permeability porous materials, inorganic binder, corncobs and other slow-release carbon sources to prepare ecological matrix particles, and applies the ecological matrix particles to an ecological filter tank and an artificial wetland to achieve the purpose of slowly releasing carbon sources so as to enhance nitrogen removal. In recent years, researches show that part of quinone substances can be used as an electron carrier to improve the efficiency of electron transfer among microorganisms, so that the speed of removing nitrate and nitrite by the microorganisms is effectively improved, and the filter can be suitable for a traditional heterotrophic denitrification filter and a novel sulfur autotrophic-heterotrophic denitrification filter, and provides a new idea for strengthening denitrification in biochemical tail water treatment.
From the aspect of deep removal of phosphorus, with the development of the technology, aluminide shows relatively good performance in the aspect of total phosphorus removal, but the traditional mode of adding aluminum and iron compounds into a filter tank causes burden on the aspects of filter tank operation and cost, and the mode of removing total phosphorus by adopting a filter material for fixedly carrying aluminide becomes a potential feasible mode; in addition, titanium dioxide or micro/nano catalytic oxidation in a limited space is adopted, so that trace novel pollutants such as endocrine disruptors, personal care products and the like remained in tail water can be effectively degraded, the toxicity of final effluent is reduced, and the safety of sewage recycling after treatment is ensured. Therefore, by arranging the functional filter material layer, the purification effect of the denitrification filter on total phosphorus and novel pollutants in biochemical tail water is synchronously improved, the method is a potential effective technical means and is also an important development direction for advanced treatment of the denitrification filter, and the synchronous removal of the total phosphorus and the novel pollutants in the existing patent is hardly involved.
Meanwhile, the 'slime' and the like formed in the aging process of the biomembrane also have certain negative effects on the operation of the denitrification filter system, are not beneficial to deeply removing pollutants by the reactor, and carry out periodic back washing on the biomembrane, so that the activity of the biomembrane in the system is recovered, and the method is also an important means for improving the deep purification efficiency of the biomembrane reactor and saving energy for operation.
Disclosure of Invention
The invention aims to solve the problem of low denitrification efficiency caused by operation burden and low temperature condition caused by adding medicament or carbon source in the process of removing total nitrogen and total phosphorus in the deep purification of sewage in a denitrification filter, and provides a novel device and an operation method for the deep purification and safe recycling of sewage by considering the reduction of toxicity in sewage treatment.
The technical scheme of the invention is as follows: a biofilm reactor for deep purification of wastewater comprising:
the biofilm reactor is of a cuboid structure and is provided with a back flush component, a water inlet area, a cobble layer, a ceramsite layer and a functional filter material layer which is prepared from aluminum oxide and titanium dioxide or is composed of a polyhydroxy complex modified montmorillonite layer from the bottom to the top; an overflow weir is arranged on the outer side of the top of the biofilm reactor;
the water inlet tank is used for storing sewage and is connected with the water inlet area through a water inlet pipe with a water inlet pump, and a stirrer is arranged in the water inlet tank;
the system comprises a first reagent storage tank, a second reagent storage tank and a third reagent storage tank, wherein the first reagent storage tank is used for storing quinone redox mediators, the second reagent storage tank is used for storing sulfur sources, the third reagent storage tank is used for storing carbon sources, and the first reagent storage tank, the second reagent storage tank and the third reagent storage tank are respectively connected with a water inlet pool through reagent adding pipes with metering pumps;
the water outlet pool is used for storing purified water, is connected with the overflow weir through a water outlet pipe and is also connected with the backwashing component through a backwashing pipe with a backwashing water pump; the upper part of the water outlet pool is provided with a water outlet with a valve for discharging the treated wastewater in time and ensuring that enough water for back flushing can be reserved in the water outlet pool;
and the PLC is used for controlling the whole operation of the device and is respectively and electrically connected with the water inlet pump, the stirrer, the metering pump and the backwashing water pump.
Furthermore, the back washing component comprises filter bricks and a frame plate positioned below the filter bricks, the bottom of the frame plate and the bottom of the biomembrane reactor are a back washing water distribution area connected with a back washing water pump, and a back washing gas distribution pipe positioned in the back washing water distribution area, and the back washing gas distribution pipe is connected with the water outlet pool through a back washing pipe with the back washing water pump;
the two sides of the filter brick are provided with a connecting cylinder and a connecting column which are connected with the adjacent filter bricks and divide the adjacent filter bricks into slits with equal width, the four apex angles inside the filter bricks are respectively provided with inclined partition plates, the four inclined partition plates are provided with a plurality of water distribution and air distribution holes, the four inclined partition plates divide the inside of the filter brick into a hexagonal prism cavity channel positioned at the central position and cavities positioned at the four apex angles, the tops of the two cavities positioned at the upper layer are provided with first back flushing holes which vertically penetrate through the filter bricks, the side surfaces of the two cavities positioned at the lower layer are provided with second back flushing holes which horizontally penetrate through the filter bricks,
the inner part of the hexagonal prism cavity is horizontally and transversely provided with a partition plate for dividing the hexagonal prism cavity into an upper air distribution cavity and a lower water distribution cavity, the bottom of the water distribution cavity is provided with a notch for water inlet, the frame plate is positioned below the water distribution cavity and is provided with a water inlet groove communicated with the notch, the frame plate is used for introducing back washing water into the water distribution cavity and then sequentially passes through the water distribution and air distribution holes of the lower inclined partition plate to reach the two lower cavities for secondary water distribution, finally flows to a slit between two adjacent filter bricks from first back washing holes at two sides, and performs water flow back washing upwards through the slit, the back washing air distribution pipe is provided with a plurality of air distribution nozzles, the air distribution nozzles upwards sequentially penetrate through the frame plate and reserved holes on the partition plate to extend to the air distribution cavity and are used for causing back washing air flow to enter the air distribution cavity and then sequentially reach the air distribution holes of the upper inclined partition plate to reach the two upper cavities for secondary air distribution, finally, the water is sprayed out from a second backwashing hole positioned at the top of the filter brick to perform air washing on the filter layer. During back flushing, the air distribution and the water distribution can be carried out independently or simultaneously. The interior of the filter brick is formed by pouring concrete, and the inclined partition plate and the partition plate are internally provided with reinforcing ribs for resisting impact force.
Further, the preparation method of the functional filter material layer comprises the following steps:
the preparation method of the functional filter material layer comprises the following steps:
step 1: preparing an aluminum sulfate solution with the concentration of 10-12g/L by taking aluminum ions as a reference, adding sodium hydroxide to adjust the pH value of the solution to about 7.0, stirring for 5-10 minutes, adding titanium dioxide powder into the solution according to 1-2g/L after aluminum hydroxide precipitates are generated in the reaction, uniformly stirring, placing the solution in a closed container, heating to 110 ℃ in 100 ℃, and oscillating for 24-36 hours to form an aluminum sulfate-titanium dioxide mixed solution with the particle diameter of 20-30 mu m;
step 2: adding 5-10 wt% of fly ash sintered porous ceramsite into the aluminum sulfate-titanium dioxide mixed solution, cleaning, soaking into the prepared solution for 20-30 minutes, taking out, attaching micron-sized aluminum sulfate and nano-sized titanium dioxide to a pore channel structure of the ceramsite by using molecular acting force, and naturally drying.
The invention also provides another functional filter material layer consisting of the polyhydroxy complex modified montmorillonite layer, wherein montmorillonite in the polyhydroxy complex modified montmorillonite layer comprises the following components in percentage by weight: 65.5% SiO2、14.3％Al2O3、1.78％Fe2O3、1.08％CaO、1.42％MgO、0.2％K2O、0.19％TiO2。
The preparation method of the polyhydroxy complex modified montmorillonite comprises the following steps:
step 1: and (3) mixing the solid-liquid ratio of 1: the 100 montmorillonite suspension was swelled for 24h and then dispersed for 5min under 22kHz ultrasound.
Step 2: at 0.1M FeCl30.1M NaOH solution was added to the solution to make [ OH ]]/[Fe]An iron polyhydroxy complex was formed to make a modified solution, 2.0.
And step 3: the modified solution was added dropwise to the clay suspension so that the ratio of iron to clay was 1.0mmol/g, and the mixed suspension was maintained at room temperature for 24 hours. The clay was separated by centrifugation and washed with distilled water to be chlorine-free, dried at room temperature and then calcined at 500 ℃ for 2 hours.
The invention also provides an operation method for deep purification of sewage by using the biofilm reactor, which comprises the following steps:
s1: detecting biochemical tail water to be treated, measuring the carbon-nitrogen ratio of the biochemical tail water, calculating the total nitrogen load of inlet water according to the water inlet condition, selecting a heterotrophic denitrification mode or a sulfur autotrophic-heterotrophic denitrification mode according to the calculation result for treatment, and performing subsequent treatment and medicament addition on the biofilm reactor according to the selected treatment mode;
s2: when the heterotrophic denitrification mode is selected to treat wastewater, after the filter is successfully started, continuously or intermittently adding 50-120nM quinone redox mediator into the inlet water according to the operating environment temperature;
when the sulfur autotrophic-heterotrophic denitrification mode is selected to treat wastewater, a certain amount of sulfur source is additionally added according to the carbon-nitrogen ratio in the wastewater, after the filter is successfully started by culturing the biological membrane, 70-150nM quinone redox mediator is continuously or intermittently added into the inlet water according to the operating environment temperature, so that the aim of enhancing denitrification is fulfilled.
Further, the biochemical tail water is one of biochemical treatment tail water of a municipal sewage treatment plant and biochemical tail water of industrial wastewater, and the total nitrogen concentration is not higher than 20 mg/L.
Further, the selection conditions of the heterotrophic denitrification mode are as follows: when the COD/TN is more than or equal to 3, and the total nitrogen load of the inlet water is designed to be 0.25-0.60 kg-TN/(m)3When d) is present;
the selection conditions of the sulfur autotrophic-heterotrophic denitrification mode are as follows: when COD/TN<3, and designing the total nitrogen load of inlet water to be 0.05-0.35kg & TN/(m) according to inlet water3D) is used.
Further, in the heterotrophic denitrification mode, a mode of adding quinone redox mediators every other day is adopted when the temperature is 15-25 ℃, and the adding concentration is 80-120 nM; when the temperature is 10-15 ℃, a continuous feeding mode is adopted, and the feeding concentration is 50-100 nM; the quinone redox mediator is any one of anthraquinone-2-sodium sulfonate, 1, 2-naphthoquinone-4-sodium sulfonate and anthraquinone-2, 6-disodium disulfonate.
Further, in the sulfur autotrophic-heterotrophic denitrification mode, in the heterotrophic denitrification mode, the sulfur source is any one of elemental sulfur, sodium sulfide, or sodium thiosulfate. Setting the ratio of the total nitrogen removal amount of the heterotrophic denitrification and the autotrophic denitrification to be 1:1-1:2, wherein the ratio of the sulfur source addition amount to the total nitrogen removal amount required by the sulfur autotrophic denitrification mode is as follows: 3-5kg of elemental sulfur/kg. TN, 5-6kg of sodium sulfide/kg. TN and 8-10kg of sodium thiosulfate/kg. TN are added according to the proportion.
The invention has the beneficial effects that:
(1) the invention makes up the defect of higher cost caused by an external carbon source by adopting sulfur autotrophic-heterotrophic denitrification, and improves the metabolism rate of microorganisms by adding a trace amount of quinone redox mediator substances under the condition of basically not changing the concentration of influent organic matters, thereby improving the denitrification efficiency without harming the microorganisms.
(2) The invention adopts the alumina and the carbon dioxide ceramsite as the filter material layer or the functional filter material layer consisting of the polyhydroxy complex modified montmorillonite layer, greatly simplifies the medicament adding system, improves the effect of removing the total phosphorus and effectively reduces the toxicity of the discharged water.
(3) The invention obviously improves the removal of total nitrogen, total phosphorus and biological toxicity in the sewage treatment process of the biofilm reactor, has obvious deep purification effect and enhances the recycling safety of the treated sewage.
(4) The backwashing component of the invention has the water distribution uniformity reaching more than 90 percent and the backwashing energy consumption reduced by 30 to 40 percent.
Drawings
FIG. 1 is a schematic view of the overall structure of the apparatus of the present invention;
FIG. 2 is a schematic cross-sectional view of a filter block of the present invention;
FIG. 3 is a top view of a filter block of the present invention;
FIG. 4 is a right side view of the filter block of the present invention;
FIG. 5 is a schematic plan view of a separator plate of the present invention;
FIG. 6 is a schematic assembly view of the backwash assembly of the present invention;
FIG. 7 is a diagram of the operation effect of deep purification of secondary effluent by using the heterotrophic denitrification filter under the enhanced normal temperature condition;
FIG. 8 is a diagram showing the operation effect of the secondary biochemical tail water of the industrial wastewater deeply purified by the sulfur autotrophic-heterotrophic denitrification filter under the condition of intensified low temperature;
FIG. 9 is a diagram showing the operation effect of the enhanced low-temperature heterotrophic denitrification filter for deep purification of municipal wastewater by secondary biochemical tail water denitrification;
FIG. 10 is a diagram showing the operation effect of the sulfur autotrophic-heterotrophic denitrification filter for deeply purifying the secondary biochemical tail water of the municipal sewage treatment plant under the enhanced normal temperature condition.
Wherein, 1-biomembrane reactor, 2-backwashing component, 21-filter brick, 22-frame plate, 23-backwashing water pump, 24-backwashing water distribution area, 25-backwashing air pump, 26-backwashing air distribution pipe, 27-connecting cylinder, 28-connecting column, 29-inclined clapboard, 210-water distribution hole, 211-hexagonal prism cavity channel, 212-cavity, 213-first backwashing hole, 214-second backwashing hole, 215-separating plate, 216-air distribution cavity, 217-water distribution cavity, 218-notch, 219-water inlet groove, 220-air distribution nozzle, 221-reserved hole, 3-water inlet area, 4-cobble layer, 5-ceramsite layer, 6-functional filter material layer, 7-overflow weir, 8-water inlet pool, 9-water inlet pump, 10-water inlet pipe, 11-stirrer, 12-first reagent storage tank, 13-second reagent storage tank, 14-metering pump, 15-reagent adding pipe, 16-water outlet pool, 161-water outlet, 17-backwashing pipe, 18-PLC controller, 19-water outlet pipe and 20-third reagent storage tank.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following examples.
Example 1
As shown in fig. 1, a biofilm reactor for deep purification of wastewater includes: the bioreactor 1 is a cuboid structure, and the bottom to the top of the bioreactor 1 are respectively a back flush component 2, a water inlet area 3, a cobble layer 4, a ceramsite layer 5 and a functional filter material layer 6 prepared from alumina and titanium dioxide; the outer side of the top of the biomembrane reactor 1 is provided with an overflow weir 7; when the inflow water flow velocity is too large, the inflow water area 3 can be arranged below the backwashing component 2, so that the inflow water is uniformly distributed by means of the backwashing component 2, and the impact on the cobble layer 4 is reduced.
As shown in fig. 1, fig. 2, fig. 3, fig. 4, fig. 5 and fig. 6, the backwashing assembly 2 comprises filter bricks 21 and a frame plate 22 positioned below the filter bricks 21, the frame plate 22 and the bottom of the biofilm reactor 1 are a backwashing water distribution area 24 connected with a backwashing water pump 23, and a backwashing gas distribution pipe 26 positioned in the backwashing water distribution area 24, and the backwashing gas distribution pipe 26 is connected with the effluent pool 16 through a backwashing pipe 17 with the backwashing water pump 23;
the two sides of the filter brick 21 are provided with a connecting cylinder 27 and a connecting column 28 which are connected with the adjacent filter brick 21 and divide the adjacent filter brick 21 into slits with equal width, the four top corners inside the filter brick 21 are respectively provided with an inclined clapboard 29, the four inclined clapboards 29 are provided with a plurality of water distribution and air distribution holes 210, the four inclined clapboards 29 divide the inside of the filter brick 21 into a hexagonal prism cavity channel 211 positioned at the central position and cavities 212 positioned at the four top corners, the tops of the two cavities 212 positioned at the upper layer are provided with second back flushing holes 214 which vertically penetrate through the filter brick 21, the side surfaces of the two cavities 212 positioned at the lower layer are provided with first back flushing holes 213 which horizontally penetrate through the filter brick 21,
a partition plate 215 is horizontally and transversely arranged in the hexagonal prism cavity 211 and is used for dividing the hexagonal prism cavity 211 into an air distribution cavity 216 positioned above and a water distribution cavity 217 positioned below, the bottom of the water distribution cavity 217 is provided with a notch 218 for water inlet, the frame plate 22 is positioned below the water distribution cavity 217 and is provided with a water inlet groove 219 communicated with the notch 218 and is used for introducing back washing water into the water distribution cavity 217 and then sequentially passing through the water distribution and air distribution holes 210 of the lower inclined partition plate 29 to reach the two lower cavities 212 for secondary water distribution, finally, the back washing water flows to a slit between two adjacent filter bricks 21 from the first back washing holes 213 at two sides and is backwashed upwards through the slit for water flow backwashing, the back washing air distribution pipe 26 is provided with a plurality of air distribution nozzles 220, the air distribution nozzles 220 upwards sequentially pass through the frame plate 22 and the reserved holes 221 positioned on the partition plate 215 to extend to the air distribution cavity 216 and are used for causing back washing air to sequentially reach the water distribution holes 210 of the upper inclined partition plate 29 after entering the air distribution cavity 216 and then sequentially reaching the upper inclined partition plate 29 to reach the upper cavities 212 for secondary air distribution, finally, the water is sprayed out from the second backwashing holes 214 positioned at the top of the filter bricks 21 to perform air washing on the filter layer. During back flushing, the air distribution and the water distribution can be carried out independently or simultaneously. The filter bricks 21 of the present invention are formed by casting concrete, and reinforcing ribs for resisting impact force are provided in the inclined partition plates 29 and the partition plates 215.
As shown in fig. 1, a water inlet tank 8 for storing sewage, the water inlet tank 8 is connected with the water inlet area 3 through a water inlet pipe 10 with a water inlet pump 9, and a stirrer 11 is arranged in the water inlet tank 8; a first reagent storage tank 12 for storing quinone redox mediators, a second reagent storage tank 13 for storing a sulfur source, the first reagent storage tank 12, the second reagent storage tank 13, and a third reagent storage tank 20 being connected to the inlet tank 8 through reagent addition pipes 15 having metering pumps 14, respectively; the water outlet pool 16 is used for storing purified water, the water outlet pool 16 is connected with the overflow weir 7 through a water outlet pipe 19, and the water outlet pool 16 is also connected with the backwashing component 2 through a backwashing pipe 17 with a backwashing water pump 23; the upper part of the water outlet tank is provided with a water outlet 161 with a valve for discharging the treated wastewater in time and ensuring that enough water for back flushing can be reserved in the water outlet tank 16; and the PLC 18 is used for controlling the whole operation of the device, and the PLC 18 is respectively in electric wire connection with the water inlet pump 9, the stirrer 11, the metering pump 14 and the backwashing water pump 23.
The working method of the device comprises the following steps: firstly, detecting the wastewater, wherein the detected objects comprise COD concentration, TN concentration, nitrate nitrogen concentration, ammonia nitrogen concentration, nitrite nitrogen concentration, total phosphorus, pH and environment temperature. Selecting a nitrification mode according to COD/TN, and designing the total nitrogen load of inlet water to be 0.25-0.60 kg-TN/(m) according to inlet water when the COD/TN is more than or equal to 33D) when the heterotrophic denitrification mode is selected, as COD/TN<3, and designing the total nitrogen load of inlet water to be 0.05-0.35kg & TN/(m) according to inlet water3D) selecting the sulfur autotrophic-heterotrophic denitrification mode.
Introducing wastewater into a water inlet tank 8 for water storage, when a heterotrophic denitrification mode is selected, opening a metering pump 14 of a first reagent storage tank 12, continuously adding quinone redox mediators into the water inlet tank 8 or adding quinone redox mediators into the water inlet tank 8 at intervals according to requirements, uniformly stirring and mixing by using a stirrer 11, conveying the wastewater in the water inlet tank 8 from a water inlet pipe 10 to an area A221 of a water inlet area 3 through a water inlet pump 9, enabling the wastewater to overflow upwards to an area B222 through a communicating pipe 223, sequentially performing layer-by-layer purification and filtration on a cobble layer 4, a ceramsite layer 5 and a functional filter material layer 6, enabling the purified water to flow into an overflow weir 7 and then flow into a water outlet tank 16 through a water outlet pipe 19, and when the total nitrogen of effluent of a reactor cannot meet the discharge requirement, opening a third reagent storage tank 20 and adding a carbon source according to the requirements.
When the sulfur autotrophic-heterotrophic denitrification mode is selected, the metering pump 14 of the second reagent storage tank 13 is firstly opened, a certain amount of sulfur source is additionally added according to the carbon-nitrogen ratio in the wastewater, the biofilm culture is successful, the water inlet pump 9 is started to feed water into the biofilm reactor 1, the metering pump 14 of the first reagent storage tank 12 is selectively opened according to the running environment temperature, and quinone redox mediators are continuously or intermittently added into the fed water, so that the purpose of enhancing denitrification is achieved.
When the bio-membrane reactor 1 needs to be backwashed after running for a period of time, the water inlet pump 9 is closed to stop water inlet, the backwash water pump 17 is opened to pump the purified water stored in the water outlet tank 16 to the zone B222, the backwash air pump 25 is opened simultaneously, the purified water and the backwash air circulate in the water flow channel 211 of the filter bricks 21 and disperse outwards from the flow control gap 212, the water and the air are uniformly distributed upwards through the gap between two adjacent filter bricks 21 for backwashing, and the purified water also uniformly backflushes the upper-layer filter material through the backwash hole 214 arranged at the top of the filter bricks 21 when circulating in the water flow channel 211. The filter bricks 21 are fixedly connected to the connection pipes 223 of the separator frames 22 through the connection holes 216, thereby preventing the filter bricks 21 from being displaced. The filter bricks can be effectively prevented from being blocked by partitioning the water inlet and the backwashing, the backwashing efficiency is improved, and the backwashing energy consumption is reduced.
Example 2
The embodiment relates to a method for enhancing denitrification by adding quinone redox mediator when a denitrification filter tank deeply purifies secondary biochemical tail water by adopting a heterotrophic denitrification mode.
And detecting the secondary biochemical tail water to be treated to obtain the secondary biochemical tail water with the COD concentration of 50-65 mg/L, the TN concentration of 16-19 mg/L, the nitrate nitrogen concentration of 14-17 mg/L, the ammonia nitrogen concentration of 0.4-0.6 mg/L, the nitrite nitrogen concentration of 0.2-0.8 mg/L, the total phosphorus concentration of 0.50-0.58 mg/L, the pH value of 7.4-7.6 and the ambient temperature of 18 ℃. According to the detection result, the COD/TN is larger than 3, the designed hydraulic retention time is 1.0h, and the total nitrogen load of inlet water is 0.5 kg-TN/(m)3D), selecting a heterotrophic denitrification filter for treatment, wherein the temperature is normal temperature, and therefore, the denitrification filter is operated in an intermittent feeding mode and an upward flow mode.
Two groups of nitration devices of a blank group and an experimental group are arranged to respectively treat the wastewater, and the blank group is operated by adopting the device without the functional filter material layer 6 in the embodiment 1. The experimental group was run using a nitrification apparatus with a functional filter bed 6 in example 1.
Preparation of the functional Filter Material layer 6 As shown below, 10g/L (in terms of aluminum ions) of an aluminum sulfate solution (Al) was prepared2(SO4)3·18H2O), adding sodium hydroxide to adjust the pH of the solution to about 7.0, stirring for 6 minutes, and adding 1.8g/L titanium dioxide (TiO)2) Putting the powder into the solution, heating the solution to 100 ℃ in a closed container, oscillating for 24 hours, selecting porous ceramsite doped with 5 wt% of fly ash, cleaning, immersing into the prepared solution for 30 minutes, taking out and naturally drying to obtain a functional filter material layer.
The water quality of total nitrogen inlet and outlet water during the operation of the nitrification device is shown in figure 7, the outlet water of the nitrification device is relatively stable after the nitrification device is operated for about 70 days, the outlet water of the denitrification filter tank is detected, the concentration of TN in the effluent is 8-11 mg/L, the total nitrogen removal is low, at the moment, 120mM of 1, 2-naphthoquinone-4-sodium sulfonate is added into the influent of the experimental group every other day, the concentration of TOC and TN in the effluent is detected, in the subsequent 35-day operation, the TOC concentration in inlet and outlet water is almost unchanged after the redox mediator is added, the total nitrogen concentration of the outlet water is 3.5-8.5 mg/L, compared with a blank group, the average total nitrogen removal is effectively improved to 3.75mg/L, the total nitrogen removal rate is improved by 24.6 percent, the purpose of strengthening denitrification is achieved, meanwhile, the total phosphorus in the effluent reaches 0.20-0.28 mg/L, and the relative inhibition rate of the effluent in the stationary phase of the experimental group is reduced by 26-32% compared with that of the effluent in the blank group by adopting a phototrophic bacteria determination biotoxicity experiment. The cost can be saved by 0.022 yuan/m by calculating that the mass of sodium acetate which is additionally added for removing the total nitrogen of unit mass is 6g of sodium acetate/g of TN, 22.5mg/L of sodium acetate is additionally added according to the price of the sodium acetate of 2500 yuan/ton and the price of the 1, 2-naphthoquinone-4-sodium sulfonate of 2200 yuan/kg (95 percent of pure)3And the carbon source adding cost is saved by 38.7 percent. The water distribution uniformity of the backwashing component reaches 93 percent, and the backwashing energy consumption is reduced by 34 percent.
Example 3
The embodiment relates to a method for enhancing denitrification by adding quinone redox mediator when a denitrification filter tank deeply purifies secondary biochemical tail water of industrial wastewater (textile wastewater) at low temperature by adopting a sulfur autotrophic-heterotrophic denitrification mode.
And detecting the secondary biochemical tail water to be treated to obtain the secondary biochemical tail water with the COD concentration of 30-35 mg/L, the TN concentration of 15-18 mg/L, the nitrate nitrogen concentration of 13-15 mg/L, the ammonia nitrogen concentration of 0.1-0.3 mg/L, the nitrite nitrogen concentration of 0.1-0.4 mg/L, the total phosphorus concentration of 0.15-0.26 mg/L and the pH value of 7.5-7.8, and the ambient temperature is 10 ℃. The COD/TN is less than 3 by detection, the hydraulic retention time is designed to be 2.0h, and the total nitrogen load of the inlet water is 0.15 kg-TN/(m)3D), adopting a sulfur autotrophic-heterotrophic denitrification filter tank for treatment, wherein the temperature is a low-temperature condition, adopting a continuous feeding mode, adopting an upward flow mode to operate the denitrification filter tank, setting the hydraulic retention time to be 2.0h, selecting sodium sulfide as a sulfur source, and adding the sodium sulfide according to the proportion that the heterotrophic denitrification and the autotrophic denitrification are 1:1, so that the concentration of the added sodium sulfide is 40 mg/L.
Two groups of nitration devices of a blank group and an experimental group are arranged to respectively treat the wastewater, and the blank group is operated by adopting the device without the functional filter material layer 6 in the embodiment 1. The experimental group was run using a nitrification apparatus with a functional filter bed 6 in example 1.
The preparation method of the functional filter material layer 6 comprises the following steps: montmorillonite is prepared according to the following weight proportion: 65.5% SiO2、14.3％Al2O3、1.78％Fe2O3、1.08％CaO、1.42％MgO、0.2％K2O、0.19％TiO2And then, setting the solid-liquid ratio as 1: the 100 montmorillonite suspension was swelled for 24h and then dispersed for 5min under 22kHz ultrasound. At 0.1M FeCl30.1M NaOH solution was added to the solution to make [ OH ]]/[Fe]An iron polyhydroxy complex was formed to make a modified solution, 2.0. The modified solution was added dropwise to the clay suspension so that the ratio of iron to clay was 1.0mmol/g, and the mixed suspension was maintained at room temperature for 24 hours. The clay is separated by centrifugation, washed by distilled water until no chlorine exists, dried at room temperature, and calcined at 500 ℃ for 2 hours to be used as a functional layer filter material.
The operation result of the reactor is shown in fig. 8, when the reactor is operated for 70 days, the effluent of the reactor is relatively stable, the effluent of the denitrification filter tank is detected, the TN concentration of the effluent is 9-12 mg/L, the total nitrogen removal is low, at the moment, 70mM of anthraquinone-2, 6-disodium disulfonate is continuously added into the inlet water of the experimental group, the TOC and TN concentrations of the effluent are detected, after the redox mediator is added in the subsequent 35-day operation, the TOC concentration of the inlet water and the outlet water is hardly changed, the total nitrogen concentration of the effluent is 5.8-9.6 mg/L, compared with the blank group, the average total nitrogen removal is effectively improved to 3.10mg/L, the total nitrogen removal rate is improved to 18.2%, and the total nitrogen removal rate is up to 5.8-9.6 mg/LThe aim of enhancing denitrification is achieved, the total phosphorus in the effluent reaches 0.08-0.14 mg/L, and the experiment of determining the biological toxicity by adopting the luminescent bacteria shows that the relative inhibition rate of the effluent in the stationary phase of the experimental group is reduced by 48-52% compared with that of the effluent in the blank group. The cost can be saved by 0.020 yuan/m by calculating that the mass of sodium acetate which needs to be additionally added for removing the total nitrogen of unit mass is 6g of sodium acetate/g of TN, 18.6mg/L of sodium acetate needs to be additionally added, and the cost is calculated according to the price of the sodium acetate of 2500 yuan/ton and the price of the anthraquinone-2, 6-disulfonic acid disodium of 1200 yuan/kg (90 percent of pure)3And the cost for adding the carbon source is saved by 42.3 percent. The water distribution uniformity of the backwashing component reaches 94.5 percent, and the backwashing energy consumption is reduced by 35 percent.
Example 4
The embodiment relates to a method for enhancing denitrification by adding quinone redox mediators when a denitrification filter tank deeply purifies municipal wastewater secondary biochemical tail water at low temperature in a heterotrophic denitrification mode.
The municipal wastewater to be treated is detected, and the COD concentration is 40-60mg/L, the TN concentration is 14-16 mg/L, the nitrate nitrogen concentration is 13-15 mg/L, the ammonia nitrogen concentration is 0.4-0.6 mg/L, the nitrite nitrogen concentration is 0.2-0.5 mg/L, the total phosphorus is 0.56-0.64 mg/L, the pH is 7.0-7.2, and the environmental temperature is 12 ℃. The COD/TN is basically larger than 3 by detection, the hydraulic retention time is designed to be 1.5h, and the total nitrogen load of inlet water is 0.4 kg-TN/(m)3D), so the heterotrophic denitrification filter is adopted for treatment, the temperature is low, so the denitrification filter is operated in a continuous feeding mode and a gravity flow mode.
Two groups of nitration devices of a blank group and an experimental group are arranged to respectively treat the wastewater, and the blank group is operated by adopting the device without the functional filter material layer 6 in the embodiment 1. The experimental group was run using a nitrification apparatus with a functional filter bed 6 in example 1.
The preparation method of the functional filter material layer 6 comprises the following steps: 10g/L (calculated by aluminum ions) of aluminum sulfate solution (Al) is prepared2(SO4)3·18H2O), adding sodium hydroxide to adjust the pH of the solution to about 7.0, stirring for 6 minutes, and adding 1.0g/L titanium dioxide (TiO)2) Putting the powder into the solution, heating the solution to 105 ℃ in a closed container, oscillating for 48 hours, and selecting the solution doped with 10 wt% of fly ashAnd after being cleaned, the porous ceramsite is soaked in the prepared solution for 30 minutes, and then fished out and naturally dried to be used as a functional filter material layer.
The operation result of the reactor is shown in fig. 9, when the reactor is operated for about 70 days, the effluent is relatively stable, the effluent of the denitrification filter tank is detected, the TN concentration of the effluent is 9-11 mg/L, the total nitrogen removal is low, at the moment, 80mM anthraquinone-2-sodium sulfonate is continuously added into the inlet water of an experimental group, the TN concentration of the effluent is detected, in the subsequent 35-day operation, the total nitrogen concentration of the effluent is 4.5-6.4 mg/L after adding a redox mediator, compared with a blank group, the average total nitrogen removal is effectively improved to 4.55mg/L, the total nitrogen removal rate is improved by 42.5%, the purpose of enhancing denitrification is achieved, meanwhile, the total phosphorus of the effluent reaches 0.26-0.36 mg/L, and a biological toxicity test by using luminescent bacteria shows that the relative inhibition rate of the effluent in the stable period of the experimental group is reduced by 18-24% compared with the blank group. The cost can be saved by 0.028 yuan/m calculated according to that the mass of sodium acetate which is additionally added for removing the total nitrogen of unit mass is 6g of sodium acetate/g of TN, 27.3mg/L of sodium acetate is additionally added, and the total nitrogen removal amount is calculated according to 2500 yuan/ton of sodium acetate and 1600 yuan/kg (92% pure) of anthraquinone-2-sodium sulfonate3And the carbon source adding cost is saved by 41.8 percent. The water distribution uniformity of the backwashing component reaches 95%, and the backwashing energy consumption is reduced by 38%.
Example 5
The embodiment relates to a method for enhancing denitrification by adding quinone redox mediator when a denitrification filter tank deeply purifies secondary biochemical tail water of a certain municipal sewage treatment plant at normal temperature by adopting a sulfur autotrophic-heterotrophic denitrification mode.
Firstly, preparing polyhydroxy complex modified montmorillonite as a functional filter material layer 6, and the main method is as follows:
the method comprises the steps of detecting the micro-polluted water on the ground surface to be treated, and obtaining the micro-polluted water with the COD concentration of 20-30 mg/L, the TN concentration of 15-20 mg/L, the nitrate nitrogen concentration of 14-19 mg/L, the ammonia nitrogen concentration of 0.2-0.3 mg/L, the nitrite nitrogen concentration of 0.2-0.4 mg/L, the total phosphorus concentration of 0.20-0.28 mg/L, the pH value of 7.4-7.6 and the ambient temperature of 22 ℃. The COD/TN is detected to be less than 3, so the sulfur autotrophic-heterotrophic denitrification filter is adopted for treatment, the temperature is normal temperature, so the intermittent feeding is adopted, the denitrification filter is operated in a gravity flow mode, the hydraulic retention time is set to be 2.5h, sulfur simple substance is selected as a sulfur source, the sulfur is added according to the proportion that the heterotrophic denitrification and the autotrophic denitrification are 1:1.5, and the amount of the added sulfur simple substance is 80 mg/L.
Two groups of nitration devices of a blank group and an experimental group are arranged to respectively treat the wastewater, and the blank group is operated by adopting the device without the functional filter material layer 6 in the embodiment 1. The experimental group was run using a nitrification apparatus with a functional filter bed 6 in example 1.
The preparation of the functional filter material layer 6 is as follows, the functional filter material layer 6 adopts a polyhydroxy complex modified montmorillonite layer, and montmorillonite in the polyhydroxy complex modified montmorillonite layer comprises the following components in percentage by weight: 65.5% SiO2、14.3％Al2O3、1.78％Fe2O3、1.08％CaO、1.42％MgO、0.2％K2O、0.19％TiO2。
The preparation method of the polyhydroxy complex modified montmorillonite comprises the following steps: and (3) mixing the solid-liquid ratio of 1: the 100 montmorillonite suspension was swelled for 24h and then dispersed for 5min under 22kHz ultrasound. A 0.1M NaOH solution was added to a 0.1M FeCl3 solution to make [ OH ]/[ Fe ] ═ 2.0 to form an iron polyhydroxy complex, thereby preparing a modified solution. The modified solution was added dropwise to the clay suspension so that the ratio of iron to clay was 1.0mmol/g, and the mixed suspension was maintained at room temperature for 24 hours. The clay was separated by centrifugation and washed with distilled water until chlorine-free, dried at room temperature and calcined at 500 ℃ for 2h to serve as a functional filter layer.
The result of the reactor is shown in fig. 10, when the reactor is operated for about 70 days, the effluent is relatively stable, the effluent of the denitrification filter tank is detected, the TN concentration of the effluent is 10-13 mg/L, the total nitrogen removal is low, at the moment, 120mM of anthraquinone-2, 6-disodium disulfonate is added into the inlet water of an experimental group every other day, the TN concentration of the effluent is detected, in the subsequent 35-day operation, the total nitrogen concentration of the effluent is 5.8-7.6 mg/L after adding an oxidation reduction mediator, compared with a blank group, the average total nitrogen removal is effectively improved to 4.8mg/L, the total nitrogen removal rate is improved by 41.7%, the aim of enhancing denitrification is achieved, the total phosphorus of the effluent is 0.12-0.16 mg/L, and a biological toxicity test by adopting luminescent bacteria to measure the biological toxicity shows that the effluent of the experimental group is outputted at the stable periodThe water relative inhibition rate is reduced by 12 to 20 percent compared with that of a blank group. The weight of sodium acetate which needs to be additionally added for removing the total nitrogen of unit mass is 6g of sodium acetate/g of TN, 28.8mg/L of sodium acetate needs to be additionally added, and the cost can be saved by 0.032 yuan/m according to the calculation of 2500 yuan/ton of sodium acetate and 1800 yuan/kg (95% pure) of anthraquinone-2, 6-disodium disulfonate3And the carbon source adding cost is saved by 44.8 percent. The water distribution uniformity of the backwashing component reaches 96 percent, and the backwashing energy consumption is reduced by 40 percent.
It should be noted that, for those skilled in the art, in light of the present disclosure and the specific embodiments thereof, modifications can be made and still other methods can be used to implement the functions and effects described in the present invention without departing from the scope of the present invention.
Claims (8)
1. A biofilm reactor for deep purification of wastewater, comprising:
the biofilm reactor (1) is of a cuboid structure, and the biofilm reactor (1) is provided with a water inlet area (3), a backwashing component (2), a cobble layer (4), a ceramsite layer (5) and a functional filter material layer prepared from alumina and titanium dioxide or a functional filter material layer (6) composed of a polyhydroxy complex modified montmorillonite layer from bottom to top; an overflow weir (7) is arranged on the outer side of the top of the biomembrane reactor (1);
the sewage treatment device comprises a water inlet tank (8) for storing sewage, wherein the water inlet tank (8) is connected with a water inlet area (3) through a water inlet pipe (10) with a water inlet pump (9), and a stirrer (11) is arranged in the water inlet tank (8);
a first reagent storage tank (12) for storing quinone redox mediators, a second reagent storage tank (13) for storing a sulfur source, and a third reagent storage tank (20) for storing a carbon source, wherein the first reagent storage tank (12), the second reagent storage tank (13), and the third reagent storage tank (20) are respectively connected with the water inlet tank (8) through reagent adding pipes (15) with metering pumps (14);
the water outlet pool (16) is used for storing purified water, the water outlet pool (16) is connected with the overflow weir (7) through a water outlet pipe (19), the water outlet pool (16) is also connected with the backwashing component (2) through a backwashing pipe (17) with a backwashing water pump (23), and the upper part of the water outlet pool (16) is provided with a water outlet (161) with a valve;
and the PLC (18) is used for controlling the whole operation of the device, and the PLC (18) is respectively in electric wire connection with the water inlet pump (9), the stirrer (11), the metering pump (14) and the backwashing water pump (23).
2. A biofilter for deep purification of wastewater according to claim 1, wherein said functional filter bed made of alumina and titania is prepared by a method comprising the steps of:
step 1: preparing an aluminum sulfate solution with the concentration of 10-12g/L by taking aluminum ions as a reference, adding sodium hydroxide to adjust the pH value of the solution to about 7.0, stirring for 5-10 minutes, adding titanium dioxide powder into the solution according to 1-2g/L after aluminum hydroxide precipitates are generated in the reaction, uniformly stirring, placing the solution in a closed container, heating to 110 ℃ in 100 ℃, and oscillating for 24-36 hours to form an aluminum sulfate-titanium dioxide mixed solution with the particle diameter of 20-30 mu m;
step 2: adding 5-10 wt% of fly ash sintered porous ceramsite into the aluminum sulfate-titanium dioxide mixed solution, cleaning, soaking into the prepared solution for 20-30 minutes, taking out, attaching micron-sized aluminum sulfate and nano-sized titanium dioxide to a pore channel structure of the ceramsite by using molecular acting force, and naturally drying.
3. A biofilter for advanced wastewater purification according to claim 1, wherein said functional filter layer consisting of a polyhydroxy complex modified montmorillonite layer is prepared by a method comprising the steps of:
wherein, the montmorillonite in the polyhydroxy complex modified montmorillonite layer is prepared according to the following weight percentage: 65.5% SiO2、14.3％Al2O3、1.78％Fe2O3、1.08％CaO、1.42％MgO、0.2％K2O、0.19％TiO2。
Step 1: and (3) mixing the solid-liquid ratio of 1: the 100 montmorillonite suspension was swelled for 24h and then dispersed for 5min under 22kHz ultrasound.
Step 2: at 0.1M FeCl30.1M NaOH solution was added to the solution to make [ OH ]]/[Fe]An iron polyhydroxy complex was formed to make a modified solution, 2.0.
And step 3: the modified solution was added dropwise to the clay suspension so that the ratio of iron to clay was 1.0mmol/g, and the mixed suspension was maintained at room temperature for 24 hours. The clay was separated by centrifugation and washed with distilled water to be chlorine-free, dried at room temperature and then calcined at 500 ℃ for 2 hours.
4. A method of operating a biofilter (1) for deep purification of contaminated water according to any of claims 1 to 3, comprising the steps of:
s1: detecting biochemical tail water to be treated, measuring the carbon-nitrogen ratio of the biochemical tail water, calculating the total nitrogen load of inlet water according to the water inlet condition, selecting a heterotrophic denitrification mode or a sulfur autotrophic-heterotrophic denitrification mode according to the calculation result for treatment, and performing subsequent treatment and medicament addition on the biological filter (1) according to the selected treatment mode;
s2: when the heterotrophic denitrification mode is selected to treat wastewater, after the filter is successfully started, continuously or intermittently adding 50-120nM quinone redox mediator into the inlet water according to the operating environment temperature;
when the sulfur autotrophic-heterotrophic denitrification mode is selected to treat wastewater, a certain amount of sulfur source is additionally added according to the carbon-nitrogen ratio in the wastewater, after the filter is successfully started by culturing the biological membrane, 70-150nM quinone redox mediator is continuously or intermittently added into the inlet water according to the operating environment temperature, so that the aim of enhancing denitrification is fulfilled.
5. The operating method according to claim 4, wherein the biochemical tail water is one of biochemical tail water of municipal sewage treatment plants and biochemical tail water of industrial wastewater, and the total nitrogen concentration is not higher than 20 mg/L.
6. An operating method according to claim 4, characterized in that the heterotrophic denitrification mode is selected under the following conditions: when the COD/TN is more than or equal to 3, and the total nitrogen load of the inlet water is designed to be 0.25-0.60 kg-TN/(m)3When d) is present;
the selection conditions of the sulfur autotrophic-heterotrophic denitrification mode are as follows: when COD/TN<3, and designing the total nitrogen load of inlet water to be 0.05-0.35kg & TN/(m) according to inlet water3D) is used.
7. An operating method according to claim 4, characterized in that in the heterotrophic denitrification mode, the quinone redox mediator is added every other day at a concentration of 80-120nM, at a temperature of 15-25 ℃; when the temperature is 10-15 ℃, a continuous feeding mode is adopted, and the feeding concentration is 50-100 nM; the quinone redox mediator is any one of anthraquinone-2-sodium sulfonate, 1, 2-naphthoquinone-4-sodium sulfonate and anthraquinone-2, 6-disodium disulfonate.
8. An operating method according to claim 4, characterized in that in the sulfur autotrophic-heterotrophic denitrification mode, in the heterotrophic denitrification mode, the sulfur source is any one of elemental sulfur, sodium sulfide or sodium thiosulfate.
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