CN103359873A - Method for processing and recycling MBR-NF (membrane bioreactor-nanofiltration) antibiotic wastewater based on thick water backflow - Google Patents
Method for processing and recycling MBR-NF (membrane bioreactor-nanofiltration) antibiotic wastewater based on thick water backflow Download PDFInfo
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- CN103359873A CN103359873A CN2012100842871A CN201210084287A CN103359873A CN 103359873 A CN103359873 A CN 103359873A CN 2012100842871 A CN2012100842871 A CN 2012100842871A CN 201210084287 A CN201210084287 A CN 201210084287A CN 103359873 A CN103359873 A CN 103359873A
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Abstract
The invention discloses a method for processing and recycling antibiotic wastewater. According to the method, the antibiotic wastewater aerobic section effluent containing high concentration ammonia nitrogen, COD (chemical oxygen demand) and inorganic salt is taken as the processing object, the technologies of MBR and NF are combined, the NF thick water flows back to the MBR through the biodegradation of MBR and efficient interception and other effects of NF to organic matters and inorganic multivalent ions and the like, the water recovery rate of the MBR-NF is improved, and the antibiotic wastewater is processed and recycled. The method has simple technological processes, can be used for recycling the antibiotic wastewater (which is difficult to process) at low cost, and is applicable to the antibiotic wastewater capable of being subjected to aerobic biological treatment after pretreatment.
Description
Technical field
The present invention relates to a kind of MBR-NF antibiotic waste water treatment and reuse method based on concentrate recirculation.
Background technology
2009, China's microbiotic output and export volume occupied the first in the world, and wherein microbiotic output is approximately 14.7 ten thousand tons.At present domestic existing 300 many enterprises are engaged in antibiotic production, nearly 70 of product categories.Yet, in the preparation process of microbiotic related products, can produce a large amount of antibiotic waste waters, comprise waste liquor and flushing waste water etc. one ton of microbiotic of every production just can produce 150～850m
3Waste liquor adds flushing waste water, more than one hundred million tons of antibiotic waste waters of the annual generation of microbiotic enterprise.
The antibiotic waste water complicated component mainly contains insoluble antibiotic fermented liquid, fermentation produce in the extraction liquid, water of fermentation remaining matrix and nutrition, solvent leaching process microbial bacteria filament etc.Waste water quality feature main manifestations is: high COD, high salinity, bio-toxicity are large, high chroma and turbidity etc.Because residual microbiotic and high salinity can suppress microbic activity in the waste water, directly adopt aerobe method to process the antibiotic waste water effect relatively poor.High for the antibiotic waste water organic content, be difficult to the characteristics directly processed by aerobic microbiological, the method for processing antibiotic waste water both at home and abroad mainly contains physico-chemical process and the combination process take biological process as core.
The physico-chemical process of having reported has physisorphtion (slag, charcoal, gac etc.), advanced oxidation processes (Fenton oxidation, O
3Oxidation, Q
3/ H
2O
2Oxidation, TiO
2Photochemical catalysis etc.), electrolytic process (the little electrolysis of Fe/C, the little electrolysis of iron filings etc.) and membrane separation process (NF/RO).Use physico-chemical process to process antibiotic waste water, often need to add a large amount of chemical reagent, cause running cost high, be difficult to realize the mass-producing application.Therefore physico-chemical process is applied in the pretreatment stage of antibiotic waste water mostly.
Biological process has the characteristics such as the low and environmental friendliness of running cost, and it occupies dominant position in the technology of processing antibiotic waste water.The biological method of processing antibiotic waste water mainly contains anaerobic process (upflow anaerobic sludge blanket process method, baffling type anaerobic reactor method and anaerobic composite bed method etc.) and aerobic method (contact oxidation method, sequencing batch active sludge, biomembrance process and membrane bioreactor etc.).In biological process, anaerobic process is mainly used in the pre-treatment of antibiotic waste water, and the organism in the further degrading waste water of aerobic method satisfies the qualified discharge requirement.
On the whole, present treatment process only is that antibiotic waste water is processed to satisfying state specified standards qualified discharge, its another water source as domestic water or process water is not treated.Along with China's microbiotic output increases year by year, it is also increasingly huge that antibiotic waste water produces quantity, so the regeneration of antibiotic waste water has important practical significance to the Sustainable development that realizes enterprise, the energy-saving and emission-reduction policy of response country.
Summary of the invention
The object of the present invention is to provide a kind of antibiotic waste water treatment process of economical and efficient.
Antibiotic waste water treatment process provided by the present invention comprises the steps:
1) pretreated antibiotic waste water is pumped into membrane bioreactor and carry out organic degraded, the separatory membrane separation of the waste water after the degraded in membrane bioreactor obtains the membrane bioreactor water outlet, and described water outlet is extracted out by vacuum primingpump;
2) described membrane bioreactor water outlet is pumped into nanofiltration device by high-pressure pump behind cartridge filter, but the fresh water direct reuse of production, the concentrate recirculation of producing in the nanofiltration device is to step 1) described in the membrane bioreactor.
Wherein, the aeration rate of membrane bioreactor step 1) is 3.6～6.0m
3/ (m
2H), the concentration of active sludge is 4000～10000mg/L in the described membrane bioreactor, and sludge loading is 0.15～0.22Kg COD/ (KgMLVSSd
-1), membrane flux is 6～20L/ (m
2H), transmembrane pressure is controlled in the 40KPa, the temperature of described membrane bioreactor is controlled at 4 ℃～30 ℃, dissolved oxygen is controlled at more than the 2mg/L, the pH value of mixed solution (the mixed liquid of waste water and mud) maintains between 6～8 in the described membrane bioreactor, and the hydraulic detention time in the described membrane bioreactor is 24～48h.Used separatory membrane specifically can be flat sheet membrane in the membrane bioreactor.
Step 1) be used for extracting out the vacuum primingpump employing gap operation scheme of membrane bioreactor water outlet in, actual conditions is: operation 5～10min, standby 2min.
Step 2) pump into the pH value of water in the nanofiltration device (being the nanofiltration water inlet) between 5.0～7.0, its pH is that the hydrochloric acid of 1mol/L is regulated by volume pump implantation concentration in the nanofiltration inlet channel.The pressure that pumps into the water in the nanofiltration device is 0.05～0.15MPa, flooding velocity 1～3m
3/ (m
2H), the permeation flux of nanofiltration membrane is 0.02～0.07m in the nanofiltration device
3/ (m
2H), the volume enrichment factor of nanofiltration water inlet is 3～4.
Step 2) the dense water that nanofiltration device is produced in is back in the membrane bioreactor according to a certain percentage to improve the water rate of recovery of whole system.Usually the backflow ratio is 50%～80% of concentrated stream amount.
Pretreated antibiotic waste water of the present invention refers to carry out after pretreatment the antibiotic waste water that aerobe is processed, and namely contains ammonia nitrogen in high density (300～450mgL
-1), COD (1000～2000mgL
-1) and inorganic salt (7～12mScm
-1) the antibiotic waste water oxygen section water outlet of holding concurrently.
The inventive method is to contain ammonia nitrogen in high density, the antibiotic waste water of COD and inorganic salt is held concurrently the water outlet of oxygen section for processing object, adopt membrane bioreactor (MBR) and nanofiltration (NF) combination process, utilize the biological degradation of MBR and NF to effects such as efficiently holding back of organism and inorganic polyvalent ion, the nanofiltration water outlet can be satisfied the water requirement of production of antibiotics enterprise, dense water with nanofiltration device is back to front stage membrane bioreactor by a certain percentage simultaneously, so both can reduce the dense water generates amount of nanofiltration, can improve the rate of recovery of antibiotic waste water again, thereby realize the treatment and reuse of antibiotic waste water.The method utilizes two membrane techniquies to process antibiotic waste water, both can reduce the fresh water amount that microbiotic enterprise needs, and has solved simultaneously the problem of environmental pollution that the antibiotic waste water discharging produces.
Compare with existing antibiotic waste water treatment process, method of the present invention has following advantage:
(1) reduces the hydraulic detention time of MBR water inlet, thereby reduced first cost of investment and the running cost of antibiotic waste water;
(2) use nanofiltration membrane as the advanced treatment unit of MBR water outlet, not only can under low operating pressure, efficiently hold back organism and polyvalent ion in the water, but simultaneously nanofiltration water outlet direct reuse has been saved the tap water consumption of microbiotic pharmaceutical factory.
Description of drawings
Fig. 1 is the process flow sheet that the present invention processes waste water.
Embodiment
Below by specific embodiment method of the present invention is described, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Embodiment 1:
The hold concurrently water quality of oxygen section water outlet of certain microbiotic Sewage Treatment at Pharmaceutical Factory station sees Table 1, and its NF effluent quality after the MBR-NF associated plant is processed can be satisfied reuse requirement (its technical process is shown in 1).
Concrete steps are as follows: 1) pump into membrane bioreactor (MBR) through pretreated antibiotic waste water, membrane bioreactor adopts the SINAP-10 flat sheet membrane, and material is PVDF (polyvinylidene difluoride (PVDF)), shares 4, and membrane area amounts to 0.4m
2Hydraulic detention time in membrane bioreactor is 36h, and membrane flux is 10L/ (m
2H), aeration rate is 3.6m
3/ (m
2H), transmembrane pressure is controlled in the 40KPa, and temperature is controlled at 18～25 ℃, and dissolved oxygen is controlled at more than the 2mg/L, and the pH of mixed value maintains between 6～8, and activated sludge concentration is 6500mg/L, and sludge loading is 0.19Kg COD/ (KgMLVSSd
-1); By biological treatment, remove the biodegradable organic in the waste water, create conditions for follow-up nanofiltration device simultaneously, the penetrating fluid behind the membrane sepn (being water outlet) is extracted out from the separatory membrane discontinuous by vacuum primingpump, wherein, the operation scheme of vacuum primingpump is 6min (operation)/2min standby;
2) the membrane bioreactor water outlet is pumped into nanofiltration device (NF) by topping-up pump behind cartridge filter; Used nanofiltration membrane is rolling, model GE-DK1812C-34D, and material is modified Teflon; The water inlet pH value of nanofiltration device is between 5.0～7.0, and the regulative mode of pH is for being the hydrochloric acid of 1mol/L by volume pump implantation concentration in the nanofiltration inlet channel; Make intake pressure be increased to 0.1MPa by topping-up pump, flooding velocity 1.5m
3/ (m
2H), water inlet volume enrichment factor is 4, and the nanofiltration membrane permeation flux is 56L/ (m
2H); But nanofiltration water outlet direct reuse; 3) the 60% nanofiltration concentrate recirculation that nanofiltration device is produced so not only can improve the waste water reclamation rate of whole system to membrane bioreactor, also can reduce the dense aquatic products amount of nanofiltration.
Table 1 Inlet and outlet water water quality and fermentation water water quality standard
Claims (7)
1. an antibiotic waste water treatment process comprises the steps:
1) pretreated antibiotic waste water is pumped into membrane bioreactor and carry out organic degraded, the separatory membrane separation of the waste water after the degraded in membrane bioreactor obtains percolate, i.e. membrane bioreactor water outlet, and described water outlet is extracted out by vacuum primingpump;
2) described membrane bioreactor water outlet is pumped into nanofiltration device by high-pressure pump behind cartridge filter, but the fresh water direct reuse of production, the concentrate recirculation of producing in the nanofiltration device is to step 1) described in the membrane bioreactor.
2. method according to claim 1 is characterized in that: step 1) described in the aeration rate of membrane bioreactor be 3.6～6.0m
3/ (m
2H), the concentration of active sludge is 4000～10000mg/L in the described membrane bioreactor, and sludge loading is 0.15～0.22Kg COD/ (KgMLVSSd
-1), membrane flux is 6～20L/ (m
2H), transmembrane pressure is controlled in the 40KPa, the temperature of described membrane bioreactor is controlled at 4 ℃～30 ℃, dissolved oxygen is controlled at more than the 2mg/L, the pH value of the mixed solution of waste water and mud maintains between 6～8 in the described membrane bioreactor, and the hydraulic detention time in the described membrane bioreactor is 24～48h.
3. method according to claim 1 and 2 is characterized in that: step 1) described in separatory membrane in the membrane bioreactor be flat sheet membrane.
4. method according to claim 1 and 2 is characterized in that: step 1) described vacuum primingpump employing gap operation scheme; Actual conditions is: operation 5～10min, standby 2min.
5. each described method is characterized in that: step 2 according to claim 1-4) in pump into the pH value of intaking in the nanofiltration device between 5.0～7.0, the pressure of described water inlet is 0.05～0.15MPa, the flow 1～3m of described water inlet
3/ (m
2H), the volume enrichment factor of water inlet is 3～4, and the permeation flux of nanofiltration membrane is 0.02～0.07m in the described nanofiltration device
3/ (m
2H).
6. each described method is characterized in that: step 2 according to claim 1-5) described in concentrate recirculation to the ratio of membrane bioreactor be 50%～80% of concentrated stream amount.
7. each described method is characterized in that: step 1 according to claim 1-6) described in pretreated antibiotic waste water refer to carry out after pretreatment the antibiotic waste water that aerobe is processed.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174639A (en) * | 2015-10-08 | 2015-12-23 | 罗秋斌 | Method for removing antibiotics from turtle aquaculture wastewater |
| CN105399205A (en) * | 2015-12-15 | 2016-03-16 | 华东师范大学 | Device and method for landfill in-situ removal of antibiotics and antibiotic resistance genes in leachate |
| CN106434467A (en) * | 2016-10-13 | 2017-02-22 | 南京大学 | High-efficiency antibiotic wastewater treatment agent and preparation method and application thereof |
| CN106477810A (en) * | 2016-10-31 | 2017-03-08 | 上海明诺环境科技有限公司 | A kind of combined modified NF membrane of MBR realizes the processing method of high salt organic waste water reuse |
| CN105753247B (en) * | 2016-03-04 | 2019-08-06 | 石家庄经济学院 | A kind of penicillin composite waste low-temperature treatment plant and its method |
| CN111871236A (en) * | 2020-07-27 | 2020-11-03 | 四川春语环保科技有限公司 | Double-membrane combined membrane separation and biological activity method wastewater treatment system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174639A (en) * | 2015-10-08 | 2015-12-23 | 罗秋斌 | Method for removing antibiotics from turtle aquaculture wastewater |
| CN105174639B (en) * | 2015-10-08 | 2017-07-21 | 湖州师范学院 | The method for removing antibiotic in Terrapin raising waste water |
| CN105399205A (en) * | 2015-12-15 | 2016-03-16 | 华东师范大学 | Device and method for landfill in-situ removal of antibiotics and antibiotic resistance genes in leachate |
| CN105753247B (en) * | 2016-03-04 | 2019-08-06 | 石家庄经济学院 | A kind of penicillin composite waste low-temperature treatment plant and its method |
| CN106434467A (en) * | 2016-10-13 | 2017-02-22 | 南京大学 | High-efficiency antibiotic wastewater treatment agent and preparation method and application thereof |
| CN106434467B (en) * | 2016-10-13 | 2019-08-06 | 南京大学 | A kind of penicillin wastewater efficient process microbial inoculum and its preparation method and application |
| CN106477810A (en) * | 2016-10-31 | 2017-03-08 | 上海明诺环境科技有限公司 | A kind of combined modified NF membrane of MBR realizes the processing method of high salt organic waste water reuse |
| CN111871236A (en) * | 2020-07-27 | 2020-11-03 | 四川春语环保科技有限公司 | Double-membrane combined membrane separation and biological activity method wastewater treatment system |
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Application publication date: 20131023 |