CN104671597A - Treatment process of antibiotic wastewater - Google Patents
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Abstract
The invention discloses a treatment process of antibiotic wastewater. The treatment process comprises the following steps: firstly carrying out coagulating sedimentation pretreatment on wastewater, and adding acidized supernate into a hydrolysis acidification pool; mixing returned sludge, anaerobic effluent and hydrolysis acidification effluent in proportion in a water distribution pool, and simultaneously regulating the pH value; feeding the regulated wastewater into a anaerobic treatment stage, converting most pollutants into water and carbon dioxide, simultaneously producing marsh gas, carrying out gas-solid-liquid separation by virtue of a three-phase separator, collecting marsh gas in a gas chamber, returning the sludge to a reaction region, returning partial supernate to the water distribution pool, and sequentially feeding rest supernate into an aerobic treatment stage and an advanced treatment stage. The antibiotic wastewater treated by virtue of the treatment process can thoroughly reach the emission standard, and the removal rate of various pollutants reaches above 99%; furthermore, facilities are simple and are easy and convenient to operate.
Description
Technical field
The present invention relates to field of industrial waste water treatment, relate to the treatment process of antibiotic waste water of high ammonia nitrogen, high organic waste water in particular.
Background technology
Chlortetracycline wastewater complicated component, organic concentration height about CODcr10000mg/l, solvability and colloidality solids concn high, pH value often changes, and temperature is higher, with color and smell, suspension content high (SS=2000-3000mg/l), easy generation foam, containing hard-degraded substance and have inhibiting microbiotic etc., belongs to antibiotics used water difficult to degradate.But Ke Shengization≤0.3 of such waste water, namely B/C is than high, and biodegradability is strong, and the most energy-conservation effective treatment process adopts microbiological treatment technology exactly.Traditional technique is generally anaerobism+aerobic process technology, but because of the impact of high antibiotic remains, high ammonia nitrogen (NH3-N=600-800mg/l), high-sulfur (SO42-=2000-3000mg/l) and high chlorine, common anaerobic technique is difficult to effect even complete failure of bringing into normal play, follow-up aerobic system is caused also cannot normally to run, thus energy consumption is high, fluctuation of service, and do not reach emission standard and requirement at all, treatment system is often in maintenance or state of paralysis, causes enterprise normally to produce and even stops production.Break away from the predicament of Pollution abatement in enterprise's production, seek a kind of microbiotic sewage treatment process of efficient stable, for Enterprise Healthy Development escorts, become the cardinal task that current antibiotic is produced, pharmaceutical industry is extremely urgent.
Summary of the invention
For the technical problem solved, the object of the invention is to provide a kind for the treatment of process of antibiotic waste water, this treatment process can ensure that each pollutant produced in enterprise production process all can effectively be administered, simultaneously the running cost of this technique and maintenance cost low, effective.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A treatment process for antibiotic waste water, is characterized in that, mainly comprises the following steps:
(s1) raw water collection: rely on run by gravity to carry out collecting equalizing tank in all sewage in production area, is uniformly mixed by whipping appts under water, mixes well water quality and quantity, guarantees that system can continuous uniform water inlet;
(s2) coagulating sedimentation pre-treatment: sewage enters coagulating sedimentation reactor, in coagulating sedimentation reactor, first by PH range regulation to 6.5-7.0, add deployed PAC and PAM successively again, by adjusting pH, dosing coagulant PAC, polymer coagulant aids PAM, most of suspended solid impurities in precipitation sewage, supernatant liquor enters hydrolysis acidification pool;
(s3) acidication: arrange diving propelling stirrer bottom hydrolysis acidification pool, prevents the deposition of mud; In middle and upper part, pond, combined stuffing is set, in order to adhere to mud, increase sludge concentration in pond, and reduce water outlet ss suspended solid value, change the non-solubility organism in original waste water into dissolved organic matter, and weaken the restraining effect of trade effluent to microorganism, the organism of wherein difficult for biological degradation is changed into the organism of readily biodegradable, improve BOD/COD(B/C ratio and the biodegradability of waste water), be beneficial to follow-up biochemical treatment;
(s4) water distribution: in distribution reservoir, by returned sluge, anaerobic effluent (EGSB anaerobic effluent), acidication water outlet mixing match (1:1:4), adjusts pH value (6.0-6.5) simultaneously;
(s5) anaerobic treatment: the water outlet of distribution reservoir enters from the water distributor bottom EGSB anaerobic reactor, in the reactor, pH(6.8-7.2 suitable) and temperature under carry out middle temperature (33-35 DEG C) anaerobism, macromolecule organic changes into micromolecular VFA and methane, organism in sewage is decomposed utilization by anerobe, most of pollution substance is converted into water and carbonic acid gas, produce biogas simultaneously, carry out gas-solid-liquid finally by the triphase separator in reactor to be separated, biogas is collected by air chamber, solid particulate mud returns to reaction zone by gravitational settling and continues DeR, the water outlet part that namely supernatant liquor is handled well returns after distribution reservoir carries out dilution proportioning and again enters anaerobic system by water distributor, another part enters aerobic treatment stage next stage.
(s6) aerobic treatment: anaerobic effluent enters aerobic system, the free oxygen of aerobic microbiological inside O pond is using organic pollutant as nutrition source, organic pollutant is degraded, stable, autotrophic type microorganism carries out nitrification simultaneously, NH3 is oxidized to nitrite, be reoxidised into nitrate, in A pond, NO3-N and NO2-N passes through denitrifying bacterium, be converted into gaseous nitrogen and Nitrous Oxide, A pond is stirred, the oxygen supply of O pond, intake from front end, A pond, O pond outlet water at tail end is back to A pond, mixed solution enters biogenic sediment pond precipitation, sludge part refluxes, excess sludge enters sludge thickener and outward transport after dehydration, supernatant liquor overflow penetration depth governing system,
(s7) advanced treatment: four phase catalytic oxidizing equipments of supernatant liquor penetration depth treatment system, add catalyst sulfuric acid ferrous iron and oxidant hydrogen peroxide, produce hydroxyl radical free radical OH, and blast aeration 1 hour, containing alloy catalyst in described four catalytic oxidizing equipments; The reaction water outlet of four phase catalytic oxidizing equipments enters into catalytic oxidation pond, continues oxidizing reaction by micro-pore aeration, and exhaustive oxidation decomposes not biodegradable COD and colourity, and forms a large amount of tawny flock, is suspended in mixed solution; The mixed solution in catalytic oxidation pond enters chemical precipitation pond, add the alkali lye that concentration is 30% in mixed solution, mixed solution PH is adjusted to neutrality, then dosing coagulant PAC and polymer coagulant aids PAM, carried out by described flock tackling, collecting, mud enters concentration basin treatment system.
Wherein, described alloy catalyst with training wall arranged in form in described four phase catalytic oxidizing equipments.
Wherein, be provided with some groups of perforation water distributors bottom described hydrolysis acidification pool, this pond is divided into five regions by vertical traverse baffle, combined stuffing described in each areal distribution, described diving propelling stirrer is arranged in the 2nd, 3rd district and the 4th, 5th district.
Wherein, described triphase separator, form by a main separator and around several separator that this main separator is evenly arranged, each separator is cylindric, the inside of separator is provided with the funnelform isolated part that is back-off, reflector is provided with below this isolated part, by this isolated part, the upper space of reactor is separated into gas passage, air chamber, settling region, above described reactor, both sides are equipped with overflow weir notch, and offer sludge reflux mouth respectively on the face that main separator is relative with each separator.
Wherein, described reflector is umbrella, and is formed in 15 ° of angles between horizontal plane, and have diameter 300mm hole in the middle of plate, this reflector edge of this reflector is welded on the sidewall of separator by some stainless steel tubes.
Wherein, described water distributor is detachable, and it is uniformly distributed in bottom by some perforation water distributors and forms, and two ends stretch out in reactor outside, and the two ends of every root water distributor are equipped with valve, and pending sewage enters inside reactor via water distributor one end.
Wherein, described time separator is 8, and connect with main separator after in parallel between each, each separator works alone.
Wherein, described water distributor is made up of 8 water distributors of independently boring a hole.
Compared with prior art, the present invention has following beneficial effect:
1. the thorough facility qualified discharge of antibiotics waste water, all kinds of pollutants removal rate reaches more than 99%.
2. facility is simple, easy and simple to handle, labour intensity is low, stable, be convenient to management, high-efficient operation.
3.(EGSB) anaerobic system power consumption is few, and running cost is low, produces the cleanliness without any pollution energy-------biogas.
4.(A/O) aerobic system anti-shock loading is strong, and denitrification effect is good, and COD, ammonia nitrogen removal frank are high.
5. four phase catalytic oxidation technologies are that whole treatment system is rigid in checking up, and guarantee that sewage strictly implements qualified discharge.
6. aerobic, the four phase catalytic oxidation technologies of acidication, (EGSB) anaerobism, (A/O) are that microbiotic enterprise development escorts.
Accompanying drawing explanation
Fig. 1 is antibiotic waste water processing flow chart of the present invention;
Fig. 2 is anaerobic reactor structural representation;
Fig. 3 is anaerobic reactor structure sectional view
Fig. 4 is triphase separator structural representation in anaerobic reactor;
Fig. 5 is triphase separator operating diagram;
Fig. 6 is triphase separator sectional view;
Fig. 7 is hydrolysis acidification pool structural representation.
Main Reference Numerals explanation
10 water distributors
11 valves
20 reaction zones
3 triphase separators
31 main separators
32 separators
321 isolated parts
322 reflectors
323 gas passages
324 air chambers
326 Road narrows
327 skew walls
328 sludge reflux mouths
4 overflow weir notches
51 water distributors
52 combined stuffings
53 diving mixers.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, realized object and effect, accompanying drawing is coordinated to be explained in detail below in conjunction with embodiment.
Referring to Fig. 1, is antibiotic waste water processing flow chart of the present invention.The treatment process of antibiotic waste water, comprises the following steps:
A treatment process for antibiotic waste water, mainly comprises the following steps:
(s1) raw water collection: rely on run by gravity to carry out collecting equalizing tank in all sewage in production area, is uniformly mixed by whipping appts under water, mixes well water quality and quantity, guarantees that system can continuous uniform water inlet;
(s2) coagulating sedimentation pre-treatment: sewage enters coagulating sedimentation reactor, in coagulating sedimentation reactor, first by PH range regulation to 6.5-7.0, add deployed PAC and PAM successively again, by adjusting pH, dosing coagulant PAC, polymer coagulant aids PAM, most of suspended solid impurities in precipitation sewage, supernatant liquor enters hydrolysis acidification pool;
(s3) acidication: arrange diving propelling stirrer bottom hydrolysis acidification pool, prevents the deposition of mud; In middle and upper part, pond, combined stuffing is set, in order to adhere to mud, increase sludge concentration in pond, and reduce water outlet ss suspended solid value, change the non-solubility organism in original waste water into dissolved organic matter, and weaken the restraining effect of trade effluent to microorganism, the organism of wherein difficult for biological degradation is changed into the organism of readily biodegradable, improve BOD/COD(B/C ratio and the biodegradability of waste water), be beneficial to follow-up biochemical treatment;
(s4) water distribution: in distribution reservoir, carries out mixing match by returned sluge, anaerobic effluent (EGSB anaerobic effluent), acidication water outlet with volume ratio 1:1:4, adjusts pH value to 6.0-6.5 simultaneously; Here returned sluge refers to enter the sludge reflux of the rear gained of settling tank precipitation in distribution reservoir from the supernatant liquor in anaerobic reactor.
(s5) anaerobic treatment: the water outlet of distribution reservoir enters from the water distributor bottom EGSB anaerobic reactor, in the reactor, anaerobic reaction is carried out at pH6.8-7.2 and temperature 33-35 DEG C, macromolecule organic changes into micromolecular VFA and methane, organism in sewage is decomposed utilization by anerobe, most of pollution substance is converted into water and carbonic acid gas, produce biogas simultaneously, carry out gas-solid-liquid finally by the triphase separator in reactor to be separated, biogas is collected by air chamber, and by fully utilizing after secondary water seal and desulphurization system desulfurization, solid particulate mud returns to reaction zone by gravitational settling and continues DeR, the water outlet part that namely supernatant liquor is handled well returns after distribution reservoir carries out dilution proportioning and again enters anaerobic system by water distributor, another part enters aerobic treatment stage next stage.
(s6) aerobic treatment: anaerobic effluent enters aerobic system, the free oxygen of aerobic microbiological inside O pond is using organic pollutant as nutrition source, organic pollutant is degraded, stable, autotrophic type microorganism carries out nitrification simultaneously, NH3 is oxidized to nitrite, be reoxidised into nitrate, in A pond, NO3-N and NO2-N passes through denitrifying bacterium, be converted into gaseous nitrogen and Nitrous Oxide, A pond is stirred, the oxygen supply of O pond, intake from front end, A pond, O pond outlet water at tail end is back to A pond, mixed solution enters biogenic sediment pond precipitation, sludge part refluxes, excess sludge enters sludge thickener and outward transport after dehydration, supernatant liquor overflow penetration depth governing system,
(s7) advanced treatment: four phase catalytic oxidizing equipments of supernatant liquor penetration depth treatment system, add catalyst sulfuric acid ferrous iron and oxidant hydrogen peroxide, produce hydroxyl radical free radical OH, and blast aeration 1 hour, containing alloy catalyst in described four catalytic oxidizing equipments; The reaction water outlet of four phase catalytic oxidizing equipments enters into catalytic oxidation pond, continues oxidizing reaction by micro-pore aeration, and exhaustive oxidation decomposes not biodegradable COD and colourity, and forms a large amount of tawny flock, is suspended in mixed solution; The mixed solution in catalytic oxidation pond enters chemical precipitation pond, add the alkali lye that concentration is 30% in mixed solution, mixed solution PH is adjusted to neutrality, then dosing coagulant PAC and polymer coagulant aids PAM, carried out by described flock tackling, collecting, mud enters concentration basin treatment system.
As one preferred embodiment, alloy catalyst with training wall arranged in form in described four phase catalytic oxidizing equipments.
Consider the singularity of such waste water, coagulating sedimentation pretreatment work must be strengthened, remove or transform hazardous and noxious substances, eliminate the unfavorable factor hindering biochemical reaction, then after the effective pre-treatment of acidication workshop section, the EGSB anaerobic reactor that comprehensive wastewater enters follow-up mature and reliable again processes accordingly, just can guarantee the working cost reducing waste water processing station, remove a large amount of COD, cut down a large amount of pollutent organic loadings, guarantee the stably reaching standard discharge that waste water is final.
High density antibiotics organic waste water is after coagulating sedimentation+acidication+EGSB anaerobic biological treatment, its contamination index BOD, COD, SS, NH3-N concentration is still very high, BOD=1000-1500mg/l, COD=3000-4000mg/l, ammonia nitrogen=600-800mg/l, SS=400-500mg/l, emission request can not be met far away, also must carry out Aerobic biological process and A/O Wastewater Treated by Activated Sludge Process, by the decomposition of high-effective microorganism to organic pollutant, guarantee that dirty water pollutant can be degraded elimination further.Antibiotic waste water because of its pollution concentration high, biodegradability is strong, after microbiological treatment technology (anaerobism+aerobic process) process,
Although each pollutant has all had degraded by a relatively large margin, its contamination index can reach national secondary discharge standard and BOD5≤60mg/l, COD≤300mg/l substantially, ammonia nitrogen≤50mg/l, SS=100mg/l.But along with the development of society, require that enterprise must adhere to " overall control to pollutant control discharge in active response national policy, energy-saving and emission-reduction " call under, Environmental Protection Agency of Fujian Province issues associated documents in September, 2008, namely Environmental Protection Agency of Fujian Province is about the notice issuing strict implement pharmaceutical industry pollution discharge standard and cut down further gross contamination emission, be strict with the sewage discharge before 1 day July in 2010 of each pharmacy corporation and must reach " fermentation class pharmaceutical industry pollution discharge standard " (GB21903-2008) namely: BOD5≤30mg/l, COD≤100mg/l, An Dan≤25mg/l, SS≤60mg/l.
So, after anaerobism, aerobic biological treatment process terminate, also must in conjunction with deep treatment technique, i.e. high-level oxidation technology------four phase catalytic oxidation technologies.This Technology collection is solid, liquid, the leggy one such as gas, by controlling various reaction conditions (as alloy catalyst, drug concentration, response intensity, medicament adds point, reaction times etc.), at electricity, magnetic, hydroxyl radical free radical OH is transferred under completing normal temperature and pressure under the microscopic integrative field conditions such as gas, that deep oxidation (AOP) oxidation rate achieved truly up to the strong oxidation of the hydroxyl radical free radical OH of 2.80V and the chain reaction of various free radicals (OO2H2O etc.) that produces thereupon based on oxidizing potential improves greatly, organic pollutant efficient removal at short notice can be realized.Bio-chemical effluent is linked into catalytic oxidizer (alloy catalyst is housed), add strong oxidizer, discoloring agent simultaneously, aeration 1 hour, water outlet adds liquid caustic soda, PAC and PAM, precipitate in chemical precipitation pond, precipitating sludge introduces sludge thickener, and supernatant liquor overflows and enters sewage plant sewage effluent standard mouth, monitors qualified discharge by on-line computing model.
The reaction principle of advanced treatment: by ferrous sulfate catalyzed oxidation hydrogen peroxide, in special four catalytic oxidizing equipments, produce hydroxyl radical free radical, and the reaction mechanism of hydroxyl radical free radical degradable organic pollutant is as the principle of high-level oxidation technology, its superpower oxidation susceptibility is utilized to realize the deep oxidation being difficult to degradation material exactly.The method is a kind of four homogeneous catalytic oxidation methods, when adding hydrogen peroxide in containing the acidic solution of ferrous ion, under catalyzer (preferred titanium alloy) acts on, and H
2o
2two kinds of active hydroxyl free radicals can be produced, thus cause and propagate radical chain reaction, accelerate the oxidation of organism and reducing substances.In reaction system, hydroxyl radical free radical (OH) first reacts with organic pollutant RH and generates radical R, and R is oxidized further and generates CO
2and H
2o, thus organic pollutant is finally degraded.
Antibiotic waste water advanced treatment link collection of the present invention solid (alloy catalyst), liquid (sewage, ferrous sulfate, hydrogen peroxide), gas (air), light (arc light, photoelectromagnetism reaction produce in reaction process) etc. leggy one, by controlling various reaction conditions (as alloy catalyst, four pieces, training wall is with baffle plate type S type upper entering and lower leaving arranged in form), control hydraulic flow to (object lengthens the reaction times, improve reaction uniformity coefficient, guarantee to react completely), drug concentration (27.5% hydrogen peroxide, 25% copperas solution, add ratio 1:10), (air capacity is 10m to response intensity
3/ min, for blast aeration, boring aeration pipe distributes, on aeration tube, the arrangement of hole symmetric double is placed in aeration tube down either side, and every side cavities radius is approximately 3mm, and between two round holes 45 ° symmetrical, adjacent holes spacing 100mm, medicament (ferrous sulfate, hydrogen peroxide) add point (with bio-chemical effluent enter simultaneously catalytic oxidation reaction device mixing, reaction, reaction times is 1 hour), at electricity, magnetic, hydroxyl radical free radical OH is transferred under completing normal temperature and pressure under the microscopic integrative field conditions such as gas, up to the strong oxidation of the hydroxyl radical free radical OH of 2.80V and the chain reaction of various free radicals (OO2H2O etc.) that produces thereupon based on oxidizing potential, deep oxidation (AOP) oxidation rate achieved truly improves greatly, organic pollutant efficient removal at short notice can be realized.Bio-chemical effluent is linked into and is equipped with in alloy catalyst four phase catalyzed oxidation apparatus, add strong oxidizer (oxydol H 2O2), discoloring agent (ferrous sulfate FeSO4) simultaneously, aeration 1 hour, water outlet adds liquid caustic soda (30%NaOH), PAC (thousandth polymerize aluminum chloride) and PAM(ten thousand/polymer coagulant aids polyacrylamide), precipitate in chemical precipitation pond, precipitating sludge introduces sludge thickener, supernatant liquor overflows and enters sewage plant sewage effluent standard mouth, monitors qualified discharge by on-line computing model.
Acidication is the pre-treatment workshop section of anaerobic system, by this workshop section, change the non-solubility organism in original waste water into dissolved organic matter, and weaken the restraining effect of trade effluent to microorganism, the organism of wherein difficult for biological degradation is changed into the organism of readily biodegradable, improve the biodegradability of waste water, be beneficial to follow-up biochemical treatment.As a kind of embodiment, some groups of perforation water distributors are provided with bottom hydrolysis acidification pool in step (s3), this pond is divided into five regions by vertical traverse baffle, combined stuffing described in each areal distribution, described diving propelling stirrer is arranged in the 2nd, 3rd district and the 4th, 5th district.
Preferably, water distributor is detachable, and it is uniformly distributed in bottom by some perforation water distributors and forms, and two ends stretch out in reactor outside, and the two ends of every root water distributor are equipped with valve, and pending sewage enters inside reactor via water distributor one end.Here, water distributor is made up of 8 water distributors of independently boring a hole.
As a kind of embodiment, triphase separator in step (s5), form by a main separator and around several separator that this main separator is evenly arranged, each separator is cylindric, the inside of separator is provided with the funnelform isolated part that is back-off, reflector is provided with below this isolated part, by this isolated part, the upper space of reactor is separated into gas passage, air chamber, settling region, above described reactor, both sides are equipped with overflow weir notch, and on the face that main separator is relative with each separator, offer sludge reflux mouth respectively.In this embodiment, reflector is umbrella, and is formed in 15 ° of angles between horizontal plane, and have diameter 300mm hole in the middle of plate, this reflector edge is welded on the sidewall of separator by some stainless steel tubes.
Preferably, secondary separator is 8, and connect with main separator after in parallel between each, each separator works alone.
Existing hydrolysis acidification pool is due to reasons in structure, often there is mud layering, dreg accumulation is too much, acidifying is excessive, harden the phenomenons such as blocking, not only only play the effect of a simple settling tank, and residue can cause the accumulation of volatile acid to be become sour, acidifying is excessive, negative interaction is produced to follow-up anaerobic treatment, in the present invention, acidication transformation comprises three aspects: 1, set up diving propelling stirrer, acid hydrolysis system internal reflux mud and residue are in and mix completely, flow expanded state, contact wide be unlikely to deposition, can not block and sufficient reacting, 2, distribute a large amount of Ball-type packings, a large amount of microorganic adhesion can not be run off in carrier, sufficient reacting, 3, adopt vertical traverse baffle carry out water conservancy diversion hydraulic flow to layout, reduce cost of investment, also reach the effect of one-level anaerobic treatment.Existing acidication is just equivalent to an equalizing tank or settling tank, play a precipitation or the function of the regulating water quality water yield, and improved acidication has the clearance of more than 30%, and decrease the alkaline consumption that PH is adjusted in anaerobism EGSB water inlet, very there is practical value.
As a kind of preferred implementation, triphase separator in EGSB anaerobic reactor, form primarily of a main separator and around several separator that this main separator is evenly arranged, each separator is cylindric, the inside of separator is provided with the funnelform isolated part that is back-off, is provided with reflector, by this isolated part below this isolated part, the upper space of reactor is separated into gas passage, air chamber, settling region, and above described reactor, both sides are equipped with overflow weir notch.
Enter EGSB anaerobic system through pretreated waste water, waste water evenly enters reaction zone by the water distributor of reactor bottom.In the process that uniform fluid flow upwards flows, the organism in waste water fully contacts with the anaerobic sludge in reaction zone, decompose by anerobe utilization.By the biochemical reaction of series of complex, macromolecule organic is converted into micromolecular VFA and methane.Eventually pass the triphase separator of particular design, Gu after carrying out gas--liquid separation, biogas is collected by air chamber, mud returns to reaction zone after being precipitated by settling region voluntarily, process water after precipitation flows out from reactor top in the mode of overflow, through this workshop section COD clearance up to more than 70%, produce clean energy-----biogas simultaneously.
Three phase separation principle: gas, liquid, Gu mixed solution rises in triphase separator, when bubble encounters the reflector of separator bottom, be folded to air chamber and by with solid, liquid is separated, with the mud after bubble separation under gravity a part to fall back reaction zone, the Road narrows that another part is formed along wall of reactor and separator edge with fluid rise, enter settling region, mud flocculates in settling region, sedimentation is with concentrated, then glide along separator skew wall, reaction zone is returned to by sludge reflux mouth, due to liquid bubble-free in settling region, the water column density of more than Gu Wunihuiliukou is greater than fluid density in reactor, the mud after concentrating is enable to return to reaction zone, reach solid-liquid separation, part supernatant liquor is expelled to next processing links by overflow weir, part supernatant liquor returns the feed-water end of bottom water distributor by overflow weir notch.
In the above-described embodiments, secondary separator is 8, and connect with main separator after in parallel between each, each separator works alone.Triphase separator due to separator each naturally independently, when one of them go wrong need maintenance time, can not affect the operation of other separators, simple to operate, easily overhaul, influential system does not run.
As another kind of preferred implementation, water distributor is detachable, and it is uniformly distributed in bottom by some perforation water distributors and forms, and two ends stretch out in reactor outside, the two ends of every root water distributor are equipped with valve, and pending sewage enters inside reactor via water distributor one end.
As an embodiment, water distributor by 8 independently bore a hole water distributors form, 8 independently perforated pipe be evenly distributed in EGS reactor, every root two ends are controlled outward at reactor by two valves, one end control water inlet, one end can emptying.When a wherein blocking, close other valve, this root perforated pipe can be washed open by pressure, if blocking is serious, can water inlet control valve be turned off, open blow-off valve and dredge, do not affect other 7 groups namely whole EGSB system normally run, because in reactor peripheral operation, very convenient, simple, practical; By valve adjustment cloth water flow velocity, regulate according to mud granule formational situation, improve treatment effect.
Consider singularity (the high ammonia nitrogen of such antibiotic waste water, high antibiotic remains), coagulating sedimentation pretreatment work must be strengthened, by dosing coagulant PAC, polymer coagulant aids PAM, within the scope of pH6.0-6.5, reduce antibiotic remains, remove or transform hazardous and noxious substances, remove most of suspended solid impurities, reduce antibiotic remains, detoxification, eliminate the unfavorable factor hindering biochemical reaction, be hydrolyzed through acidication workshop section again, fermentation, after improving effective pre-treatment such as B/C ratio, the EGSB anaerobic reactor that comprehensive wastewater enters follow-up mature and reliable again carries out corresponding anaerobism post-processed, just can guarantee the effect of this new combined process technology, greatly reduce the working cost of whole Waste Water Treatment, remove a large amount of COD, cut down a large amount of pollutent organic loadings, guarantee that waste water is finally sure can discharge by stably reaching standard.
In the present invention, acidication arranges diving mixer, i.e. QJB diving mixer on the one hand bottom pond, is sewage disposal specific equipment, is stirred by current, thus prevent the deposition of mud by three pieces of blade rotaries as water screw; On the other hand combined stuffing is set in middle and upper part, pond, in order to adhere to mud, increases sludge concentration in pond, and reduce water outlet SS value.By acidication process, change the non-solubility organism in original waste water into dissolved organic matter, and weaken the restraining effect of trade effluent to microorganism, the organism of wherein difficult for biological degradation is changed into the organism of readily biodegradable, improve the biodegradability of waste water, be beneficial to follow-up biochemical treatment.In addition, hydrolysis acidification pool is retaining SS and while removing part BOD, is also having certain percent hydrolysis to mud.
EGSB anaerobic reactor is a kind of novel efficient anaerobe reactor come out earlier 1990s.It is the third generation anaerobic biological reactor after UASB, it is the distortion of UASB reactor, which increase water outlet recycling part, the liquid in reactor is made to obtain higher surface liquid up-flow speed, strengthen the contact between sewage and microorganism, just because of the technical superiority of this uniqueness, make it may be used for the process of multiple organic sewage, and obtain higher processing efficiency.Due to granular anaerobic sludge can be formed in reactor, and granule sludge layer is operationally in swelling state, so anaerobe can contact more abundant with the organism in sewage, reactor volume utilization ratio is higher, under the metabolism of anaerobe, the object that can more efficiently reach degradation of organic substances, purify water.Meanwhile, because potential energy organic in sewage can be that biogas discharges by anaerobic biological treatment, change waste water is the energy, so EGSB low, the simply constructed bio-reactor that is a kind of energy consumption.
The characteristic feature of EGSB anaerobic reactor has larger aspect ratio, and larger aspect ratio is also improve required for raw Flow Velocity.Anerobe in EGSB reactor exists with the form of granule sludge, and granule sludge has good settleability and very high methane phase, so reactor can maintain the comparatively high sludge concentration of 50-60 KgVSS/m3, thus reactor organic matter removal ability is strong.The settleability that granule sludge is good, makes reactor have higher waterpower lift velocity, and hydraulic mixing dynamics is strengthened, therefore granule sludge is in swelling state, and contact more abundant with the organism in waste water, thus mass-transfer efficiency is high, organic removal rate is high.Waste water is entered by the bottom even of reactor, on current direction Uniform Flow process in organism degraded, eventually pass the triphase separator of the present invention's design, Gu after carrying out gas--liquid separation, biogas is collected by air chamber, mud returns to reaction zone after being precipitated by settling region voluntarily, and the waste water good through precipitation aftertreatment enters subsequent disposal workshop section through overflow groove from a reactor top part in the mode of overflow, and another part is back to distribution reservoir and reenters reactor by water distributor.So whether triphase separator design is reasonable, be EGSB reactor high loading, high efficiency key.EGSB reactor passes through effluent recycling, make it have the ability of anti-shock loading, make to be diluted to into the concentration of poisons in water no longer there is toxic action to microorganism, so EGSB reactor can process the high concentrated organic wastewater containing toxic substance in certain limit, effluent recycling can make full use of basicity and the pH value of the basicity raising waste water that anaerobic degradation process basic substances produces, keep the PH in reactor to stablize, reduce the throwing alkali number in order to PH adjustment, thus contribute to reducing working cost.
Compared with prior art, the present invention has following beneficial effect:
1. the thorough facility qualified discharge of antibiotics waste water, all kinds of pollutants removal rate reaches more than 99%.
2. facility is simple, easy and simple to handle, labour intensity is low, stable, be convenient to management, high-efficient operation.
3.(EGSB) anaerobic system power consumption is few, and running cost is low, produces the cleanliness without any pollution energy-------biogas.
4.(A/O) aerobic system anti-shock loading is strong, and denitrification effect is good, and COD, ammonia nitrogen removal frank are high.
5. four phase catalytic oxidation technologies are that whole treatment system is rigid in checking up, and guarantee that sewage strictly implements qualified discharge.
6. aerobic+four phase catalytic oxidation technologies of acidication+(EGSB) anaerobism+(A/O) are that microbiotic enterprise development escorts.
The treatment process of antibiotic waste water of the present invention, mainly comprises coagulating sedimentation, acidication, (EGSB) anaerobic treatment, (A/O) aerobic treatment, four phase catalytic oxidation technologies.First by the pre-treatment of dosing coagulating sedimentation, remove a large amount of suspended solidss and impurity in waste water, again through acidication technique, improve wastewater biodegradability and greatly reduce wastewater treatment difficulty level toxicity simultaneously, EGSB anaerobic system efficient stable is played, and produce clean energy-biogas, reduce running cost and lay the foundation for follow-up aerobic system efficient stable plays simultaneously.But due to the limitation of biotreatment microorganisms, namely there is the contamination indexs such as quite a few COD that can not be degraded by microorganisms, still can not reach the requirement that (GB21903-2008) specifies, also must carry out further deep treatment to pollutent, namely high-level oxidation technology-four phase catalytic oxidation technologies is adopted, mandatory exhaustive oxidation decomposition is carried out to pollutents such as not biodegradable COD, colourities, reach removal effect, guarantee that sewage can implement qualified discharge according to country, province, city's environmental requirement.
In the present invention, pending antibiotic waste water complicated component, organic concentration is high, solvability and colloidality solids concn high, pH value often changes, temperature is higher, with color and smell, suspension content is high, easily produces foam, containing hard-degraded substance and have inhibiting microbiotic etc., belong to antibiotics used water difficult to degradate.Consider that the biodegradability of such waste water is 0.3, namely B/C is than high, and biodegradability is strong, and the most energy-conservation effective treatment process adopts microbiological treatment technology exactly, i.e. the bioremediation of anaerobism+aerobic.
Because former Organic substance in water concentration is high especially, COD=8000-10000mg/l, NH3-N=600-800mg/l, and there is certain biodegradability, BOD=3000-5000mg/l.Again due in waste water because COD concentration, ammonia nitrogen concentration, SS content are high, if directly enter traditional aerobic treatment system, organic loading is too high, and microorganism active is suppressed, follow-up aerobic system cannot normally run at all, and working cost can be caused high.Therefore this technological subject technique adopts anaerobion treatment technology, and namely based on the technique of anaerobic biochemical treatment method, this technique is the most energy-conservation effective means, can significantly degradable organic pollutant, while can obtain clean useful bioenergy-biogas.
Consider the singularity of such waste water, coagulating sedimentation pretreatment work must be strengthened, remove or transform hazardous and noxious substances, eliminate the unfavorable factor hindering biochemical reaction, mainly comprise and sewage is all collected equalizing tank, adopt coagulation-settlement process, by adding PAC and PAM, carry out coagulating when adjusting PH, primary deposition, science and engineering section SS clearance is up to more than 80% herein; And then after the effective pre-treatment of acidication workshop section, the EGSB anaerobic reactor that comprehensive wastewater enters follow-up mature and reliable again processes accordingly, just can guarantee the working cost reducing waste water processing station, remove a large amount of COD, cut down a large amount of pollutent organic loadings, guarantee the stably reaching standard discharge that waste water is final.
Wherein, acidication is the pre-treatment workshop section of anaerobic system, by this workshop section, change the non-solubility organism in original waste water into dissolved organic matter, and weaken the restraining effect of trade effluent to microorganism, the organism of wherein difficult for biological degradation is changed into the organism of readily biodegradable, improve the biodegradability of waste water, be beneficial to follow-up biochemical treatment.Enter EGSB anaerobic system through pretreated waste water, waste water evenly enters reaction zone by the water distributor of reactor bottom.In the process that uniform fluid flow upwards flows, the organism in waste water fully contacts with the anaerobic sludge in reaction zone, decompose by anerobe utilization.
EGSB anaerobic reactor is a kind of novel efficient anaerobe reactor come out earlier 1990s.It is the third generation anaerobic biological reactor after UASB, due to granular anaerobic sludge can be formed in reactor, and granule sludge layer is operationally in swelling state, so anaerobe can contact more abundant with the organism in sewage, reactor volume utilization ratio is higher, under the metabolism of anaerobe, the object that can more efficiently reach degradation of organic substances, purify water.Meanwhile, because potential energy organic in sewage can be that biogas discharges by anaerobic biological treatment, change waste water is the energy, so EGSB low, the simply constructed bio-reactor that is a kind of energy consumption.
In anaerobic system, by the biochemical reaction of series of complex, macromolecule organic is converted into micromolecular VFA and methane, eventually pass the specially designed triphase separator of the present invention, Gu after carrying out gas--liquid separation, biogas is collected by air chamber, mud returns to reaction zone after being precipitated by settling region voluntarily, process water after precipitation flows out from reactor top in the mode of overflow, through this workshop section COD clearance up to more than 70%, produces clean energy-----biogas simultaneously.
High density antibiotics organic waste water is after coagulating sedimentation, acidication, EGSB anaerobic biological treatment, its contamination index BOD, COD, SS, NH3-N concentration is still very high, BOD=1000-1500mg/l, COD=3000-4000mg/l, ammonia nitrogen=600-800mg/l, SS=400-500mg/l, emission request can not be met far away, also must carry out Aerobic biological process and A/O Wastewater Treated by Activated Sludge Process, by the decomposition of high-effective microorganism to organic pollutant, guarantee that dirty water pollutant can be degraded elimination further.
Anaerobic effluent enters (A/O) aerobic system, A is anoxic pond, and O is Aerobic Pond.Under heterotroph microorganism and aerobic microbiological have the prerequisite of free oxygen inside O pond, using organic pollutant as nutrition source, organic pollutant degraded, stablize.Autotrophic type microorganism carries out nitrification at this simultaneously, NH3 is oxidized to nitrite, is reoxidised into nitrate.In A pond, NO3-N and NO2-N, by denitrifying bacterium, is converted into gaseous nitrogen and Nitrous Oxide.A pond is stirred, the oxygen supply of O pond, and from the water inlet of front end, A pond, O pond outlet water at tail end is back to A pond, and mixed solution enters biogenic sediment pond precipitation, and sludge part refluxes, and excess sludge enters sludge thickener and outward transport after dehydration, supernatant liquor overflow penetration depth governing system.By high-effective microorganism degradation function, by contaminant degradation to the limit, namely except except non-biodegradable pollutent, be all degraded.
Antibiotic waste water in the present invention because of its pollution concentration high, biodegradability is strong, after microbiological treatment technology (anaerobism+aerobic process) process, although each pollutant has all had degraded by a relatively large margin, its contamination index can reach national secondary discharge standard and BOD5≤60mg/l substantially, COD≤300mg/l, An Dan≤50mg/l, SS=100mg/l.But along with the development of society, require that enterprise must adhere to " overall control to pollutant control discharge in active response national policy, energy-saving and emission-reduction " call under, Environmental Protection Agency of Fujian Province issues associated documents in September, 2008, namely Environmental Protection Agency of Fujian Province is about the notice issuing strict implement pharmaceutical industry pollution discharge standard and cut down further gross contamination emission, be strict with the sewage discharge before 1 day July in 2010 of each pharmacy corporation and must reach " fermentation class pharmaceutical industry pollution discharge standard " (GB21903-2008) namely: BOD5≤30mg/l, COD≤100mg/l, An Dan≤25mg/l, SS=60mg/l.
So, after anaerobism, aerobic biological treatment process terminate, also must in conjunction with deep treatment technique, i.e. high-level oxidation technology------four phase catalytic oxidation technologies.This Technology collection is solid, liquid, the leggy one such as gas, by controlling various reaction conditions (as alloy catalyst, drug concentration, response intensity, medicament adds point, reaction times etc.), at electricity, magnetic, hydroxyl radical free radical OH is transferred under completing normal temperature and pressure under the microscopic integrative field conditions such as gas, that deep oxidation (AOP) oxidation rate achieved truly up to the strong oxidation of the hydroxyl radical free radical OH of 2.80V and the chain reaction of various free radicals (OO2H2O etc.) that produces thereupon based on oxidizing potential improves greatly, organic pollutant efficient removal at short notice can be realized.Bio-chemical effluent is linked into catalytic oxidizer (alloy catalyst is housed), add strong oxidizer, discoloring agent simultaneously, aeration 1 hour, water outlet adds liquid caustic soda, PAC and PAM, precipitate in chemical precipitation pond, precipitating sludge introduces sludge thickener, and supernatant liquor overflows and enters sewage plant sewage effluent standard mouth, monitors qualified discharge by on-line computing model.
Waste water after anaerobism and Aerobic biological process again by chemical Strong oxdiative deep treatment technique---catalytic oxidation technique process, sewage discharge reaches " fermentation class pharmaceutical industry pollution discharge standard " (GB21903-2008) namely: BOD5≤30mg/l, COD≤100mg/l An Dan≤25mg/l, SS=60mg/l.
By above Technology, thoroughly all kinds of pollution of antibiotics pharmaceutical industry is effectively processed, guarantee to implement qualified discharge, for enterprise's high speed development puts down obstacle, remove trouble and worry.
The comprehensive acidication for the treatment of process of the present invention, (EGSB) anaerobism, (A/O) are aerobic, four phase catalytic oxidation technologies, this treatment process technology can ensure that each pollutant produced in enterprise production process all can effectively be administered, qualified discharge is implemented according to national requirements for environmental protection, this system cloud gray model efficient stable, simple to operate, maintenance management convenience simultaneously, running cost and maintenance cost low, effective, thoroughly can reach emission standard and require and the policy meeting national current energy-saving and emission-reduction.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (8)
1. a treatment process for antibiotic waste water, is characterized in that, mainly comprises the following steps:
(s1) raw water collection: rely on run by gravity to carry out collecting equalizing tank in all sewage in production area, is uniformly mixed by whipping appts under water, mixes well water quality and quantity, guarantees that system can continuous uniform water inlet;
(s2) coagulating sedimentation pre-treatment: sewage enters coagulating sedimentation reactor, in coagulating sedimentation reactor, first by PH range regulation to 6.5-7.0, add deployed PAC and PAM successively again, by adjusting pH, dosing coagulant PAC, polymer coagulant aids PAM, most of suspended solid impurities in precipitation sewage, supernatant liquor enters hydrolysis acidification pool;
(s3) acidication: arrange diving propelling stirrer bottom hydrolysis acidification pool, prevents the deposition of mud; In middle and upper part, pond, combined stuffing is set, in order to adhere to mud, increase sludge concentration in pond, and reduce water outlet ss suspended solid value, change the non-solubility organism in original waste water into dissolved organic matter, and weaken the restraining effect of trade effluent to microorganism, the organism of wherein difficult for biological degradation is changed into the organism of readily biodegradable, improve the biodegradability BOD/COD ratio of waste water, be beneficial to follow-up biochemical treatment;
(s4) water distribution: in distribution reservoir, carries out mixing match by returned sluge, EGSB anaerobic effluent, acidication water outlet with 1:1:4, adjusts pH value to 6.0-6.5 simultaneously;
(s5) anaerobic treatment: the water outlet of distribution reservoir enters from the water distributor bottom EGSB anaerobic reactor, in the reactor, pH(6.8-7.2 suitable) and temperature under carry out middle temperature (33-35 DEG C) anaerobism, macromolecule organic changes into micromolecular VFA and methane, organism in sewage is decomposed utilization by anerobe, most of pollution substance is converted into water and carbonic acid gas, produce biogas simultaneously, carry out gas-solid-liquid finally by the triphase separator in reactor to be separated, biogas is collected by air chamber, solid particulate mud turns back to reaction zone by gravitational settling and continues DeR, the water outlet part that namely supernatant liquor is handled well returns after distribution reservoir carries out dilution proportioning and again enters anaerobic system by water distributor, another part enters aerobic treatment stage next stage,
(s6) aerobic treatment: anaerobic effluent enters aerobic system, the free oxygen of aerobic microbiological inside O pond is using organic pollutant as nutrition source, organic pollutant is degraded, stable, autotrophic type microorganism carries out nitrification simultaneously, NH3 is oxidized to nitrite, be reoxidised into nitrate, in A pond, NO3-N and NO2-N passes through denitrifying bacterium, be converted into gaseous nitrogen and Nitrous Oxide, A pond is stirred, the oxygen supply of O pond, intake from front end, A pond, O pond outlet water at tail end is back to A pond, mixed solution enters biogenic sediment pond precipitation, sludge part refluxes, excess sludge enters sludge thickener and outward transport after dehydration, supernatant liquor overflow penetration depth governing system,
(s7) advanced treatment: four phase catalytic oxidizing equipments of supernatant liquor penetration depth treatment system, add catalyst sulfuric acid ferrous iron and oxidant hydrogen peroxide, produce hydroxyl radical free radical OH, and blast aeration 1 hour, containing alloy catalyst in described four catalytic oxidizing equipments; The reaction water outlet of four phase catalytic oxidizing equipments enters into catalytic oxidation pond, continues oxidizing reaction by micro-pore aeration, and exhaustive oxidation decomposes not biodegradable COD and colourity, and forms a large amount of tawny flock, is suspended in mixed solution; The mixed solution in catalytic oxidation pond enters chemical precipitation pond, add the alkali lye that concentration is 30% in mixed solution, mixed solution PH is adjusted to neutrality, then dosing coagulant PAC and polymer coagulant aids PAM, carried out by described flock tackling, collecting, mud enters concentration basin treatment system.
2. the treatment process of antibiotic waste water according to claim 1, is characterized in that, described alloy catalyst with training wall arranged in form in described four phase catalytic oxidizing equipments.
3. the treatment process of antibiotic waste water according to claim 1, it is characterized in that, some groups of perforation water distributors are provided with bottom described hydrolysis acidification pool, this pond is divided into five regions by vertical traverse baffle, combined stuffing described in each areal distribution, described diving propelling stirrer is arranged in the 2nd, 3rd district and the 4th, 5th district.
4. the treatment process of antibiotic waste water according to claim 1, it is characterized in that, described triphase separator, form by a main separator and around several separator that this main separator is evenly arranged, each separator is cylindric, the inside of separator is provided with the funnelform isolated part that is back-off, reflector is provided with below this isolated part, by this isolated part, the upper space of reactor is separated into gas passage, air chamber, settling region, above described reactor, both sides are equipped with overflow weir notch, and on the face that main separator is relative with each separator, offer sludge reflux mouth respectively.
5. the treatment process of antibiotic waste water according to claim 4, it is characterized in that, described reflector is umbrella, and is formed in 15 ° of angles between horizontal plane, have diameter 300mm hole in the middle of plate, this reflector edge is welded on the sidewall of separator by some stainless steel tubes.
6. according to the treatment process of any one of claim 4 antibiotic waste water, it is characterized in that, described water distributor is detachable, it is uniformly distributed in bottom by some perforation water distributors and forms, and two ends stretch out in reactor outside, the two ends of every root water distributor are equipped with valve, and pending sewage enters inside reactor via water distributor one end.
7. the treatment process of antibiotic waste water according to claim 4, is characterized in that, described time separator is 8, and connect with main separator after in parallel between each, each separator works alone.
8. the treatment process of the antibiotic waste water stated according to claim 6, is characterized in that, described water distributor is made up of 8 water distributors of independently boring a hole.
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