CN115108686B - Treatment method of refractory organic wastewater - Google Patents
Treatment method of refractory organic wastewater Download PDFInfo
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- CN115108686B CN115108686B CN202210903197.4A CN202210903197A CN115108686B CN 115108686 B CN115108686 B CN 115108686B CN 202210903197 A CN202210903197 A CN 202210903197A CN 115108686 B CN115108686 B CN 115108686B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 22
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- 239000012528 membrane Substances 0.000 claims abstract description 101
- 230000003647 oxidation Effects 0.000 claims abstract description 101
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 101
- 239000010865 sewage Substances 0.000 claims abstract description 52
- 238000010992 reflux Methods 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract 2
- 238000006731 degradation reaction Methods 0.000 claims abstract 2
- 230000003197 catalytic effect Effects 0.000 claims description 51
- 239000010802 sludge Substances 0.000 claims description 31
- 239000000945 filler Substances 0.000 claims description 27
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 26
- 239000002033 PVDF binder Substances 0.000 claims description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 18
- 238000005374 membrane filtration Methods 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000000149 chemical water pollutant Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 abstract description 28
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 description 25
- 230000014759 maintenance of location Effects 0.000 description 20
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- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012510 hollow fiber Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 108090000790 Enzymes Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000005352 clarification Methods 0.000 description 1
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- 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]
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/18—PO4-P
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Microbiology (AREA)
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Abstract
The invention provides a method for treating degradation-resistant sewage. The treatment method of the invention comprises the following steps: (1) Carrying out anaerobic biochemical treatment or hydrolytic acidification treatment on sewage to be treated; (2) Performing anoxic biochemical treatment on the treated water in the step (1); (3) Carrying out aerobic biochemical treatment on the treated water in the step (2); (4) Treating the treated water in the step (3) by an MBR (Membrane bioreactor); (5) Performing advanced oxidation treatment on the treated water in the step (4); (6) Refluxing the treated water in the step (5) to the step (1) or the step (2), and continuing to circulate until the water after the advanced oxidation treatment reaches the discharge standard; the ratio of the treatment time of the step (1), the step (2), the step (3) and the step (5) is (10-15): 2-5): 4-8): 1. The invention can realize the high-efficiency and low-cost treatment of the organic wastewater difficult to degrade.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a method for treating organic wastewater difficult to degrade.
Background
For organic wastewater which is difficult to biochemically degrade and is generated in industrial activities, such as pharmaceutical wastewater, chemical wastewater, printing and dyeing wastewater, landfill leachate and the like, a special treatment method is needed to achieve a certain discharge standard. Common treatment methods comprise combined treatment such as standing clarification, biochemical treatment, physical adsorption and the like, and for wastewater with particularly high treatment difficulty or high requirement standard, the requirements of a few simple combined processes are difficult to reach. In recent years, the membrane bioreactor is widely applied to municipal sewage and industrial wastewater treatment, and the effluent quality of the effluent passing through the membrane tank is good and stable, and the water-producing bacteria, suspended matters, turbidity and the like can be further reduced. For the organic wastewater difficult to degrade, a plurality of reaction tanks have to be designed to achieve higher emission standards, and different treatment methods are combined, so that the whole treatment facility is huge, the flow is long, the occupied area is large, the investment requirement is high, the treatment time and the treatment effect are generally contradictory, and therefore, the development of an efficient and low-cost treatment method for the organic wastewater difficult to degrade is required.
Disclosure of Invention
The invention aims to provide a method for treating refractory organic wastewater, which is efficient and low in cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for treating refractory sewage comprises the following steps:
(1) Carrying out anaerobic biochemical treatment or hydrolytic acidification treatment on sewage to be treated;
(2) Performing anoxic biochemical treatment on the treated water in the step (1);
(3) Carrying out aerobic biochemical treatment on the treated water in the step (2);
(4) Treating the treated water in the step (3) by an MBR (Membrane bioreactor);
(5) Performing advanced oxidation treatment on the treated water in the step (4);
(6) Refluxing the treated water in the step (5) to the step (1), and circularly carrying out the steps (2) to (6) until the water after the advanced oxidation treatment reaches the discharge standard;
or the treated water in the step (5) is returned to the step (2), and the steps (3) to (6) are circularly carried out until the water after the advanced oxidation treatment reaches the discharge standard;
Wherein the ratio of the treatment time of the step (1), the step (2), the step (3) and the step (5) is (10-15): 2-5): 4-8): 1.
Preferably, the ratio of the treatment time of the step (1), the step (2), the step (3) and the step (5) is (11-13): 3-5): 7-8): 1.
Preferably, the pH=6-9 of the sewage to be treated, the temperature is between 5-45 ℃, the mineral oil content is less than 50mg/L, the particle size of the particles is less than 2mm, and the CODcr is less than 20000mg/L.
Further preferably, the number of cycles is 2 to 5.
According to some embodiments, the treatment time of step (1) is 10 to 15 hours, e.g. 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.
According to some embodiments, the treatment time of step (2) is 2 to 5 hours, e.g. 2 hours, 3 hours, 4 hours, 5 hours.
According to some embodiments, the treatment time of step (3) is 4 to 8 hours, e.g. 4 hours, 5 hours, 6 hours, 7 hours, 8 hours.
According to some embodiments, the treatment time of step (5) is 0.5 to 1.5h, e.g. 0.6h,0.7h,0.8h,0.9h,1.0h,1.1h,1.3h,1.4h,1.5h.
According to some embodiments, the intermittent sewage treatment system comprises an anaerobic tower or a hydrolysis acidification tank, an anoxic tank, an aerobic tank, an MBR membrane tank and an advanced oxidation device, wherein the anaerobic tower or the hydrolysis acidification tank is provided with a water inlet and a water outlet, the water inlet of the anaerobic tower or the hydrolysis acidification tank is communicated with the water inlet of the anoxic tank, the water outlet of the anoxic tank is communicated with the water inlet of the aerobic tank, the water outlet of the aerobic tank is communicated with the water inlet of the MBR membrane tank, the water outlet of the MBR membrane tank is communicated with the water inlet of the advanced oxidation device, the water outlet of the advanced oxidation device is communicated with a drain pipe, and the water outlet of the advanced oxidation device is also communicated with the anoxic tank through a reflux device and/or is communicated with the water inlet of the anaerobic tower or the hydrolysis acidification tank.
Preferably, the advanced oxidation device is an ozone catalytic oxidation device, a micro-electrolysis catalytic oxidation device, an electrocatalytic oxidation device, a Fenton oxidation device, a wet oxidation device or a photocatalytic oxidation device.
When the advanced oxidation device is an ozone catalytic oxidation device, the ozone adding amount is controlled to be 200-400 mg/L.
Preferably, the MBR membrane in the MBR membrane pool is a PVDF membrane with a filtration pore diameter smaller than 0.3 μm.
Further preferably, the MBR membrane in the MBR membrane pool is PVDF membrane with a filtration pore size smaller than 0.1 μm.
Further preferably, the PVDF membrane is a reinforced hollow fiber membrane curtain membrane or a flat membrane.
Preferably, the anaerobic tower is internally provided with suspended filler or elastic filler, the hydrolytic acidification tank is internally provided with elastic filler or soft filler, the anoxic tank is internally provided with elastic filler or soft filler, and the aerobic tank is internally provided with suspended filler or soft filler.
Further preferably, suspended filler is arranged in the anaerobic tower, soft filler is arranged in the hydrolysis acidification tank, elastic filler is arranged in the anoxic tank, and suspended filler is arranged in the aerobic tank.
Further preferably, the filler is a fixed or suspended filler to increase the concentration of sludge and age of sludge.
According to some embodiments, the effective volume of the anaerobic column or hydrolytic acidification tank is 450-550L, such as 450L,460L,470L,480L,490L,500L,510L,520L,530L,540L,550L.
The effective volume of the anoxic tank is 150 to 250L, such as 150L,160L,170L,180L,190L,200L,210L,220L,230L,240L and 250L.
The effective volume of the aerobic tank is 250-350L, such as 250L,260L,270L,280L,290L,300L,310L,320L,330L,340L and 350L.
The effective volume of the MBR membrane tank is 80-150L, such as 80L,90L,100L,110L,120L,130L,140L and 150L.
The effective volume of the advanced oxidation unit is 40-60L, such as 40L,50L and 60L.
Preferably, the sewage to be treated is one or more of chemical wastewater, medical wastewater, printing and dyeing wastewater, papermaking wastewater, biological fermentation wastewater, landfill leachate or kitchen waste wastewater.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
According to the invention, by designing a sewage treatment method of the intermittent sewage treatment system, aiming at the refractory organic wastewater, the water quality of the treated refractory organic wastewater meets the emission standard of urban sewage emission standard GB18918-2002 on the premise of reducing the occupied area, the input cost and the treatment duration of the treatment system.
Drawings
FIG. 1 is a schematic diagram of a batch sewage treatment system in an embodiment;
wherein, 1, an anaerobic tower or a hydrolytic acidification tank; 2. an anoxic tank; 3. an aerobic tank; 4. an MBR membrane pool; 5. advanced oxidation means; 6. a return valve; 7. and a discharge valve.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides an intermittent sewage treatment system, as shown in fig. 1, which comprises an anaerobic tower or a hydrolysis acidification tank 1, an anoxic tank 2, an aerobic tank 3, an MBR membrane tank 4 and an advanced oxidation device 5 which are sequentially connected in series, wherein a water inlet of the anaerobic tower or the hydrolysis acidification tank 1 is connected with a water inlet pipe, a water outlet of the anaerobic tower or the hydrolysis acidification tank 1 is communicated with a water inlet of the anoxic tank 2 through a pipeline, the anoxic tank 2 is communicated with a water inlet of the aerobic tank 3 through a pipeline, the aerobic tank 3 is communicated with a water inlet of the MBR membrane tank 4 through a pipeline, a water outlet of the MBR membrane tank 4 is communicated with a water inlet of the advanced oxidation device 5, a water outlet of the advanced oxidation device 5 is also communicated with a water outlet pipe provided with a discharge valve 7, and a water outlet of the advanced oxidation device 5 is also communicated with the anoxic tank 2 through a reflux pipe provided with a reflux valve 6 and a reflux pump. The anaerobic tower or the hydrolytic acidification tank 1, the anoxic tank 2, the aerobic tank 3 and the MBR membrane tank 4 are respectively connected with a sludge treatment system 8 through sludge discharge pipes. Wherein the anaerobic tower is provided with an internal reflux circulating device, the effective volume of the anaerobic tower is 550L, and the anaerobic filler adopts hundred-source environment-friendly polyurethane sponge filler; the effective volume of the hydrolytic acidification tank is 500L, and soft enzyme floating filler in Hongji environment is filled in the hydrolytic acidification tank; the effective volume of the anoxic tank 2 is 220L, and the anoxic tank 2 is provided with an elastic filler 20m 3 and adopts an environment-friendly Nantai elastic filler; the effective volume of the aerobic tank 3 is 330L, the aerobic tank 3 is provided with 30m 3 of suspended filler, and the Yudu environment-friendly MBBR suspended filler is adopted; the effective volume of the MBR membrane tank 4 is 100L, an immersed PVDF hollow fiber curtain membrane assembly (vast-rich membrane) or an immersed PVDF flat membrane assembly (high-Fu membrane) is arranged in the MBR membrane tank 4, the aperture of the PVDF membrane is 0.1 mu m, the effective volume of the advanced oxidation device 5 is 50L, and a micro-electrolysis catalytic oxidation tower (environmental protection of open source), an ozone catalytic oxidation tower (Long Antai environmental protection) or a Fenton oxidation tower (environmental protection of clean spring) can be selected.
Example 2
The sewage to be treated is water pretreated by mechanical grille, primary sedimentation, homogenization, pH adjustment and the like, and the water quality indexes are as follows: codcr=1220 mg/L, BOD 5＝230mg/L,NH3 -n=35 mg/L, tn=42 mg/L, tp=5.6 mg/L, ss=43 mg/L.
In the embodiment, the anaerobic tower or the hydrolytic acidification tank 1 is an anaerobic tower, an immersed PVDF hollow fiber curtain type membrane component is arranged in the MBR membrane tank 4, and the aperture of the PVDF membrane is 0.1 mu m; the advanced oxidation device 5 is a micro-electrolysis catalytic oxidation tower.
In the embodiment, a reflux valve on a reflux pipeline between the micro-electrolysis catalytic oxidation tower and the anoxic tank is opened, so that the effluent of the electrolysis catalytic oxidation tower is refluxed to the anoxic tank.
The system state before water inflow is as follows: the anaerobic tower is provided with 50L of last-batch retention sludge, the anoxic tank is provided with 20L of last-batch retention sludge, the aerobic tank is provided with 30L of last-batch retention sludge, the MBR membrane tank is provided with 100L of last-batch retention sewage, and the micro-electrolysis catalytic oxidation tower is provided with 50L of last-batch retention sewage.
The wastewater sample treatment operation comprises the following steps: injecting 500L wastewater sample into an anaerobic tower at one time, and circularly treating the inside of the anaerobic tower for 12hr, wherein 2L of sludge is discharged; then delivering the wastewater treated by the anaerobic tower to an anoxic tank water inlet at a flow rate of 50L/hr, delivering the wastewater to an aerobic tank water inlet at a flow rate of 50L/hr from a water outlet of the anoxic tank after the anoxic tank reaches a high level, delivering the wastewater to an MBR membrane tank at a flow rate of 50L/hr from a water outlet of the aerobic tank after the aerobic tank reaches a high level, starting an MBR membrane filtration water producing operation when the aerobic tank wastewater starts to flow into the MBR membrane tank, delivering the MBR membrane filtration water producing at a flow rate of 50L/hr to a micro-electrolysis catalytic oxidation tower, starting water producing from the MBR membrane tank and the micro-electrolysis catalytic oxidation tower after the anaerobic tower accumulates 498L wastewater and the anoxic tank, and completely delivering the produced water of the micro-electrolysis catalytic oxidation tower to the anoxic tank at a flow rate of 50L/hr through a reflux device, thereby starting a biochemical-membrane filtration-advanced oxidation cycle operation, maintaining two cycles of the cycle, and discharging sludge 1L from the anoxic tank, aerobic Chi Paini L, and MBR membrane Chi Paini L; and then discharging the produced water of the micro-electrolysis catalytic oxidation tower out of the system until the water discharge quantity reaches 494L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=33 mg/L, BOD 5＝6.3mg/L,NH3 -n=0.6 mg/L, tn=7.8 mg/L, tp=0.36 mg/L, ss=2.7 mg/L, complying with the first class a standard in town sewage discharge standard GB 18918-2002.
Example 3
The sewage to be treated is water pretreated by mechanical grating, primary sedimentation, homogenization, pH adjustment and the like of the wastewater of a certain synthetic raw material medicine enterprise, and the water quality indexes are as follows: codcr=2450 mg/L, BOD 5＝330mg/L,NH3 -n=110 mg/L, tn=233 mg/L, tp=35.6 mg/L, ss=66 mg/L.
In the embodiment, the anaerobic tower or the hydrolytic acidification tank 1 is an anaerobic tower, an immersed PVDF hollow fiber curtain membrane component is arranged in the MBR membrane tank 4, and the aperture of the PVDF membrane is 0.04 mu m; the advanced oxidation device 5 is an ozone catalytic oxidation tower, and the addition amount of ozone is controlled to be 200mg/L.
In the embodiment, a reflux valve on a reflux pipeline between the ozone catalytic oxidation tower and the anaerobic tower is opened, so that the effluent of the electrolytic catalytic oxidation tower is refluxed to the anaerobic tower.
The system state before water inflow is as follows: the anaerobic tower is provided with 50L of last-batch retention sludge, the anoxic tank is provided with 20L of last-batch retention sludge, the aerobic tank is provided with 30L of last-batch retention sludge, the MBR membrane tank is provided with 100L of last-batch retention sewage, and the ozone catalytic oxidation tower is provided with 50L of last-batch retention sewage.
The wastewater sample treatment operation comprises the following steps: injecting 500L wastewater sample into an anaerobic tower at one time, and circularly treating the inside of the anaerobic tower for 12hr, wherein 2L of sludge is discharged; then the wastewater treated by the anaerobic tower is conveyed to an anoxic tank water inlet at the flow rate of 50L/hr, the anoxic tank reaches a high liquid level, the wastewater is conveyed to an aerobic tank water inlet at the flow rate of 50L/hr from a water outlet of the anoxic tank, the wastewater is conveyed to an MBR membrane tank at the flow rate of 50L/hr from a water outlet of the aerobic tank after the anoxic tank reaches the high liquid level, when the aerobic tank wastewater starts to flow into the MBR membrane tank, MBR membrane filtration water production operation is started, MBR membrane filtration water production is conveyed to an ozone catalytic oxidation tower at the flow rate of 50L/hr, when the anaerobic tower accumulates 498L wastewater and is driven into the anoxic tank and the aerobic tank, the MBR membrane tank and the ozone catalytic oxidation tower start to produce water, and the produced water of the ozone catalytic oxidation tower is all driven into the anaerobic tower at the front end at the flow rate of 50L/hr through a reflux device, so that biochemical-membrane filtration-advanced oxidation cycle operation is started, three cycles of the cycle are maintained, and mud 1L, chi Paini L and MBR Chi Paini L are discharged from the anoxic tank; and then discharging the produced water of the micro-electrolysis catalytic oxidation tower out of the system until the water discharge quantity reaches 494L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=45 mg/L, BOD 5＝5.7mg/L,NH3 -n=0.85 mg/L, tn=8.4 mg/L, tp=0.40 mg/L, ss=2.9 mg/L, meeting the first class a standard in town sewage discharge standard GB 18918-2002.
Example 4
The sewage to be treated is water pretreated by mechanical grating, homogenization, preliminary sedimentation, pH adjustment and the like of sewage of a certain printing and dyeing factory, and the water quality indexes are as follows: codcr=1060 mg/L, BOD 5＝200mg/L,NH3 -n=24 mg/L, tn=56 mg/L, tp=17.7 mg/L, ss=150 mg/L, chromaticity=210 times.
In the embodiment, the anaerobic tower or the hydrolytic acidification tank 1 is a hydrolytic acidification tank, an immersed PVDF hollow fiber curtain membrane component is arranged in the MBR membrane tank 4, and the aperture of the PVDF membrane is 0.04 mu m; the advanced oxidation unit 5 is a Fenton oxidation tower.
In the embodiment, a reflux valve on a reflux pipeline between the ozone catalytic oxidation tower and the anoxic tank is opened, so that the effluent of the electrolytic catalytic oxidation tower is refluxed to the anoxic tank.
The system state before water inflow is as follows: the hydrolysis acidification tank is provided with 50L of last-batch retention sludge, the anoxic tank is provided with 20L of last-batch retention sludge, the aerobic tank is provided with 30L of last-batch retention sludge, the MBR membrane tank is provided with 100L of last-batch retention sewage, and the Fenton oxidation tower is provided with 50L of last-batch retention sewage.
The wastewater sample treatment operation comprises the following steps: injecting 500L wastewater sample into the hydrolytic acidification tank at one time, and circularly treating with internal plug flow for 12hr while discharging sludge 2L; then delivering the wastewater treated by the hydrolysis acidification tank to an anoxic tank water inlet at a flow rate of 50L/hr, delivering the wastewater to an aerobic tank water inlet from a water outlet of the anoxic tank at a flow rate of 50L/hr after the anoxic tank reaches a high liquid level, pumping the wastewater into an MBR membrane tank from a water outlet of the aerobic tank at a flow rate of 50L/hr after the aerobic tank reaches a high liquid level, starting an MBR water production operation when the wastewater in the aerobic tank starts to flow into the MBR membrane tank, and delivering membrane filtration water to an ozone catalytic oxidation tower at a flow rate of 50L/hr; after the anaerobic tower accumulates 498L wastewater and enters the anoxic tank and the aerobic tank, the MBR membrane tank and the Fenton oxidation tower just start producing water, and the produced water of the Fenton oxidation tower is completely entered into the anoxic tank at the front end, so that the biochemical-membrane filtration-advanced oxidation cycle operation of the batch is started, the cycle is maintained to continuously run for two periods, and mud 2L, aerobic Chi Paini L and MBR membrane Chi Paini L are discharged from the anoxic tank during the period; and (3) discharging the produced water of the Fenton oxidation tower out of the system until the quantity of discharged water reaches 490L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=43 mg/L, BOD 5＝10.6mg/L,NH3 -n=0.8 mg/L, tn=9.0 mg/L, tp=0.44 mg/L, ss=5.5 mg/L, chroma=26 times, meeting the first class a standard in town sewage discharge standard GB 18918-2002.
Example 5
The sewage to be treated is water pretreated by mechanical grating, homogenization, preliminary sedimentation, pH adjustment and the like of sewage of a landfill leachate treatment plant, and the water quality indexes are as follows: codcr=16260 mg/L, BOD 5＝2000mg/L,NH3 -n=476 mg/L, tn=502 mg/L, tp=45.7 mg/L, ss=112 mg/L.
In the embodiment, the anaerobic tower or the hydrolytic acidification tank 1 is an anaerobic tower, an immersed PVDF flat membrane component is arranged in the MBR membrane tank 4, and the aperture of the PVDF membrane is 0.08 mu m; the advanced oxidation device 5 is an ozone catalytic oxidation tower, and the addition amount of ozone is controlled to be 200mg/L.
In the embodiment, a reflux valve on a reflux pipeline between the ozone catalytic oxidation tower and the anaerobic tower is opened, so that the effluent of the electrolytic catalytic oxidation tower is refluxed to the anaerobic tower.
The system state before water inflow is as follows: the anaerobic tower is provided with 50L of last-batch retention sludge, the anoxic tank is provided with 20L of last-batch retention sludge, the aerobic tank is provided with 30L of last-batch retention sludge, the MBR membrane tank is provided with 100L of last-batch retention sewage, and the ozone catalytic oxidation tower is provided with 50L of last-batch retention sewage.
The specific operation of the intermittent operation experiment is as follows: injecting 500L wastewater sample into an anaerobic tower at one time, and circularly treating the inside of the anaerobic tower for 12hr, wherein 2L of sludge is discharged; then the wastewater treated by the anaerobic tower is conveyed to the water inlet of an anoxic tank at the flow rate of 50L/hr, the wastewater is conveyed to the water inlet of an aerobic tank from the water outlet of the anoxic tank at the flow rate of 50L/hr after the anoxic tank reaches a high level, the wastewater is conveyed to an MBR membrane tank from the water outlet of the aerobic tank at the flow rate of 50L/hr after the aerobic tank reaches a high level, when the wastewater in the aerobic tank starts to flow into the MBR membrane tank, MBR water producing operation is started, and membrane filtration water is conveyed to an ozone catalytic oxidation tower at the flow rate of 50L/hr; after 498L wastewater accumulated in the anaerobic tower is pumped into the anoxic tank and the aerobic tank, the MBR membrane tank and the ozone catalytic oxidation tower just start producing water, and all the produced water of the ozone catalytic oxidation tower is pumped into the anaerobic tower at the front end, so that four cycles of advanced oxidation-biochemistry-membrane filtration cyclic operation of the batch are started, and 3L of mud, chi Paini L of aerobic water and Chi Paini L of MBR membrane are discharged from the anoxic tank in each cycle; and (3) discharging the produced water of the ozone catalytic oxidation tower out of the system until the quantity of discharged water reaches 488L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=36 mg/L, BOD 5＝11mg/L,NH3 -n=1.4 mg/L, tn=6.6 mg/L, tp=0.25 mg/L, ss=3.6 mg/L, meeting the first level of urban sewage discharge standard GB 18918-2002.
Comparative example 1
The sewage to be treated in this comparative example was the same as in example 2.
In this comparative example, the advanced oxidation device 5 is arranged in front, the intermittent sewage treatment system comprises an advanced oxidation device 5, an anaerobic tower or hydrolysis acidification tank 1, an anoxic tank 2, an aerobic tank 3 and an MBR membrane tank 4 which are sequentially connected in series, wherein the water inlet of the advanced oxidation device 5 is connected with a water inlet pipe, the water outlet of the advanced oxidation device 5 is communicated with the water inlet of the anaerobic tower or hydrolysis acidification tank 1 through a pipeline, the anaerobic tower or hydrolysis acidification tank 1 is communicated with the water inlet of the anoxic tank 2 through a pipeline, the anoxic tank 2 is communicated with the water inlet of the aerobic tank 3 through a pipeline, the water outlet of the aerobic tank 3 is communicated with the water inlet of the MBR membrane tank 4, the water outlet of the MBR membrane tank 4 is also communicated with a water outlet pipe provided with a discharge valve 7, and the water outlet of the MBR membrane tank 4 is also communicated with the water inlet of the advanced oxidation device 5 through a backflow pipe provided with a backflow valve 6 and a backflow pump.
In the comparative example, the advanced oxidation device 5 is a micro-electrolysis catalytic oxidation tower, the anaerobic tower or the hydrolytic acidification tank 1 is an anaerobic tower, the submerged PVDF hollow fiber curtain membrane component is arranged in the MBR membrane tank 4, and the aperture of the PVDF membrane is 0.1 mu m.
In this comparative example, a return valve on a return pipe between the MBR membrane tank 4 and the advanced oxidation device 5 was opened to return the effluent of the MBR membrane tank 4 to the advanced oxidation device 5.
The system state before water inflow is as follows: the micro-electrolysis catalytic oxidation tower is provided with 50L of upper batch of reserved sewage, the anaerobic tower is provided with 50L of upper batch of reserved sludge, the anoxic tank is provided with 20L of upper batch of reserved sludge, the aerobic tank is provided with 30L of upper batch of reserved sludge, the MBR membrane tank is provided with 100L of upper batch of reserved sewage,
The wastewater sample treatment operation comprises the following steps: delivering 500L wastewater sample into a micro-electrolysis catalytic oxidation tower at a flow rate of 50L/hr, continuously delivering wastewater treated by the micro-electrolysis catalytic oxidation tower into an anaerobic tower at one time, and circularly treating the wastewater in the anaerobic tower for 12hr to remove 2L of sludge; then, the wastewater treated by the anaerobic tower is conveyed to a water inlet of an anoxic tank at a flow rate of 50L/hr from a water outlet of the anaerobic tower, the wastewater is conveyed to an aerobic tank at a flow rate of 50L/hr from a water outlet of the anoxic tank after reaching a high liquid level, the wastewater is conveyed to an MBR membrane tank at a flow rate of 50L/hr from a water outlet of the aerobic tank after reaching a high liquid level, when the wastewater in the aerobic tank starts to flow into the MBR membrane tank, MBR water production operation is started, and membrane filtration produced water is conveyed to a micro-electrolysis catalytic oxidation tower in a backflow manner at a flow rate of 50L/hr; after 498L wastewater accumulated by the anaerobic tower is pumped into the anoxic tank and the aerobic tank, the MBR membrane tank just starts to return produced water to the micro-electrolysis catalytic oxidation tower, so that the advanced oxidation-biochemical-membrane filtration cycle operation of the batch is started for two periods, wherein 2L of sludge is discharged from the anaerobic tower, chi Paini L of anoxic is carried out, chi Paini L of aerobic is carried out, and Chi Paini L of MBR membrane is carried out in each cycle period; and (3) discharging the produced water of the MBR membrane tank out of the system until the water discharge quantity reaches 488L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=80 mg/L, BOD 5＝25mg/L,NH3 -n=0.8 mg/L, tn=10 mg/L, tp=0.42 mg/L, ss=2.7 mg/L, the effluent does not reach the first class a standard in town sewage discharge standard GB 18918-2002.
Comparative example 2
The sewage to be treated in this comparative example was the same as in example 2, and the system preparation and system start-up operation before the water inlet experiment were the same as in example 2.
The specific operation of the formal operation experiment is as follows: injecting 500L wastewater sample into an anaerobic tower at one time, and circularly treating the inside of the anaerobic tower for 6hr, wherein 1L of sludge is discharged; then delivering the wastewater treated by the anaerobic tower to an anoxic tank water inlet at a flow rate of 100L/hr, delivering the wastewater to an aerobic tank water inlet at a flow rate of 100L/hr from a water outlet of the anoxic tank after the anoxic tank reaches a high level, delivering the wastewater to an MBR membrane tank at a flow rate of 100L/hr from a water outlet of the aerobic tank after the aerobic tank reaches a high level, starting an MBR membrane filtration water producing operation when the aerobic tank wastewater starts to flow into the MBR membrane tank, delivering the MBR membrane filtration water producing at a flow rate of 100L/hr to a micro-electrolysis catalytic oxidation tower, starting water producing from the MBR membrane tank and the micro-electrolysis catalytic oxidation tower after the anaerobic tower accumulates 499L wastewater and the aerobic tank, and completely delivering the produced water of the micro-electrolysis catalytic oxidation tower to the anoxic tank at a flow rate of 100L/hr through a reflux device, thereby starting a biochemical-membrane filtration-advanced oxidation cycle operation, maintaining four cycles of mud circulation, and discharging 1L from the anoxic tank, aerobic Chi Paini L and MBR membrane Chi Paini L; and then discharging the produced water of the micro-electrolysis catalytic oxidation tower out of the system until the water discharge quantity reaches 495L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=150 mg/L, BOD 5＝36mg/L,NH3 -n=0.6 mg/L, tn=10.8 mg/L, tp=0.44 mg/L, ss=2.7 mg/L, the effluent does not reach the first class a standard in town sewage discharge standard GB 18918-2002.
Comparative example 3
The sewage to be treated in this comparative example was the same as in example 2, and the system preparation and system start-up operation before the water inlet experiment were the same as in example 2.
The specific operation of the formal operation experiment is as follows: injecting 500L wastewater sample into an anaerobic tower at one time, and circularly treating the inside of the anaerobic tower for 9hr, wherein 2L of sludge is discharged; then delivering the wastewater treated by the anaerobic tower to an anoxic tank water inlet at a flow rate of 25L/hr, delivering the wastewater to an aerobic tank water inlet at a flow rate of 25L/hr from a water outlet of the anoxic tank after the anoxic tank reaches a high level, delivering the wastewater to an MBR membrane tank at a flow rate of 25L/hr from a water outlet of the aerobic tank after the aerobic tank reaches a high level, starting an MBR membrane filtration water producing operation when the aerobic tank wastewater starts to flow into the MBR membrane tank, delivering the MBR membrane filtration water producing at a flow rate of 25L/hr to a micro-electrolysis catalytic oxidation tower, starting water producing from the MBR membrane tank and the micro-electrolysis catalytic oxidation tower after the anaerobic tower accumulates 498L wastewater and the anoxic tank, and completely delivering the produced water of the micro-electrolysis catalytic oxidation tower to the anoxic tank at a flow rate of 25L/hr through a reflux device, thereby starting a biochemical-membrane filtration-advanced oxidation cycle operation, maintaining the cycle for three periods, namely, discharging sludge 1L from the anoxic tank, aerobic Chi Paini L and MBR membrane Chi Paini L; and then discharging the produced water of the micro-electrolysis catalytic oxidation tower out of the system until the water discharge quantity reaches 494L, stopping running, ending the batch operation, and recovering the system to a state before water inflow. The quality of the discharged water was analyzed, and the results were as follows: codcr=120 mg/L, BOD 5＝30mg/L,NH3 -n=0.6 mg/L, tn=9.5 mg/L, tp=0.30 mg/L, ss=2.7 mg/L, the effluent does not reach the first class a standard in town sewage discharge standard GB 18918-2002.
The water quality test methods in the above examples and comparative examples are referred to as follows:
1) CODcr: dichromate method for measuring chemical oxygen demand of water quality in GB 11914-1989
2) BOD 5: method for measuring, diluting and inoculating five-day biochemical oxygen demand (BOD 5) of HJ 505-2009 water quality
3) TN: determination of total nitrogen in HJ 636-2012 water quality alkaline potassium persulfate digestion ultraviolet spectrophotometry
4) NH 3 -N: nahner reagent spectrophotometry for determining ammonia nitrogen in HJ 535-2009 water
5) TP: GB 11893-89 spectrophotometry for determining total phosphorus in water quality
6) SS: determination of GBT 11901-89 aqueous suspension
7) Chromaticity: GB 119023-89 determination of Water quality and chromaticity
The present invention has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the same, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (3)
1. A method for treating degradation-resistant sewage is characterized by comprising the following steps: the sewage to be treated is water obtained by mechanically grating, homogenizing, primary sedimentation and pH adjustment of sewage of a landfill leachate treatment plant, and the water quality indexes are as follows: codcr=16260 mg/L, BOD 5＝2000mg/L,NH3 -n=476 mg/L, tn=502 mg/L, tp=45.7 mg/L, ss=112 mg/L, said treatment method comprising the steps of:
(1) Anaerobic biochemical treatment is carried out on the sewage to be treated;
(2) Performing anoxic biochemical treatment on the treated water in the step (1);
(3) Carrying out aerobic biochemical treatment on the treated water in the step (2);
(4) Treating the treated water in the step (3) by an MBR (Membrane bioreactor);
(5) Performing advanced oxidation treatment on the treated water in the step (4);
(6) Refluxing the treated water in the step (5) to the step (1), circularly carrying out the steps (2) to (6) for 4 times,
The treatment method adopts an intermittent sewage treatment system, the intermittent sewage treatment system comprises an anaerobic tower, an anoxic tank, an aerobic tank, an MBR membrane tank and an advanced oxidation device which are respectively provided with a water inlet and a water outlet, the water inlet of the anaerobic tower is communicated with sewage to be treated, the water outlet of the anaerobic tower is communicated with the water inlet of the anoxic tank, the water outlet of the anoxic tank is communicated with the water inlet of the aerobic tank, the water outlet of the aerobic tank is communicated with the water inlet of the MBR membrane tank, the water outlet of the MBR membrane tank is communicated with the water inlet of the advanced oxidation device, the water outlet of the advanced oxidation device is communicated with a drain pipe, the water outlet of the advanced oxidation device is also communicated with the water inlet of the anaerobic tower through a reflux device,
The MBR membrane in the MBR membrane pool is a PVDF membrane with the filtration pore diameter smaller than 0.3 mu m,
The advanced oxidation device is an ozone catalytic oxidation tower, the addition amount of ozone is controlled to be 200-400 mg/L,
The effective volume 550L of the anaerobic tower,
The effective volume of the anoxic tank is 220L,
The effective volume of the aerobic tank is 330L,
The effective volume of the MBR membrane tank is 100L,
The effective volume of the ozone catalytic oxidation tower is 50L,
The specific operation of the treatment method is as follows: the method comprises the steps of injecting 500L of sewage to be treated into an anaerobic tower at one time, circularly treating the inside of the anaerobic tower for 12 hours, discharging 2L of sludge during the period, then transporting the wastewater treated by the anaerobic tower to an anoxic tank water inlet at a flow rate of 50L/hr, transporting the wastewater to an aerobic tank water inlet from a water outlet of the anoxic tank at a flow rate of 50L/hr after the anoxic tank reaches a high level, transporting the wastewater to an MBR membrane tank from a water outlet of the aerobic tank at a flow rate of 50L/hr after the aerobic tank reaches a high level, starting a membrane filtration water producing operation when the wastewater starts to flow into the MBR membrane tank, transporting the membrane filtration water to an ozone catalytic oxidation tower at a flow rate of 50L/hr, accumulating 498L of wastewater in the anaerobic tower, just starting the water producing by the MBR membrane tank and the ozone catalytic oxidation tower after the anaerobic tower is integrated, completely driving the water produced by the anaerobic tower at the front end, thereby starting four cycles of advanced oxidation-biochemical-membrane filtration circulating operation, discharging 3L of sludge from the tank, aerobic Chi Paini L, and stopping the membrane Chi Paini L of sewage from the anaerobic catalytic oxidation tower in each cycle period, stopping the operation of the anaerobic system until the batch of the water producing system is stopped when the water is discharged from the batch to reach an intermittent state, and the water production system is stopped after the batch is discharged.
2. The method for treating refractory sewage according to claim 1, wherein: the anaerobic tower is internally provided with suspended filler or elastic filler, the anoxic tank is internally provided with elastic filler or soft filler, and the aerobic tank is internally provided with suspended filler or soft filler.
3. The method for treating refractory sewage according to claim 1, wherein: the pore diameter of the PVDF film is 0.08 mu m.
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