CN104445814A - Process and device for treating tetracycline antibiotic wastewater - Google Patents
Process and device for treating tetracycline antibiotic wastewater Download PDFInfo
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- CN104445814A CN104445814A CN201410664259.6A CN201410664259A CN104445814A CN 104445814 A CN104445814 A CN 104445814A CN 201410664259 A CN201410664259 A CN 201410664259A CN 104445814 A CN104445814 A CN 104445814A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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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
- C02F3/005—Combined electrochemical biological processes
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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
- C02F3/301—Aerobic and anaerobic treatment in the same reactor
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
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Abstract
The invention discloses a process and a device for treating tetracycline antibiotic wastewater. The process comprises a pretreatment step and an anaerobic/aerobiotic treatment step; the pretreatment step comprises performing electrolytic treatment by taking ferric carbon microelectrolysis ceramsite as a filler; the anaerobic/aerobiotic treatment step comprises orderly performing anaerobic treatment and aerobiotic treatment on the wastewater treated by virtue of the pretreatment step, and fly ash ceramsite is taken as a filler for the anaerobic treatment, and sludge ceramsite is taken as a filler for the aerobiotic treatment. The invention also discloses the device for the process. According to the process and the device for treating the tetracycline antibiotic wastewater, the multi-stage treatment process is simplified, the capital investment is greatly reduced and the capital is saved; and the own characteristics of the wastewater are thoroughly utilized, and the dosage of a chemical agent is reduced, and therefore, secondary pollution is reduced while the cost is saved.
Description
Technical field
The present invention relates to a kind of technique for the treatment of tetracycline antibiotics waste water and device, belong to technical field of waste water processing.
Background technology
Tetracyclines pharmacy waste water belongs to high concentrated organic wastewater, and COD is 6850mg/L up to 18000mg/L, BOD, and containing oxalic acid 5000 ~ 7000mg/L, more than nitrogen 2000mg/L, waste water is in acid.Antibiotic substance in addition containing a large amount of suppression microorganism in waste water, containing the concentration of remaining tsiklomitsin between 0.7-1g/L, and tsiklomitsin content is up to 1.5g/L in crystalline mother solution aborning, and biodegradability is poor, is generally difficult to directly carry out biochemical treatment.The colourity of waste water is higher simultaneously, and crystalline mother solution is deep yellow, and colourity is between 1000-1600 times, and waste water intermittently discharged, turn increases difficulty to wastewater treatment.
Current process tetracycline antibiotics waste water many employings multilevel processing technology.Pre-treatment is generally divided into add follow-up biochemical treatment.Pre-treatment is degraded to master with electrochemical degradation and Fenton method again, and the processing cost of two kinds of methods is higher.Follow-up biochemical treatment is then various, is generally first to use anaerobic process to degrade, and then uses aerobic method to be further processed, and result two kinds of reactor floor spaces are comparatively large, and initial cost is higher.The series combination of multilevel processing technology adds investment on the one hand in addition, and processing costs raises, and on the other hand due to waste water intermittently discharged, makes the complicated technology being originally difficult to regulate and control become extremely difficult.Such as, give " pre-treatment+diphasic anaerobic+improvement SBR+ BAF+improvement coagulating sedimentation combination " technique in Chinese patent document CN101157510A, though obtain good removal effect, but multi-stage process is very complicated, regulation and control difficulty strengthens, and too increases processing cost undoubtedly.
Iron-carbon micro-electrolysis technology is a kind of new technology for sewage physicochemical process on the other hand.Such as, utilize iron-carbon micro-electrolysis technical finesse containing Cu in Chinese patent document CN101941749A
2+berberine waste water, a part of berberine of degrading reclaims copper simultaneously, obtains certain effect.But owing to being directly add iron powder and carbon dust in technology implementation, cause iron powder oxidizable, waste a part of iron powder, reduce iron-carbon micro-electrolysis ability simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of easy, efficiently, initial cost is supported, and runs simple and easy to control, the technique of the process tetracycline antibiotics waste water that working cost is lower and device.
Technical solution of the present invention is as follows:
For the treatment of a technique for tetracycline antibiotics waste water, comprise pre-treatment step and aerobic/anaerobic treatment step;
Described pre-treatment step is using iron-carbon micro-electrolysis haydite as filler, carries out electrolysis treatment; The particle diameter of described iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 850-950kg/m
3, packed height is 80-100cm, and hydraulic detention time is 4-8h, and air water volume ratio is (5-8): 1;
Described aerobic/anaerobic treatment step be by pre-treatment step process after waste water carry out anaerobic treatment and aerobic treatment successively, anaerobic treatment take lytag as filler, the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 400-500kg/m
3, the height of filler is 60-100cm; Aerobic treatment take sludge ceramsite as filler, particle diameter 5-10mm, pellet density 900-1000kg/m
3, tap density 450-550kg/m
3, the height of filler is 50-80cm, and air water volume ratio is (13-17): 1; Described anaerobic treatment and the hydraulic detention time of aerobic treatment are 12-16h.
According to the present invention, preferably, the inlet flow-patterm 3.5-4.5 of pre-treatment step; Water outlet pH6-7 after pre-treatment step, further preferably, adjusting water outlet pH6.5-7 after pre-treatment step, more preferably regulates with CaO.
According to the present invention, preferably, reflux in pre-treatment step to waste water, reflux ratio is (2-4): 1; Carry out back flushing to filler, backwashing period is 3-5 days;
Preferably, reflux in anaerobic treatment and Aerobic to waste water, reflux ratio is (2-3): 1, carries out back flushing to filler, and backwashing period is 5-7 days.
According to the present invention, described iron-carbon micro-electrolysis haydite, lytag and sludge ceramsite can select the conventional haydite of sewage treatment area.Wherein, iron-carbon micro-electrolysis haydite can prepare with reference to Chinese patent document CN103253741A, and sludge ceramsite can prepare with reference to Chinese patent document CN101638312A.
According to the present invention, a kind of device for the treatment of tetracycline antibiotics waste water, comprise pretreatment unit and aerobic/anaerobic treatment unit, described pretreatment unit comprises pretreatment unit packing area, lower end, pretreatment unit packing area is provided with pretreatment unit filter plate, pretreatment unit bottom is fixedly connected with by pretreatment unit joint flange and the pretreatment unit buffer zone that intakes, pretreatment unit aeration plate is provided with between pretreatment unit joint flange and pretreatment unit filter plate, pretreatment unit top is provided with pretreatment unit top cover, pretreatment unit top cover is provided with perforate, pretreatment unit is provided with pretreatment unit recycling effluent mouth between pretreatment unit top cover and pretreatment unit packing area, pretreatment unit back flushing water-in and pretreatment unit water outlet, pretreatment unit water inlet setting buffers has pretreatment unit backflow water-in and pretreatment unit water-in, pretreatment unit water-in is connected with pretreatment unit intake pump, pretreatment unit recycling effluent mouth is connected by pretreatment unit reflux pump with pretreatment unit backflow water-in,
Described aerobic/anaerobic treatment unit comprises anaerobic zone and aerobic zone, anaerobic effluent buffer zone and aerobic water inlet buffer zone is disposed with between anaerobic zone and aerobic zone, be fixedly connected with by anaerobic effluent buffer zone joint flange between anaerobic effluent buffer zone and aerobic water inlet buffer zone, be fixedly connected with by aerobic zone joint flange between aerobic water inlet buffer zone and aerobic zone, aerobic zone water inlet valve is provided with between anaerobic effluent buffer zone and aerobic water inlet buffer zone, anaerobic effluent setting buffers has anaerobic zone back flushing water-in, triphase separator and airway, aerobic water inlet setting buffers has aerobic zone aeration plate and aerobic zone back flushing water outlet, bottom, aerobic zone is provided with aerobic zone filter plate, aerobic/anaerobic treatment unit top is provided with aerobic/anaerobic treatment unit top cover, aerobic/anaerobic treatment unit top cover arranges porose, is provided with aerobic/anaerobic treatment unit recycling effluent mouth, aerobic zone back flushing water-in and aerobic/anaerobic treatment unit water outlet between aerobic/anaerobic treatment unit top cover and aerobic zone,
Lower end, anaerobic zone is provided with anaerobic zone filter plate, aerobic/anaerobic treatment unit bottom is fixedly connected with by anaerobic zone joint flange and the anaerobism buffer zone that intakes, anaerobism water inlet setting buffers has aerobic/anaerobic treatment unit backflow water-in and aerobic/anaerobic treatment unit water-in, connected by aerobic/anaerobic treatment unit reflux pump between aerobic/anaerobic treatment unit recycling effluent mouth and aerobic/anaerobic treatment unit backflow water-in, connected by aerobic/anaerobic treatment unit intake pump between pretreatment unit water outlet and aerobic/anaerobic treatment unit water-in.
According to the present invention, preferably, also regulating tank is provided with between described pretreatment unit water outlet and aerobic/anaerobic treatment unit water-in.
According to the present invention, preferably, described pretreatment unit bottom is provided with pretreatment unit base, and described aerobic/anaerobic treatment unit bottom is provided with aerobic/anaerobic treatment unit base.
According to the present invention, preferably, described pretreatment unit packing area is filled with iron-carbon micro-electrolysis haydite, and further preferably, the particle diameter of iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 850-950kg/m
3, packed height is 80-100cm;
Described anaerobic zone is filled with lytag, further preferably, and the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 400-500kg/m
3, the height of filler is 60-100cm;
Described aerobic zone is filled with sludge ceramsite, further preferably, and the particle diameter 5-10mm of sludge ceramsite, pellet density 900-1000kg/m
3, tap density 450-550kg/m
3, the height of filler is 50-80cm.
According to the present invention, preferably, described pretreatment unit and aerobic/anaerobic treatment unit are the capable structure of cylinder, and described pretreatment unit water inlet buffer zone and anaerobism water inlet buffer zone are pyramidal structure.
According to the present invention, preferably, the total height of described anaerobic effluent buffer zone and aerobic water inlet buffer zone is 20-50cm.
According to the present invention, preferably, the height between pretreatment unit top cover and pretreatment unit packing area is 20-30cm, and the height between aerobic/anaerobic treatment unit top cover and aerobic zone is 20-30cm.
According to the present invention, the method for work of the above-mentioned device for the treatment of tetracycline antibiotics waste water, step is as follows:
Iron-carbon micro-electrolysis haydite, lytag and sludge ceramsite are loaded respectively in pretreatment unit packing area, anaerobic zone and aerobic zone, waste water is pumped into by pretreatment unit intake pump, aeration is carried out by pretreatment unit aeration plate, the hydraulic detention time controlled in pretreatment unit is 4-8h, and air water volume ratio is (5-8): 1; Refluxed to the process waste water in pretreatment unit by pretreatment unit reflux pump, controlling reflux ratio is (2-4): 1; Regularly carry out back flushing to pretreatment unit, backwashing period is 3-5 days, and backwashing water is discharged by pretreatment unit water-in;
Waste water after pretreatment unit process enters into aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit intake pump, the hydraulic detention time controlled in aerobic/anaerobic treatment unit is 12-16h, carry out aeration by aerobic zone aeration plate to aerobic zone, controlling air water volume ratio is (13-17): 1; Refluxed to the waste water in aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit reflux pump, controlling reflux ratio is (2-3): 1, and regularly carry out back flushing to anaerobic zone and aerobic zone, backwashing period is 5-7 days; Backwashing water in anaerobic zone is discharged by aerobic/anaerobic treatment unit water-in, and triphase separator is separated with waste water the gas produced in anaerobic zone, is discharged by the gas produced by airway in anaerobic zone; Waste water, after the process of aerobic/anaerobic treatment unit, is discharged from aerobic/anaerobic treatment unit water outlet.
According to the present invention, preferably, the waste water after pretreatment unit process is introduced in regulating tank and regulates pH to 6.5-7.0, then enters into aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit intake pump; Preferred further, the pH of waste water in regulating tank is regulated by adding CaO.
Pretreatment unit of the present invention adopts iron-carbon micro-electrolysis haydite as filler, iron-carbon micro-electrolysis haydite is with iron powder, carbon dust, red mud and clay for raw material, and according to the mixing of certain ratio, a small amount of nickel powder of outer interpolation is as catalyzer, then granulation, fires under reducing atmosphere and forms.The application of iron-carbon micro-electrolysis ceramics filling of the present invention, improves the ability of light electrolysis on the one hand, the macromolecular organism such as most of tsiklomitsin of effectively degrading, destroy chromophoric group simultaneously, remove colourity, also improve the biodegradability of waste water, for follow-up biological treatment is ready; On the other hand because haydite itself has certain adsorption, after interpolation carbon dust prepares iron-carbon micro-electrolysis haydite, adsorption strengthens, and can remove the colourity of waste water further.Meanwhile, because in iron-carbon micro-electrolysis haydite, the combination of iron powder and other materials makes iron powder not easily oxidized, solve and directly add the problem that iron powder easily exposes oxidation, the work-ing life of filler is increased.In addition, the pre-treatment of iron-carbon micro-electrolysis haydite also has the function removing part COD concurrently.
In aerobic/anaerobic treating processes of the present invention, anaerobic zone uses lytag, aerobic zone uses sludge ceramsite, and the application of lytag and sludge ceramsite shortens the start time of bio-reactor on the one hand, enhances the removal ability of reactor on the other hand.Tetracycline wastewater after pretreatment unit is pretreated, its biochemical strengthens greatly, the antibiotic substance of biocidal property greatly reduces, after larger molecular organics is changed into small-molecule substance, first through anaerobic treatment, remove most COD, simultaneously residual tsiklomitsin is degraded by anaerobion, and the biogas produced in anaerobic treatment process is collected by triphase separator and airway; After anaerobic treatment, most organic substance is removed, but the general still difficult emission standard reaching country, therefore waste water processes through aerobic zone again, further removal organic waste wherein, are back to anaerobic zone simultaneously and carry out denitrogenation dephosphorizing sulphur removal, reach emission standard to make final water outlet.
Pretreatment unit first establishes aeration plate, upwards establishes perforation filter plate again, support iron-carbon micro-electrolysis ceramics filling.Pretreatment unit water inlet buffer zone and anaerobism water inlet buffer zone are taper, solid waste when being convenient to back flushing as early as possible in discharger and backwashing wastewater.Back flushing can remove the suspended solids refuse of iron-carbon micro-electrolysis ceramics filling surface adsorption, improves light electrolysis efficiency.Discharge due to tetracycline wastewater is intermittent, therefore arranges regulating tank to adapt to the needs of follow-up biochemical treatment.
The present invention, can reach about 6-7 through its pH of the pretreated waste water of iron-carbon micro-electrolysis haydite, be suitable for follow-up biochemical treatment completely, avoid and add other chemical reagent, both saved expense, turn avoid the secondary pollution added too much reagent place and bring.Because Fe can become Fe after electrochemical action
2+, or be further oxidized to Fe
3+, can be hydrolyzed with the difference of solution ph.When waste water ph is lower, hydrolysate, with positive charge, attracts each other to colloidal solid electronegative in waste water electrification neutralizing effect and mutually assembles.Can use in CaO in regulating tank and water outlet if desired, in waste water, generate a large amount of Fe (OH)
2with Fe (OH)
3they are good flocculation agent, there is high reactivity, effective absorption, charge neutrality and bridging cohesion can be played to the colloid in waste water or subparticle, form flco, and the pollutent in further planar water, to reduce surface energy, finally be agglomerated into larger flco precipitation, thus strengthen decontamination effect improving.
The present invention, the anaerobism water inlet buffer zone of aerobic/anaerobic treatment unit is pyramidal structure, is convenient to the removal of aging mud during back flushing.The bottom of anaerobic zone is perforation filter plate, support flyash ceramic particulate filler.When Nitrogen-and Phosphorus-containing and sulfate ion more time suitably can increase the height of anaerobic zone filler.Anaerobic zone arranges independent back flushing water-in, is convenient to independent back flushing.The bottom of aerobic water inlet buffer zone arranges the water-in of aerobic zone water inlet valve as aerobic zone.Back flushing water outlet in aerobic zone is set above aerobic water-in, is convenient to the independent back flushing of aerobic zone.Anaerobic effluent buffer zone and aerobic water inlet buffer zone are collectively referred to as detests-aerobic joining region, and it is highly 20-50cm.Aerobic/anaerobic treatment unit arranges multiple flange, so that dismounting transport, and filling ceramics filling and maintenance.
Beneficial effect of the present invention is as follows:
1, this invention simplifies multilevel processing technology, greatly reduce initial cost, save fund.
2, the present invention is owing to only having two treatment unit, is convenient to control, and start time is short, the filler of pretreatment unit is long for duration of service, the filler of aerobic/anaerobic treatment unit can regenerate through process, can reduce waste water processed in units expense, have very high practical value.
3, the present invention makes full use of the characteristic of waste water itself, reduces the dosage of chemical agent, reduces secondary pollution while cost-saving.
4, process tetracycline antibiotics waste water high-efficiency of the present invention is flexible, and effectively can either remove COD, total nitrogen and total phosphorus, the macromole bacteriostatic antibiotic of tetracyclines of also effectively degrading, water outlet meets discharging standards completely.The device dismounting transport used is flexible, and combination process is simple, is convenient to large-scale application.
Accompanying drawing explanation
Fig. 1 is the agent structure schematic diagram of invention for the treatment of tetracycline antibiotics waste water plant.
Wherein: 1-1, pretreatment unit base, 1-2, aerobic/anaerobic treatment unit base, 2-1, pretreatment unit joint flange, 2-2, anaerobic zone joint flange, 2-3, aerobic zone joint flange, 2-4, anaerobic effluent buffer zone joint flange, 3-1, pretreatment unit aeration plate, 3-2, aerobic zone aeration plate, 4-1, pretreatment unit filter plate, 4-2, anaerobic zone filter plate, 4-3, aerobic zone filter plate, 5, pretreatment unit packing area, 6, pretreatment unit recycling effluent mouth, 7, pretreatment unit back flushing water-in, 8, pretreatment unit water-in, 9, pretreatment unit water outlet, 10, pretreatment unit backflow water-in, 11, anaerobic zone, 12, anaerobic zone back flushing water-in, 13, aerobic zone water inlet valve, 14, triphase separator, 15, airway, 16, aerobic/anaerobic treatment unit recycling effluent mouth, 17, aerobic zone back flushing water-in, 18, aerobic/anaerobic treatment unit backflow water-in, 19, aerobic/anaerobic treatment unit water-in, 20, aerobic zone back flushing water outlet, 21, aerobic/anaerobic treatment unit water outlet, 22, aerobic zone, 23-1, pretreatment unit top cover, 23-2, aerobic/anaerobic treatment unit top cover, 24, anaerobic effluent buffer zone, 25, aerobic water inlet buffer zone, 26, anaerobism water inlet buffer zone, 27, regulating tank, 28-1, pretreatment unit intake pump, 28-2, pretreatment unit reflux pump, 28-3, aerobic/anaerobic treatment unit intake pump, 28-4, aerobic/anaerobic treatment unit reflux pump, 29, pretreatment unit water inlet buffer zone.
Embodiment
Below by specific embodiment, also the invention will be further described by reference to the accompanying drawings, but be not limited thereto.
In embodiment, iron-carbon micro-electrolysis haydite prepares with reference to Chinese patent document CN103253741A, and sludge ceramsite prepares with reference to Chinese patent document CN101638312A, and Jinan Hai Hua filtrate company limited taken from by lytag.
Embodiment 1,
For the treatment of a technique for tetracycline antibiotics waste water, comprise pre-treatment step and aerobic/anaerobic treatment step;
Described pre-treatment step is using iron-carbon micro-electrolysis haydite as filler, carries out electrolysis treatment; The particle diameter of described iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 850kg/m
3, packed height is 100cm, and hydraulic detention time is 4h, and air water volume ratio is 5:1;
Described aerobic/anaerobic treatment step be by pre-treatment step process after waste water carry out anaerobic treatment and aerobic treatment successively, anaerobic treatment take lytag as filler, the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 400kg/m
3, the height of filler is 100cm; Aerobic treatment take sludge ceramsite as filler, particle diameter 5-10mm, pellet density 900-1000kg/m
3, tap density 450kg/m
3, the height of filler is 80cm, and air water volume ratio is 13:1; Described anaerobic treatment and the hydraulic detention time of aerobic treatment are 16h;
The inlet flow-patterm 3.5-4.5 of pre-treatment step; Water outlet pH6-7 after pre-treatment step.
Embodiment 2,
For the treatment of a technique for tetracycline antibiotics waste water, comprise pre-treatment step and aerobic/anaerobic treatment step;
Described pre-treatment step is using iron-carbon micro-electrolysis haydite as filler, carries out electrolysis treatment; The particle diameter of described iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 950kg/m
3, packed height is 80cm, and hydraulic detention time is 8h, and air water volume ratio is 8:1;
Described aerobic/anaerobic treatment step be by pre-treatment step process after waste water carry out anaerobic treatment and aerobic treatment successively, anaerobic treatment take lytag as filler, the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 500kg/m
3, the height of filler is 60cm; Aerobic treatment take sludge ceramsite as filler, particle diameter 5-10mm, pellet density 900-1000kg/m
3, tap density 550kg/m
3, the height of filler is 50cm, and air water volume ratio is 17:1; Described anaerobic treatment and the hydraulic detention time of aerobic treatment are 16h.
Embodiment 3,
As described in Example 1 for the treatment of the technique of tetracycline antibiotics waste water, unlike:
Reflux to waste water in pre-treatment step, reflux ratio is 2:1; Carry out back flushing to filler, backwashing period is 3 days;
Reflux to waste water in anaerobic treatment and Aerobic, reflux ratio is 2:1, carries out back flushing to filler, and backwashing period is 5 days.
Embodiment 4,
As described in Example 2 for the treatment of the technique of tetracycline antibiotics waste water, unlike:
Reflux to waste water in pre-treatment step, reflux ratio is 4:1; Carry out back flushing to filler, backwashing period is 5 days;
Reflux to waste water in anaerobic treatment and Aerobic, reflux ratio is 3:1, carries out back flushing to filler, and backwashing period is 7 days.
Embodiment 5,
A kind of device for the treatment of tetracycline antibiotics waste water, comprise pretreatment unit and aerobic/anaerobic treatment unit, described pretreatment unit comprises pretreatment unit packing area 5, lower end, pretreatment unit packing area 5 is provided with pretreatment unit filter plate 4-1, pretreatment unit bottom is fixedly connected with by pretreatment unit joint flange 2-1 and the pretreatment unit buffer zone 29 that intakes, pretreatment unit aeration plate 3-1 is provided with between pretreatment unit joint flange 2-1 and pretreatment unit filter plate 4-1, pretreatment unit top is provided with pretreatment unit top cover 23-1, pretreatment unit top cover 23-1 is provided with perforate, pretreatment unit is provided with pretreatment unit recycling effluent mouth 6 between pretreatment unit top cover 23-1 and pretreatment unit packing area 5, pretreatment unit back flushing water-in 7 and pretreatment unit water outlet 9, pretreatment unit water inlet buffer zone 29 is provided with pretreatment unit backflow water-in 10 and pretreatment unit water-in 8, pretreatment unit water-in 8 is connected with pretreatment unit intake pump 28-1, pretreatment unit recycling effluent mouth 6 is connected by pretreatment unit reflux pump 28-2 with pretreatment unit backflow water-in 10,
Described aerobic/anaerobic treatment unit comprises anaerobic zone 11 and aerobic zone 22, anaerobic effluent buffer zone 24 and aerobic water inlet buffer zone 25 is disposed with between anaerobic zone 11 and aerobic zone 22, be fixedly connected with by anaerobic effluent buffer zone joint flange 2-4 between anaerobic effluent buffer zone 24 and aerobic water inlet buffer zone 25, be fixedly connected with by aerobic zone joint flange 2-3 between aerobic water inlet buffer zone 25 and aerobic zone 22, aerobic zone water inlet valve 13 is provided with between anaerobic effluent buffer zone 24 and aerobic water inlet buffer zone 25, anaerobic effluent buffer zone 24 is provided with anaerobic zone back flushing water-in 12, triphase separator 14 and airway 15, aerobic water inlet buffer zone 25 is provided with aerobic zone aeration plate 3-2 and aerobic zone back flushing water outlet 20, bottom, aerobic zone 22 is provided with aerobic zone filter plate 4-3, aerobic/anaerobic treatment unit top is provided with aerobic/anaerobic treatment unit top cover 23-2, aerobic/anaerobic treatment unit top cover 23-2 arranges porose, is provided with aerobic/anaerobic treatment unit recycling effluent mouth 16, aerobic zone back flushing water-in 17 and aerobic/anaerobic treatment unit water outlet 21 between aerobic/anaerobic treatment unit top cover 23-2 and aerobic zone 22,
Lower end, anaerobic zone 11 is provided with anaerobic zone filter plate 4-2, aerobic/anaerobic treatment unit bottom is fixedly connected with by anaerobic zone joint flange 2-2 and the anaerobism buffer zone 26 that intakes, anaerobism water inlet buffer zone 26 is provided with aerobic/anaerobic treatment unit backflow water-in 18 and aerobic/anaerobic treatment unit water-in 19, connected by aerobic/anaerobic treatment unit reflux pump 28-4 between aerobic/anaerobic treatment unit recycling effluent mouth 16 and aerobic/anaerobic treatment unit backflow water-in 18, connected by aerobic/anaerobic treatment unit intake pump 28-3 between pretreatment unit water outlet 9 and aerobic/anaerobic treatment unit water-in 19,
Regulating tank 27 is also provided with between described pretreatment unit water outlet 9 and aerobic/anaerobic treatment unit water-in 19;
Described pretreatment unit bottom is provided with pretreatment unit base 1-1, and described aerobic/anaerobic treatment unit bottom is provided with aerobic/anaerobic treatment unit base 1-2;
Described pretreatment unit packing area 5 is filled with iron-carbon micro-electrolysis haydite, and the particle diameter of iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 850kg/m
3, packed height is 80cm;
Described anaerobic zone 11 is filled with lytag, the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 400kg/m
3, the height of filler is 60cm;
Described aerobic zone 22 is filled with sludge ceramsite, the particle diameter 5-10mm of sludge ceramsite, pellet density 900-1000kg/m
3, tap density 450kg/m
3, the height of filler is 50cm;
Described pretreatment unit and aerobic/anaerobic treatment unit are the capable structure of cylinder, and described pretreatment unit water inlet buffer zone 29 and anaerobism water inlet buffer zone 26 are pyramidal structure;
The total height of described anaerobic effluent buffer zone 24 and aerobic water inlet buffer zone 25 is 20cm;
Height between described pretreatment unit top cover 23-1 and pretreatment unit packing area 5 is 20cm, and the height between aerobic/anaerobic treatment unit top cover 23-2 and aerobic zone 22 is 20cm.
Embodiment 6,
As described in Example 5 for the treatment of the device of tetracycline antibiotics waste water, unlike:
The tap density 950kg/m of described iron-carbon micro-electrolysis haydite
3, packed height is 100cm;
The tap density 500kg/m of described lytag
3, the height of filler is 100cm;
The tap density 550kg/m of described sludge ceramsite
3, the height of filler is 80cm;
The total height of described anaerobic effluent buffer zone 24 and aerobic water inlet buffer zone 25 is 50cm;
Height between described pretreatment unit top cover 23-1 and pretreatment unit packing area 5 is 30cm, and the height between aerobic/anaerobic treatment unit top cover 23-2 and aerobic zone 22 is 30cm.
Embodiment 7,
Utilize device described in embodiment 5 to a method for tetracycline antibiotics wastewater treatment, step is as follows:
Iron-carbon micro-electrolysis haydite, lytag and sludge ceramsite are loaded respectively in pretreatment unit packing area 5, anaerobic zone 11 and aerobic zone 22, waste water is pumped into by pretreatment unit intake pump 28-1, aeration is carried out by pretreatment unit aeration plate 3-1, the hydraulic detention time controlled in pretreatment unit is 8h, and air water volume ratio is 8:1; Refluxed to the process waste water in pretreatment unit by pretreatment unit reflux pump 28-2, control reflux ratio is 4:1; Regularly carry out back flushing to pretreatment unit, backwashing period is 5 days, and backwashing water is discharged by pretreatment unit water-in 8;
Waste water after pretreatment unit process is introduced in regulating tank 27, and regulate pH to 6.5-7.0 by adding CaO, enter into the waste water of aerobic/anaerobic treatment unit after pretreatment unit process by aerobic/anaerobic treatment unit intake pump 28-3 again and enter into aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit intake pump 28-3, the hydraulic detention time controlled in aerobic/anaerobic treatment unit is 16h, carry out aeration by aerobic zone aeration plate 3-2 to aerobic zone, controlling air water volume ratio is 17:1; Refluxed to the waste water in aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit reflux pump 28-4, control reflux ratio is 3:1, and regularly carry out back flushing to anaerobic zone 11 and aerobic zone 22, backwashing period is 7 days; Backwashing water in anaerobic zone 11 is discharged by aerobic/anaerobic treatment unit water-in 19, and the gas produced in triphase separator 14 pairs of anaerobic zones 11 is separated with waste water, is discharged by the gas produced by airway 15 in anaerobic zone 11; Waste water, after the process of aerobic/anaerobic treatment unit, is discharged from aerobic/anaerobic treatment unit water outlet 21.
Experimental example
The device described in embodiment 5 is utilized to process simulated wastewater, specific as follows:
Artificial preparation tetracycline wastewater simulation Jinan City periphery pharmacy corporation effluent sewerage, simulated wastewater specific targets are as follows:
COD is 7136mg/L, BOD is 2127mg/L, and ammonia nitrogen is 339mg/L, pH is 4.5, and total phosphorus is 157mg/L, and residual tetracycline concentration is 469mg/L, and colourity is about 850.
Pretreatment unit does not reflux to waste water, and pretreatment stage adopts hydraulic detention time (HRT) to be 6h, and air water volume ratio is that 3.5:1, pH are adjusted to about 4, and backwashing period is 3d.
In aerobic/anaerobic treatment unit, adopt anaerobic zone hydraulic detention time (HRT) to be 16h, aerobic zone aeration air water volume ratio is 15:1, and backwashing period is that the condition of 5d continues process waste water.
Eventually passing through the waste water COD clearance after process is 96%, and ammonia nitrogen reaches 99%, and total tp removal rate is 90%, and tsiklomitsin clearance is 92%, and colourity reduces to about 30.
From the above results, present invention process and the process of device to this type of tetracycline wastewater achieve good effect.
Claims (10)
1., for the treatment of a technique for tetracycline antibiotics waste water, comprise pre-treatment step and aerobic/anaerobic treatment step;
Described pre-treatment step is using iron-carbon micro-electrolysis haydite as filler, carries out electrolysis treatment; The particle diameter of described iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 850-950kg/m
3, packed height is 80-100cm, and hydraulic detention time is 4-8h, and air water volume ratio is (5-8): 1;
Described aerobic/anaerobic treatment step be by pre-treatment step process after waste water carry out anaerobic treatment and aerobic treatment successively, anaerobic treatment take lytag as filler, the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 400-500kg/m
3, the height of filler is 60-100cm; Aerobic treatment take sludge ceramsite as filler, particle diameter 5-10mm, pellet density 900-1000kg/m
3, tap density 450-550kg/m
3, the height of filler is 50-80cm, and air water volume ratio is (13-17): 1; Described anaerobic treatment and the hydraulic detention time of aerobic treatment are 12-16h.
2. the technique for the treatment of tetracycline antibiotics waste water according to claim 1, is characterized in that, the inlet flow-patterm 3.5-4.5 of pre-treatment step; Water outlet pH6-7 after pre-treatment step, further preferably, adjusting water outlet pH6.5-7 after pre-treatment step, more preferably regulates with CaO.
3. the technique for the treatment of tetracycline antibiotics waste water according to claim 1, is characterized in that, reflux in pre-treatment step to waste water, and reflux ratio is (2-4): 1; Carry out back flushing to filler, backwashing period is 3-5 days;
Reflux to waste water in anaerobic treatment and Aerobic, reflux ratio is (2-3): 1, carries out back flushing to filler, and backwashing period is 5-7 days.
4. the device for the treatment of tetracycline antibiotics waste water, it is characterized in that, this device comprises pretreatment unit and aerobic/anaerobic treatment unit, described pretreatment unit comprises pretreatment unit packing area, lower end, pretreatment unit packing area is provided with pretreatment unit filter plate, pretreatment unit bottom is fixedly connected with by pretreatment unit joint flange and the pretreatment unit buffer zone that intakes, pretreatment unit aeration plate is provided with between pretreatment unit joint flange and pretreatment unit filter plate, pretreatment unit top is provided with pretreatment unit top cover, pretreatment unit top cover is provided with perforate, pretreatment unit is provided with pretreatment unit recycling effluent mouth between pretreatment unit top cover and pretreatment unit packing area, pretreatment unit back flushing water-in and pretreatment unit water outlet, pretreatment unit water inlet setting buffers has pretreatment unit backflow water-in and pretreatment unit water-in, pretreatment unit water-in is connected with pretreatment unit intake pump, pretreatment unit recycling effluent mouth is connected by pretreatment unit reflux pump with pretreatment unit backflow water-in,
Described aerobic/anaerobic treatment unit comprises anaerobic zone and aerobic zone, anaerobic effluent buffer zone and aerobic water inlet buffer zone is disposed with between anaerobic zone and aerobic zone, be fixedly connected with by anaerobic effluent buffer zone joint flange between anaerobic effluent buffer zone and aerobic water inlet buffer zone, be fixedly connected with by aerobic zone joint flange between aerobic water inlet buffer zone and aerobic zone, aerobic zone water inlet valve is provided with between anaerobic effluent buffer zone and aerobic water inlet buffer zone, anaerobic effluent setting buffers has anaerobic zone back flushing water-in, triphase separator and airway, aerobic water inlet setting buffers has aerobic zone aeration plate and aerobic zone back flushing water outlet, bottom, aerobic zone is provided with aerobic zone filter plate, aerobic/anaerobic treatment unit top is provided with aerobic/anaerobic treatment unit top cover, aerobic/anaerobic treatment unit top cover arranges porose, is provided with aerobic/anaerobic treatment unit recycling effluent mouth, aerobic zone back flushing water-in and aerobic/anaerobic treatment unit water outlet between aerobic/anaerobic treatment unit top cover and aerobic zone,
Lower end, anaerobic zone is provided with anaerobic zone filter plate, aerobic/anaerobic treatment unit bottom is fixedly connected with by anaerobic zone joint flange and the anaerobism buffer zone that intakes, anaerobism water inlet setting buffers has aerobic/anaerobic treatment unit backflow water-in and aerobic/anaerobic treatment unit water-in, connected by aerobic/anaerobic treatment unit reflux pump between aerobic/anaerobic treatment unit recycling effluent mouth and aerobic/anaerobic treatment unit backflow water-in, connected by aerobic/anaerobic treatment unit intake pump between pretreatment unit water outlet and aerobic/anaerobic treatment unit water-in.
5. the device for the treatment of tetracycline antibiotics waste water according to claim 4, is characterized in that, is also provided with regulating tank between described pretreatment unit water outlet and aerobic/anaerobic treatment unit water-in.
6. the device for the treatment of tetracycline antibiotics waste water according to claim 4, it is characterized in that, described pretreatment unit packing area is filled with iron-carbon micro-electrolysis haydite, further preferably, the particle diameter of iron-carbon micro-electrolysis haydite is 5-7cm, pellet density 1200-1400kg/m
3, tap density 850-950kg/m
3, packed height is 80-100cm;
Described anaerobic zone is filled with lytag, further preferably, and the particle diameter 15-20mm of lytag, pellet density 850-950kg/m
3, tap density 400-500kg/m
3, the height of filler is 60-100cm;
Described aerobic zone is filled with sludge ceramsite, further preferably, and the particle diameter 5-10mm of sludge ceramsite, pellet density 900-1000kg/m
3, tap density 450-550kg/m
3, the height of filler is 50-80cm.
7. the device for the treatment of tetracycline antibiotics waste water according to claim 4, it is characterized in that, described pretreatment unit and aerobic/anaerobic treatment unit are the capable structure of cylinder, and described pretreatment unit water inlet buffer zone and anaerobism water inlet buffer zone are pyramidal structure.
8. the device for the treatment of tetracycline antibiotics waste water according to claim 4, is characterized in that, the total height of described anaerobic effluent buffer zone and aerobic water inlet buffer zone is 20-50cm;
Height between pretreatment unit top cover and pretreatment unit packing area is 20-30cm, and the height between aerobic/anaerobic treatment unit top cover and aerobic zone is 20-30cm.
9. a method of work for the device for the treatment of tetracycline antibiotics waste water described in any one of claim 4-8, step is as follows:
Iron-carbon micro-electrolysis haydite, lytag and sludge ceramsite are loaded respectively in pretreatment unit packing area, anaerobic zone and aerobic zone, waste water is pumped into by pretreatment unit intake pump, aeration is carried out by pretreatment unit aeration plate, the hydraulic detention time controlled in pretreatment unit is 4-8h, and air water volume ratio is (5-8): 1; Refluxed to the process waste water in pretreatment unit by pretreatment unit reflux pump, controlling reflux ratio is (2-4): 1; Regularly carry out back flushing to pretreatment unit, backwashing period is 3-5 days, and backwashing water is discharged by pretreatment unit water-in;
Waste water after pretreatment unit process enters into aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit intake pump, the hydraulic detention time controlled in aerobic/anaerobic treatment unit is 12-16h, carry out aeration by aerobic zone aeration plate to aerobic zone, controlling air water volume ratio is (13-17): 1; Refluxed to the waste water in aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit reflux pump, controlling reflux ratio is (2-3): 1, and regularly carry out back flushing to anaerobic zone and aerobic zone, backwashing period is 5-7 days; Backwashing water in anaerobic zone is discharged by aerobic/anaerobic treatment unit water-in, and triphase separator is separated with waste water the gas produced in anaerobic zone, is discharged by the gas produced by airway in anaerobic zone; Waste water, after the process of aerobic/anaerobic treatment unit, is discharged from aerobic/anaerobic treatment unit water outlet.
10. method of work according to claim 9, is characterized in that, the waste water after pretreatment unit process is introduced in regulating tank and regulates pH to 6.5-7.0, then enters into aerobic/anaerobic treatment unit by aerobic/anaerobic treatment unit intake pump; Preferred further, the pH of waste water in regulating tank is regulated by adding CaO.
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