CN106746159A - A kind of processing method of antibiotic production wastewater - Google Patents
A kind of processing method of antibiotic production wastewater Download PDFInfo
- Publication number
- CN106746159A CN106746159A CN201510802486.5A CN201510802486A CN106746159A CN 106746159 A CN106746159 A CN 106746159A CN 201510802486 A CN201510802486 A CN 201510802486A CN 106746159 A CN106746159 A CN 106746159A
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- fstb
- waste water
- anaerobic
- oxidation
- treatment
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention relates to a kind of processing method of antibiotic production wastewater, including（1）Using the suspension in air-flotation process removing waste water；（2）Waste water is processed using high-level oxidation technology, improves biodegradability；（3）Coagulating sedimentation, the precipitation that filtering removal is produced are carried out to oxidation water outlet；（4）Anaerobic biochemical treatment is carried out to filtering water outlet；（5）Aerobic treatment is carried out to anaerobic effluent, and adds the de- COD denitrogenations microbial inoculum of salt tolerant.The present invention uses air supporting-coagulating sedimentation-advanced oxidation-anaerobic biological-aerobic biochemical combined treatment process, and add specifically de- COD denitrogenation microbial inoculums in aerobic unit, the antibiotic in waste water can not only be tolerated, and can be with the COD in efficient removal waste water and total nitrogen, with process is simple, treatment effeciency be high, the low feature of processing cost.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of processing method of antibiotic production wastewater.
Background technology
Antibiotic is the great discovery in human history, is widely used for the multiple fields such as medical treatment, effective guarantee human body health.But in antibiotics production and application process, a large amount of organic wastewater with difficult degradation thereby containing antibiotic can be produced.With grain or molasses as the waste water of main material production antibiotic essentially from separating, extract, the high concentrated organic wastewater of polishing purification technique, COD, ammonia nitrogen are the major pollutants in the sewage, and salt content is higher in waste water, containing a certain amount of sulfate radical and contain a small amount of Biostatic material.Antibiotic waste water is complicated due to water quality, big on environment water influence, belongs to the larger waste water of intractability.
There is the technology of various treatment antibiotic waste waters at present, physical-chemical process, anaerobic biochemical, aerobic biochemical process and correlation combiner technology etc. can be divided into by mechanism.Because antibiotic waste water content of organics is high, be difficult to the characteristics of directly being processed by aerobic microbiological, the method for the treatment of antibiotic waste water is mainly physico-chemical process and the group technology with bioanalysis as core both at home and abroad.Physico-chemical process includes coagulation-precipitation, air supporting, burning, extraction, absorption, advanced oxidation, micro-electrolysis method, counter-infiltration, evaporation etc..Carrying out pretreatment in antibiotic production wastewater before processing can improve waste water quality, and reduction has the concentration of inhibitory substance to biochemical process.Bioanalysis have operating cost low and it is environment-friendly the features such as, its treatment antibiotic waste water technology in occupy dominant position.The biological method for processing antibiotic waste water mainly has anaerobic biochemical and aerobic biochemical process.
Anaerobic biochemical is used for the degradation process of noxious material in antibiotic production wastewater, lifts the biodegradability of antibiotic production wastewater.Anaerobic biochemical is vulnerable to the influence of Coal Gas Washing Cycling Water sulfate, the residues of antibiotics of antibiotic waste water, salt and some additives, can seriously suppress the normal metabolic activity of anaerobe.There are up-flow anaerobic sludge blanket (UASB) and anaerobic composite bed (UBF) etc. for the anaerobic technique of antibiotic waste water treatment.Water outlet COD after being processed through single Anaerobic cultural methods is still higher, it is difficult to realizes standard water discharge, typically uses Aerobic Process for Treatment further to remove rest COD.Antibiotic production wastewater still produces the material of inhibition containing salt content higher, COD and a small amount of antibiotic etc. after anaerobic biochemical treatment to aerobic biochemical process, it usually needs enter aerobic biochemical section treatment after dilution.The aerobic biochemical process for being usually used in antibiotic production wastewater treatment has conventional activated sludge process, compression biochemical method, deep well aeration method, biological contact oxidation process, biological fluidized bed method and sequencing batch active sludge etc..
CN101654311A is related to a kind of method that antibiotic waste water is processed using up-flow anaerobic sludge blanket-aerobic membrane bioreactor (UASB-MBR) combined unit, the MBR technology that it is used can reduce floor space, and the water quality of water outlet also increases, but there is a problem of fouling membrane and block so that technique overall operation is relatively costly.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of processing method of antibiotic production wastewater.The present invention uses air supporting-advanced oxidation-coagulating sedimentation-anaerobic biological-aerobic biochemical combined treatment process, and add specifically de- COD denitrogenation microbial inoculums in aerobic unit, the antibiotic in waste water can not only be tolerated, and can be with the COD in efficient removal waste water and total nitrogen, with process is simple, treatment effeciency be high, the low feature of processing cost.
The processing method of antibiotic production wastewater of the present invention, comprises the following steps：
（1）Air-flotation process：Using the suspension in air-flotation process removing waste water；
（2）Advanced oxidation：Waste water is processed using high-level oxidation technology, improves biodegradability；
（3）Coagulating sedimentation：Coagulating sedimentation, the precipitation that filtering removal is produced are carried out to oxidation water outlet；
（4）Anaerobic biological：Anaerobic biochemical treatment is carried out to filtering water outlet；
（5）Aerobic biochemical：Aerobic treatment is carried out to anaerobic effluent, and adds the de- COD denitrogenations microbial inoculum of salt tolerant；The microbial inoculum includes secondary coccus（Paracoccus sp.）Microbacterium is seen in FSTB-2, north（Microbacterium kitamiense）FSTB-4, Pseudomonas stutzeri（Pseudomonas stutzeri）At least one of FSTB-5, Paracoccus denitrificans (Paracoccus denitrificans)
DN-3 and Methylobacterium (Methylobacterium
phyllosphaeraeAt least one of) SDN-3, arthrobacterium（Arthrobacter creatinolyticus）FDN-1 and Shui Shi Flavobacteriums（Flavobacterium mizutaii）At least one of FDN-2, marsh cock Salmonella（Kocuria palustris）FSDN-A and Staphylococcus cohnis (Staphylococcus cohnii）At least one in FSDN-C.Wherein secondary coccus FSTB-2, north see that microbacterium FSTB-4 and Pseudomonas stutzeri FSTB-5 are preserved in " China Committee for Culture Collection of Microorganisms's common micro-organisms center ", preservation address on June 26th, 2015：Yard 1, BeiChen xi Road, Chaoyang District, Beijing City 3 Institute of Microorganism, Academia Sinica；Deposit number is respectively CGMCC
No.10938、CGMCC No.10939、CGMCC No.10940.Paracoccus denitrificans DN-3, Methylobacterium SDN-3, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, marsh cock Salmonella FSDN-A, Staphylococcus cohnis FSDN-C are disclosed in CN102465104A, CN102465103,102465105A, 102465106A, 103103141A, 103103142A.
Antibiotic production wastewater of the present invention is mainly derived from microbial fermentation and Antibiotics separation, extraction, the waste water of polishing purification process section generation.Waste water quality is：COD is 5000-80000mg/L, and salt content is 1.2wt%-5.0wt%, and suspension is 500-25000mg/L, and ammonia nitrogen concentration is 50-800mg/L, and pH value is 2-10.
Step of the present invention（1）Described air-flotation process is conventional use of air-flotation treatment method, can such as use gas distribution air supporting or air-dissolving air-float, and air supporting air dosage, air supporting pressure difference and time determine that suspension is reduced to below 2500mg/L after treatment according to the concentration of specific suspension.
Step of the present invention（2）Described high-level oxidation technology can be ozone oxidation, iron-carbon micro-electrolysis, Fenton oxidation etc., while part COD is removed, can improve the biodegradability of waste water.It is preferred that using ozone oxidation, antibiotic production wastewater is sent into ozone-oxidizing device, by ozone oxidation agent, by the difficult for biological degradation oxidation operation in waste water into the lower-molecular substance of biodegradability, reach improvement wastewater biodegradability purpose.Described ozone-oxidizing device use reaction tower or contact-oxidation pool, ozone oxidation agent by processing unit outside ozone generator provide.The dosage of ozone oxidation agent is 20-50mg/L waste water, preferably 30-40mg/L waste water；Ozone oxidation agent gas access concentration is 50-120mg/L, preferably 100-120mg/L；Hydraulic detention time of the waste water in reaction tower or oxidation pond is 10-60min, preferably 20-30min.By the cell processing, water outlet BOD5/COD≥0.4。
Step of the present invention（3）Described coagulating sedimentation can typically be used using conventional coagulation sedimentation method to dosing coagulant, flocculant, flocculation aid or triplicity in waste water.Described coagulant can be the low-molecular inorganic materials such as alum, aluminum sulfate, chloro sulphuric acid aluminium, ferric sulfate, ferrous sulfate, iron chloride, ferric trichloride, or the inorganic polymer material such as aluminium polychloride, polyaluminium sulfate, polychloride ferro-aluminum, bodied ferric sulfate；Described flocculant can be the polymers such as polyacrylamide, polypropylene acid；Described flocculation aid can be lime, ozone, hydrogen peroxide, potassium permanganate etc..It is preferred that by the way of organic flocculant and inorganic flocculating agent combination is added, wherein organic flocculant is polyacrylamide, and dosage is 3-10mg/L；Inorganic flocculating agent uses bodied ferric sulfate or ferric trichloride, and dosage is 20-100mg/L.Purpose is to remove the suspension in waste water, and adjusts the pH value of waste water, to mitigate the processing load of subsequent biochemical unit.Dosage determines that suspension is less than 1000mg/L after treatment, and pH value is 6.0-9.0 according to concentration of suspension.
In the present invention, step（3）Filtering can use various filter plants well known to those skilled in the art.Can be such as separated by filtration using batch centrifuge, rotating speed is controlled in 1000-5000rpm, and centrifugation time is 5-10min.
In the present invention, step（4）Described anaerobic biochemical treatment can be anaerobic baffled reactor（ABR）, upflow anaerobic sludge blanket reactor（UASB）, internal-circulation anaerobic reactor（IC）, be thoroughly mixed in formula anaerobic reation pool, expanded granular sludge bed reactor reactor (EGSB) etc. any one.The service condition of anaerobic biochemical treatment is：Hydraulic detention time is 6-48 hours, and pH value is 6.0-9.0, and temperature is 20-45 DEG C.
In the present invention, step（5）Described aerobic biochemical process can be sequence batch activated sludge process（SBR）, biological contact oxidation process, loop cycle activated Sludge System（CASS）, membrane bioreactor（MBR）, BAF（BFT）, moving bed membrane bioreactor（MBBR）Any one in.The service condition of aerobic treatment is：Hydraulic detention time is 6-24 hours, and pH value is 6.0-9.0, and temperature is 20-40 DEG C.
Step of the present invention（5）In the microbial inoculum, the main morphological features of secondary coccus FSTB-2 are：Colony colour is ecru, and it is spherical that bacterial strain is individual；Physiological and biochemical property is：Gram's staining is feminine gender, and oxidase positive, catalase is negative, and decomposable asymmetric choice net utilizes several kinds of carbon source, with nitrate reduction activity；It is resistant to one or more in lincomycin, Rifamycin Sodium, acidum nalidixicum, guanidine hydrochloride etc..North sees that the main morphological features of microbacterium FSTB-4 are：Colony colour is shallower taupe brown, and it is shaft-like that bacterial strain is individual；Physiological and biochemical property is：Gram-positive, oxidase negative contacts enzyme positive, and decomposable asymmetric choice net utilizes several kinds of carbon source, with nitrate reduction characteristic；It is resistant to AZT, acidum nalidixicum etc..The main morphological features of Pseudomonas stutzeri FSTB-5 are：Colony colour is shallow ginger color, and it is shaft-like that bacterial strain is individual；Physiological and biochemical property is：Gram-negative, oxidase negative contacts enzyme positive, and with nitrate reduction performance, decomposable asymmetric choice net utilizes several kinds of carbon source；It is resistant to one or more in lincomycin, minocycline, Rifamycin Sodium, troleandomycin, vancomycin, AZT, acidum nalidixicum etc..
Step of the present invention（5）" secondary coccus in the microbial inoculum（Paracoccus sp.）Microbacterium is seen in FSTB-2, north（Microbacterium kitamiense）FSTB-4, Pseudomonas stutzeri（Pseudomonas stutzeri）At least one of FSTB-5 "; " at least one of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 "; " at least one of arthrobacterium FDN-1 and Shui Shi Flavobacterium FDN-2 "; " at least one in marsh cock Salmonella FSDN-A and Staphylococcus cohnis FSDN-C ", the thalline volume ratio of four class bacterium is preferably 5:1-5:1-5:1-5.（By thalline stereometer, thalline volume is the thalline volume for obtaining under the conditions of 10,000 turns per minute after centrifugation 5 minutes after culture, similarly hereinafter）.
Step of the present invention（5）The microbial inoculum is added after can according to a certain percentage being mixed using the dense bacterium solution for directly preparing, it is also possible to is added nutriment, preservation auxiliary agent etc. to be prepared into microbial inoculum and is added.Secondary coccus FSTB-2, north see that microbacterium FSTB-4, Pseudomonas stutzeri FSTB-5 directly prepare concretely comprising the following steps for dense bacterium solution in the microbial inoculum for being added：
（1）Respectively by secondary coccus（Paracoccus sp.）FSTB-2, north are shown in microbacterium FSTB-4, Pseudomonas stutzeri（Pseudomonas stutzeri）FSTB-5 is inoculated into the inclined-plane of FSTB solid mediums or flat board, and 25-40 DEG C is cultivated 24-48 hours；
（2）Liquid seeds liquid culture：FSTB fluid nutrient mediums are prepared, is sub-packed in triangular flask, after sterilizing and being cooled to room temperature, in the inoculation activated in picking inclined-plane or flat board under gnotobasis to triangular flask, 25-40 DEG C is cultivated 24-72 hours.The FSTB fluid nutrient mediums are：FeSO4•7H2O
25mg/L, NH4NO3286mg/L, KCl 929mg/L, CaCl22769mg/L, NaCl 21008mg/L, beef extract 5g/L, peptone 10g/L, pH value is 6.0-8.5, preferably 6.5-8.0.FSTB solid mediums are the agar of addition 20g/L in liquid medium within；
（3）Aeration culture：FSTB fluid nutrient mediums are added in the reactor for be provided with aerator, ratio inoculation liquid seed liquor according to reactor volume than 5%-25%, pH value is controlled in 6.0-8.5, aeration culture 48-96 hours, periodic feed supplement and discharge operation are carried out afterwards, withdrawal rate accounts for the 5%-90% of reactor volume, feed supplement amount accounts for the 5%-90% of reactor volume, also a small amount of carbon source, nitrogen source and microelement substance can be added, culture 24-48 hours is 1 cultivation cycle, the nutrient solution of corresponding volume is discharged according to aforementioned proportion afterwards, the dense bacterium solution containing high concentration is thus obtained.
Step of the present invention（5）Paracoccus denitrificans DN-3 in the microbial inoculum, Methylobacterium SDN-3, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, marsh cock Salmonella FSDN-A, six plants of bacterium seed liquors of Staphylococcus cohnis FSDN-C can individually amplify culture, or culture is amplified after seed liquor mixing jointly, the specific preparation method of bacteria suspension refers to the method described in CN201210130645.8 and CN 2012101306443.
In the present invention, microbial inoculum will be prepared and be added in wastewater treatment system according to the 0.01%-1% of handled wastewater volume per hour, preferably 0.1%-0.5%.
Compared with prior art, the invention has the advantages that：
（1）The present invention uses air supporting-coagulating sedimentation-advanced oxidation-anaerobic biological-aerobic biochemical combined treatment process, and add the de- COD denitrogenations microbial inoculum of salt tolerant in aerobic unit, the antibiotic in waste water can not only be tolerated, and can be with the COD in efficient removal waste water and total nitrogen, with process is simple, treatment effeciency be high, the low feature of processing cost.
（2）The microbial inoculum that the present invention is added can tolerate high content of salt, the efficient removal of COD and total nitrogen in waste water is realized simultaneously, can be applied not only to the efficient removal of COD in brine waste, the antibiotic in waste water can particularly be tolerated, it is especially suitable for the biochemical treatment of antibiotic production wastewater, it is small with dosage, the low advantage of processing cost.
Specific embodiment
Technical scheme and effect are described in detail with reference to embodiment, but are not so limited the present invention.
The embodiment of the present invention prepares bacterium solution using the specific preparation method of Paracoccus denitrificans DN-3, Methylobacterium SDN-3, arthrobacterium FDN-1, Shui Shi Flavobacterium FDN-2, marsh cock Salmonella FSDN-A and Staphylococcus cohnis FSDN-C bacterial strains with reference to embodiment methods described in CN201210130645.8 and CN 2012101306443.
The secondary coccus FSTB-2 of embodiment of the present invention use, north are shown in microbacterium FSTB-4, the cultural method of Pseudomonas stutzeri FSTB-5 includes bacterial strain activation, the culture of liquid seeds liquid, aeration culture, and detailed process is as follows：
（1）Bacterial strain is activated：Bacterial strain is individually inoculated on FSTB solid mediums and is activated, then 35 DEG C of culture 48h are stored in stand-by in 4 DEG C of refrigerators；FSTB solid culture based formulas are：FeSO4•7H2O
25mg/L, NH4NO3286mg/L, KCl 929mg/L, CaCl22769mg/L, NaCl 21008mg/L, beef extract 5g/L, peptone 10g/L, agar 20g/L, pH value 7.8；
（2）Liquid seeds liquid culture：FSTB fluid nutrient mediums are prepared, after sterilizing and being cooled to room temperature, is inoculated into triangular flask with the Pseudomonas stutzeri FSTB-5 after being activated in oese picking flat board under gnotobasis, 35 DEG C are cultivated 48 hours.The FSTB Liquid Cultures based formulas are：FeSO4•7H2O 25mg/L, NH4NO3
286mg/L, KCl
929mg/L, CaCl22769mg/L, NaCl 21008mg/L, beef extract 5g/L, peptone 10g/L, pH value is 8.0；
（3）Aeration culture：Cultivated using closed reactor,It is complete that institute is required to sterilizing using reactor and various utensils,Air inlet and exhaust position need to install bacteriological filter apparatus,Nutrient solution,Acid-base modifier and trace element solution are added after being required to sterilizing according to sterile working code,Reactor need to be equipped with aerator,And can carry out into water,Acid adjustment,Alkali tune,Feed supplement and draining discharge are operated,The fluid nutrient medium after sterilizing is put into the reactor,Ratio according to percent by volume 10% is inoculated with liquid seed liquor,After opening incubation,Use soda acid automatic control system by medium pH value scope control in 6.0-8.5 in incubation,Aeration culture carries out periodic feed supplement and discharge operation for 72 hours afterwards,Discharge is the nutrient solution of the 25% of reactor volume,Feed supplement is the fluid nutrient medium of reactor volume 25%,Culture 24 hours is 1 cultivation cycle,The nutrient solution of corresponding volume is discharged according to aforementioned proportion afterwards,Thus the dense bacterium solution of each corresponding pure bacterial strain is obtained.
Above-mentioned bacterium solution is collected and according to ratio described in table 1 compound and obtains de- COD denitrogenation microbial inoculums.
Table 1 takes off the formula of COD denitrogenation microbial inoculums
Embodiment 1
The composite waste of the generations such as certain antibiotic plant produced lincomycin, rifamycin, waste water quality is：COD（Cr methods, similarly hereinafter）It is 15000mg/L, salt content 1.2wt%, suspension 5000mg/L, ammonia nitrogen 200mg/L, pH value 7.5.
Waste water is processed using the inventive method, air is dissolved in the water under 0.35MPa first, dissolved air water is then delivered into air flotation slot, the microbubble of formation is removed partial contamination thing band to the water surface, and water outlet concentration of suspension is down to below 1500mg/L.Air supporting water outlet enters ozone reactor, ozone oxidation agent is provided by ozone generator, and the dosage of ozone oxidation agent is 40mg/L waste water, and ozone oxidation agent gas access concentration is 100mg/L, waste water is 30min, ozone oxidation water outlet BOD in the hydraulic detention time of reactor5/COD≥0.6.Oxidation water outlet carries out coagulating sedimentation, and the dosage of polyacrylamide is 5mg/L, and the dosage of bodied ferric sulfate is 40mg/L, filtering removal precipitation.Concentration of suspension is down to below 500mg/L in coagulation water outlet, and pH value is 7.8.Coagulation water outlet enters internal-circulation anaerobic reactor（IC）, service condition is：Hydraulic detention time is 24h, and pH value is 7.5-8.5, and temperature is 35 DEG C.Inner circulation reactor water outlet enters loop cycle activated Sludge System（CASS）, while adding the de- COD denitrogenations microbial inoculum A that above-mentioned culture is obtained according to the 0.7% of handled wastewater volume per hour.The service condition of aerobic treatment is：Hydraulic detention time is 12h, and pH value is 8.0-8.5, and temperature is 30 DEG C.Treatment effect is shown in Table 2.
Embodiment 2
The composite waste of the generations such as certain antibiotic plant produced acidum nalidixicum, waste water quality is：COD（Cr methods, similarly hereinafter）It is 12000mg/L, salt content 1.5wt%, suspension 10000mg/L, ammonia nitrogen 200mg/L, pH value 7.5.
Waste water is processed using the inventive method, air is dissolved in the water under 0.35MPa first, dissolved air water is then delivered into air flotation slot, the microbubble of formation is removed partial contamination thing band to the water surface, and water outlet concentration of suspension is down to below 2000mg/L.Air supporting water outlet enters ozone reactor, ozone oxidation agent is provided by ozone generator, and the dosage of ozone oxidation agent is 35mg/L waste water, and ozone oxidation agent gas access concentration is 100mg/L, waste water is 30min, ozone oxidation water outlet BOD in the hydraulic detention time of reactor5/COD≥0.4.Oxidation water outlet carries out coagulating sedimentation, and the dosage of polyacrylamide is 10mg/L, and the dosage of ferric trichloride is 50mg/L, filtering removal precipitation.Concentration of suspension is down to below 500mg/L in coagulation water outlet, and pH value is 7.5.Into formula anaerobic reactor is thoroughly mixed, service condition is for coagulation water outlet：Hydraulic detention time is 24h, and pH value is 7.5-8.5, and temperature is 30 DEG C.Inner circulation reactor water outlet enters sequencing batch active sludge（SBR）Reactor, while adding the de- COD denitrogenations microbial inoculum B that above-mentioned culture is obtained according to the 0.6% of handled wastewater volume per hour.The service condition of aerobic treatment is：Hydraulic detention time is 12h, and pH value is 8.0-8.5, and temperature is 35 DEG C.Treatment effect is shown in Table 2.
Embodiment 3
The composite waste of the generations such as certain antibiotic plant produced lincomycin, rifamycin, waste water quality is：COD（Cr methods, similarly hereinafter）It is 15000mg/L, salt content 1.2wt%, suspension 5000mg/L, ammonia nitrogen 200mg/L, pH value 7.5.
Waste water is processed using the inventive method, air is dissolved in the water under 0.35MPa first, dissolved air water is then delivered into air flotation slot, the microbubble of formation is removed partial contamination thing band to the water surface, and water outlet concentration of suspension is down to below 1500mg/L.Air supporting water outlet enters ozone reactor, ozone oxidation agent is provided by ozone generator, and the dosage of ozone oxidation agent is 40mg/L waste water, and ozone oxidation agent gas access concentration is 100mg/L, waste water is 30min, ozone oxidation water outlet BOD in the hydraulic detention time of reactor5/COD≥0.4.Oxidation water outlet carries out coagulating sedimentation, and the dosage of polyacrylamide is 5mg/L, and the dosage of ferric trichloride is 70mg/L, filtering removal precipitation.Concentration of suspension is down to below 500mg/L in coagulation water outlet, and pH value is 7.5.Into formula anaerobic reactor is thoroughly mixed, service condition is for coagulation water outlet：Hydraulic detention time is 24h, and pH value is 7.5-8.5, and temperature is 30 DEG C.Formula anaerobic reactor water outlet into moving bed membrane bioreactor is thoroughly mixed, while adding the de- COD denitrogenations microbial inoculum C that above-mentioned culture is obtained according to the 0.5% of handled wastewater volume per hour.The service condition of aerobic treatment is：Hydraulic detention time is 12h, and pH value is 8.0-8.5, and temperature is 35 DEG C.Treatment effect is shown in Table 2.
Embodiment 4
, with embodiment 1, difference is for handling process and operating condition：Aerobic treatment unit adds the de- COD denitrogenations microbial inoculum D that above-mentioned culture is obtained according to the 0.5% of handled wastewater volume per hour.Treatment effect is shown in Table 2.
Embodiment 5
, with embodiment 1, difference is for handling process and operating condition：Aerobic treatment unit adds the de- COD denitrogenations microbial inoculum E that above-mentioned culture is obtained according to the 0.5% of handled wastewater volume per hour.Treatment effect is shown in Table 2.
Embodiment 6
, with embodiment 1, difference is for handling process and operating condition：Aerobic treatment unit adds the de- COD denitrogenations microbial inoculum F that above-mentioned culture is obtained according to the 0.5% of handled wastewater volume per hour.Treatment effect is shown in Table 2.
Comparative example 1
, with embodiment 1, difference is for handling process and operating condition：Ozone oxidation is not carried out after air-flotation process, coagulating sedimentation is directly carried out.Treatment effect is shown in Table 2.
Comparative example 2
, with embodiment 1, difference is for handling process and operating condition：Anaerobic Treatment is directly carried out after ozone oxidation, coagulating sedimentation is not carried out.Treatment effect is shown in Table 2.
Comparative example 3
, with embodiment 1, difference is for handling process and operating condition：De- COD denitrogenations microbial inoculum is not added in aerobic treatment unit.Treatment effect is shown in Table 2.
The treatment effect of the different embodiments of table 2 and comparative example
From table 2, antibiotic production wastewater is processed using the inventive method, emission request can be met with the COD in efficient removal waste water and total nitrogen, high treating effect.
Claims (15)
1. a kind of processing method of antibiotic production wastewater, it is characterised in that comprise the following steps：
（1）Air-flotation process：Using the suspension in air-flotation process removing waste water；
（2）Advanced oxidation：Waste water is processed using high-level oxidation technology, improves biodegradability；
（3）Coagulating sedimentation：Coagulating sedimentation, the precipitation that filtering removal is produced are carried out to oxidation water outlet；
（4）Anaerobic biological：Anaerobic biochemical treatment is carried out to filtering water outlet；
（5）Aerobic biochemical：Carry out aerobic treatment to anaerobic effluent, and add the de- COD denitrogenations microbial inoculum of salt tolerant, the microbial inoculum includes secondary coccus（Paracoccus sp.）Microbacterium is seen in FSTB-2, north（Microbacterium kitamiense）FSTB-4, Pseudomonas stutzeri（Pseudomonas stutzeri）At least one of FSTB-5, Paracoccus denitrificans (Paracoccus denitrificans)
DN-3 and Methylobacterium (Methylobacterium phyllosphaerae)
At least one of SDN-3, arthrobacterium（Arthrobacter creatinolyticus）FDN-1 and Shui Shi Flavobacteriums（Flavobacterium mizutaii）At least one of FDN-2, marsh cock Salmonella（Kocuria palustris）FSDN-A and Staphylococcus cohnis (Staphylococcus
cohnii）At least one in FSDN-C.
2. method according to claim 1, it is characterised in that：Described antibiotic production wastewater is mainly derived from microbial fermentation and Antibiotics separation, extraction, the waste water of polishing purification process section generation, and waste water quality is：COD is 5000-80000mg/L, and salt content is 1.2wt%-5.0wt%, and suspension is 500-25000mg/L, and ammonia nitrogen concentration is 50-800mg/L, and pH value is 2-10.
3. method according to claim 1, it is characterised in that：Step（1）Described air-flotation process uses gas distribution air supporting or air-dissolving air-float, and air supporting air dosage, air supporting pressure difference and time determine that suspension is reduced to below 2500mg/L after treatment according to the concentration of specific suspension.
4. method according to claim 1, it is characterised in that：Step（2）Described high-level oxidation technology is ozone oxidation, iron-carbon micro-electrolysis or Fenton oxidation, while part COD is removed, improves the biodegradability of waste water.
5. the method according to claim 1 or 4, it is characterised in that：Step（2）Using ozone oxidation, ozone-oxidizing device uses reaction tower or contact-oxidation pool, ozone oxidation agent by processing unit outside ozone generator provide；The dosage of ozone oxidation agent is 20-50mg/L waste water, and ozone oxidation agent gas access concentration is 50-120mg/L, and hydraulic detention time of the waste water in reaction tower or oxidation pond is 10-60min.
6. method according to claim 1, it is characterised in that：Step（3）Described coagulating sedimentation is used to dosing coagulant, flocculant, flocculation aid or triplicity in waste water；Described coagulant is alum, aluminum sulfate, chloro sulphuric acid aluminium, ferric sulfate, ferrous sulfate, iron chloride or ferric trichloride low-molecular inorganic material, or is aluminium polychloride, polyaluminium sulfate, polychloride ferro-aluminum or bodied ferric sulfate inorganic polymer material；Described flocculant is polyacrylamide or polypropylene acid polymer；Described flocculation aid is lime, ozone, hydrogen peroxide or potassium permanganate.
7. the method according to claim 1 or 6, it is characterised in that：Step（3）By the way of organic flocculant and inorganic flocculating agent combination is added, wherein organic flocculant is polyacrylamide, and dosage is 3-10mg/L；Inorganic flocculating agent uses bodied ferric sulfate or ferric trichloride, and dosage is 20-100mg/L.
8. method according to claim 1, it is characterised in that：Step（4）Described anaerobic biochemical treatment be anaerobic baffled reactor, upflow anaerobic sludge blanket reactor, internal-circulation anaerobic reactor, be thoroughly mixed in formula anaerobic reation pool, expanded granular sludge bed reactor reactor any one；The service condition of anaerobic biochemical treatment is：Hydraulic detention time is 6-48 hours, and pH value is 6.0-9.0, and temperature is 20-45 DEG C.
9. method according to claim 1, it is characterised in that：Step（5）Described aerobic treatment is any one in sequence batch activated sludge process, biological contact oxidation process, loop cycle activated Sludge System, membrane bioreactor, BAF, moving bed membrane bioreactor；The service condition of aerobic treatment is：Hydraulic detention time is 6-24 hours, and pH value is 6.0-9.0, and temperature is 20-40 DEG C.
10. method according to claim 1, it is characterised in that：Step（5）In the microbial inoculum, the main morphological features of secondary coccus FSTB-2 are：Colony colour is ecru, and it is spherical that bacterial strain is individual；Physiological and biochemical property is：Gram's staining is feminine gender, and oxidase positive, catalase is negative, and decomposable asymmetric choice net utilizes several kinds of carbon source, with nitrate reduction activity；It is resistant to one or more in lincomycin, Rifamycin Sodium, acidum nalidixicum, guanidine hydrochloride；North sees that the main morphological features of microbacterium FSTB-4 are：Colony colour is shallower taupe brown, and it is shaft-like that bacterial strain is individual；Physiological and biochemical property is：Gram-positive, oxidase negative contacts enzyme positive, and decomposable asymmetric choice net utilizes several kinds of carbon source, with nitrate reduction characteristic；It is resistant to AZT or acidum nalidixicum；The main morphological features of Pseudomonas stutzeri FSTB-5 are：Colony colour is shallow ginger color, and it is shaft-like that bacterial strain is individual；Physiological and biochemical property is：Gram-negative, oxidase negative contacts enzyme positive, and with nitrate reduction performance, decomposable asymmetric choice net utilizes several kinds of carbon source；It is resistant to one or more in lincomycin, minocycline, Rifamycin Sodium, troleandomycin, vancomycin, AZT, acidum nalidixicum.
11. methods according to claim 1, it is characterised in that：Step（5）" secondary coccus in the microbial inoculum（Paracoccus sp.）Microbacterium is seen in FSTB-2, north（Microbacterium kitamiense）FSTB-4, Pseudomonas stutzeri（Pseudomonas
stutzeri）At least one of FSTB-5 "; " at least one of Paracoccus denitrificans DN-3 and Methylobacterium SDN-3 "; " at least one of arthrobacterium FDN-1 and Shui Shi Flavobacterium FDN-2 "; " at least one in marsh cock Salmonella FSDN-A and Staphylococcus cohnis FSDN-C ", the thalline volume ratio of four class bacterium is preferably 5:1-5:1-5:1-5.
12. methods according to claim 1, it is characterised in that：Step（5）The microbial inoculum is added after being mixed according to a certain percentage using the dense bacterium solution for directly preparing, or adds nutriment, preservation auxiliary agent to be prepared into microbial inoculum and added.
13. method according to claim 1 or 12, it is characterised in that：Secondary coccus FSTB-2, north see that microbacterium FSTB-4, Pseudomonas stutzeri FSTB-5 directly prepare concretely comprising the following steps for dense bacterium solution in the microbial inoculum for being added：
（1）Respectively by secondary coccus（Paracoccus sp.）FSTB-2, north are shown in microbacterium FSTB-4, Pseudomonas stutzeri（Pseudomonas stutzeri）FSTB-5 is inoculated into the inclined-plane of FSTB solid mediums or flat board, and 25-40 DEG C is cultivated 24-48 hours；
（2）Liquid seeds liquid culture：FSTB fluid nutrient mediums are prepared, is sub-packed in triangular flask, after sterilizing and being cooled to room temperature, in the inoculation activated in picking inclined-plane or flat board under gnotobasis to triangular flask, 25-40 DEG C is cultivated 24-72 hours；
（3）Aeration culture：FSTB fluid nutrient mediums are added in the reactor for be provided with aerator, ratio inoculation liquid seed liquor according to reactor volume than 5%-25%, pH value is controlled in 6.0-8.5, aeration culture 48-96 hours, carries out periodic feed supplement and discharge operation afterwards, and withdrawal rate accounts for the 5%-90% of reactor volume, feed supplement amount accounts for the 5%-90% of reactor volume, culture 24-48 hours is 1 cultivation cycle, discharges the nutrient solution of corresponding volume according to aforementioned proportion afterwards, thus obtains the dense bacterium solution containing high concentration.
14. methods according to claim 13, it is characterised in that：The FSTB fluid nutrient mediums are：FeSO4•7H2O 25mg/L, NH4NO3
286mg/L, KCl 929mg/L, CaCl22769mg/L, NaCl 21008mg/L, beef extract 5g/L, peptone 10g/L, pH value is 6.0-8.5；FSTB solid mediums are the agar of addition 20g/L in liquid medium within.
15. method according to claim 1,11 or 13, it is characterised in that：Microbial inoculum will be prepared to be added in wastewater treatment system according to the 0.01%-1% of handled wastewater volume per hour.
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