CN109879538A - A kind of high total nitrogen, high salinity antibiotics pharmacy waste water processing method - Google Patents
A kind of high total nitrogen, high salinity antibiotics pharmacy waste water processing method Download PDFInfo
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- CN109879538A CN109879538A CN201910202031.8A CN201910202031A CN109879538A CN 109879538 A CN109879538 A CN 109879538A CN 201910202031 A CN201910202031 A CN 201910202031A CN 109879538 A CN109879538 A CN 109879538A
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- waste water
- total nitrogen
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Abstract
The invention discloses the processing methods of a kind of high total nitrogen, the antibiotics pharmacy waste water of high salinity, comprising the following steps: antibiotics pharmacy waste water is passed through in coagulation floatation, the dosing coagulant into coagulation floatation, carries out coagulation air-float pretreatment；It is passed through in the hydrolysis acidification pool of built-in filler again, acidification is hydrolyzed；Then, it is passed through in intermittent anoxic/aerobic MBR reaction tank, carries out advanced treating, water outlet direct emission that treated.The present invention is directed to high total nitrogen, the antibiotics production waste water of high salinity uses coagulation air-float+hydrolysis acidification+intermittent anoxic/aerobic MBR treatment process, the efficient denitrification of total nitrogen and ammonia nitrogen can not only be realized under hypersaline environment, and the aniline in antibiotics pharmacy waste water can be efficiently removed, guarantee that stable effluent quality is up to standard.
Description
Technical field
The present invention relates to the antibiotics pharmacy of technical field of waste water processing more particularly to a kind of high total nitrogen, high salinity
The processing method of waste water.
Background technique
It is right both at home and abroad at present with the increasingly exacerbation of water pollution problems in recent years to become increasingly conspicuous with shortage of water resources problem
The discharge standard of total nitrogen is increasingly stringenter in sewage treatment.Ammonium hydroxide and n,N-Dimethylformamide (DMF) are pharmaceutical industry production
The important sources of important supplementary material and Determination of Total Nitrogen in Waste Water in the process.Meanwhile pharmacy waste water has pollutant component more multiple
The features such as miscellaneous, toxicity is big, and salt content is high, and biodegradability is poor, the attention by each field of environmental protection.
Toxic substance and higher salt content will lead to inhibition microbial activity in pharmacy waste water, and especially nitrification is thin
Bacterium activity, influences denitrification effect.The group technologies such as traditional A/O, AA/O are difficult to realize efficient denitrogenation.It is therefore proposed that a kind of
It saves floor occupying area, reasonable, efficient pharmaceutical wastewater treatment process is extremely urgent problem.
Application publication number is that the application for a patent for invention of CN107032495A discloses a kind of high COD high salinity pharmacy waste water
Biological treatment group technology, the technique successively by conditioning tank, anaerobic fixed film reactor, anoxic/aerobic tank and film biological tank processing after,
Water quality reaching standard.The group technology, can be useless compared with pharmacy of effectively degrading under high salinity environment for high COD high salinity pharmacy waste water
COD, ammonia nitrogen and total nitrogen in water, the removal rate of COD can achieve 90% or more, and the removal rate of ammonia nitrogen reaches 85% or more, always
The removal rate of nitrogen reaches 70% or more.
Application publication number is that the application for a patent for invention of CN105776740A discloses a kind of vitamins Pharmaceutical Fermentation Wastewater
The processing method and equipment of qualified discharge, technique include: that waste water passes sequentially through pretreatment unit, using IC reactor as core
Anaerobic Treatment unit, second level short-cut nitrification and denitrification and rear-mounted denitrification group technology (hereinafter referred to as D/N/D unit) and to urge
Change the advanced treatment unit etc. that ozone oxidation is core and gradually remove organic matter, ammonia nitrogen, total nitrogen, suspended matter, coloration etc., reaches row
Put standard.
However, be directed to high total nitrogen, high salinity pharmacy waste water for, especially antibiotics pharmacy waste water is above-mentioned
The treatment effect of processing method or technique is still to be improved.
Summary of the invention
It is an object of the invention to overcome the shortcomings of existing pharmaceutical wastewater treatment process, a kind of high total nitrogen, Gao Han are provided
The processing method of the antibiotics production waste water of salt amount, the processing method are particularly suitable for TN concentration and are 400~1000mg/L, contain
The processing for the antibiotics pharmacy waste water that salt amount is 1.0~1.5% can not only significantly improve the denitrogenation effect of total nitrogen and ammonia nitrogen
Fruit, additionally it is possible to efficiently remove aniline, guarantee that stable effluent quality is up to standard.
Specific technical solution is as follows:
A kind of high total nitrogen, high salinity antibiotics production waste water processing method, comprising the following steps:
(1) antibiotics pharmacy waste water is passed through in coagulation floatation, the dosing coagulant into coagulation floatation is mixed
Solidifying air bearing pretreatment；
(2) water outlet of step (1) is passed through in the hydrolysis acidification pool of built-in filler, acidification is hydrolyzed；
(3) water outlet of step (2) is passed through in intermittent anoxic/aerobic MBR reaction tank, advanced treating is carried out, after processing
Water outlet direct emission；
In the intermittent anoxic/aerobic MBR reaction tank sludge concentration be 3000~8000mg/L, pH 6.5~8.5 it
Between；Using anoxic and aerobic alternate run mode, in anoxic phases, runing time is 60~120min, controls antibiotics system
Medicine gives up content of oxygen dissolved in water < 0.5mg/L；In aerobic stage, runing time is 90~180min, controls antibiotics pharmacy
Useless content of oxygen dissolved in water is 2~4mg/L.
Antibiotics pharmacy waste water of the present invention refers to for producing the antibiotic such as Levofloxacin, Moxifloxacin when institute
The waste water of generation, the waste water have the characteristics that high total nitrogen, high salinity, and COD concentration is 3500~10000mg/L, total nitrogen concentration
For 400~1000mg/L, TDS is 8000~12000mg/L, and ammonia nitrogen concentration is 50~150mg/L, concentration of aniline is 20~
100mg/L, salt content are 1.2~1.4%.
The present invention is found by experiment that: using coagulation air-float+hydrolysis acidification+intermittent anoxic/aerobic MBR treatment process
It can not only realize the efficient removal of total nitrogen and ammonia nitrogen, and can efficiently remove the aniline in antibiotics pharmacy waste water, only
Antibiotics production waste water high-efficiency processing can be realized using three steps, the processing cost not only reduced also has higher removal effect
Rate.
The handling principle of above-mentioned processing method is:
Step (1) removes suspended matter and oily substance in waste water by coagulation floatation, and one is added into coagulation floatation
Quantitative coagulant, making colloid pollution object in waste water and fine suspension cohesion is wadding body, under the action of fine gas bubbles on
It is floating, dross is formed, after the water surface convenient for removal；Pretreated water is discharged from the water outlet of coagulation air-float bottom of pond portion.
In step (2), hydrolysis acidification pool water (flow) direction is from the bottom to top, for hardly degraded organic substance in Decomposition Wastewater.Water
Solution acidification pool can be effectively reduced COD in waste water, improve wastewater biodegradability, reduce inhibition of the noxious material to nitrobacteria.
In step (3), it is equipped with membrane module, aerator and agitating device in intermittent anoxic/aerobic MBR reaction tank, exposes
Device of air is set to the bottom of reaction tank, by controlling aerator, realizes the alternate run of anoxic/aerobic；It is also set in reaction tank
There are online pH meter, DO instrument and liquidometer.The reaction tank is for COD and total nitrogen in degrading waste water；Due to the nitrobacteria generation cycle
It is long, and the influence vulnerable to salinity, using the interval anoxic/aerobic MBR reaction tank, anoxic/aerobic alternate run can promote
The growth of nitrobacteria and denitrifying bacteria in into reaction tank；It is discharged, can effectively be maintained in reaction tank by membrane module
Nitrobacteria and denitrifying bacteria concentration.
Preferably, the coagulant is aluminium polychloride in step (1), the dosage of the aluminium polychloride is 10
~60mg/L.
Preferably, it is 7.0~8.0 that coagulation vapour, which floats the pH in pond, in step (1), water temperature is 20~30 DEG C, hydraulic retention
Time is 0.5~2h.
Built-in composite filling in hydrolysis acidification pool forms biomembrane in filler surface, improves strain amount in reactor, simultaneously
Be conducive to the strain that enrichment isolation goes out salt tolerant, can decompose hardly degraded organic substance.Preferably, in step (2), the hydrolysis acid
Change and be equipped with composite filling in pond, hydrolysis acidification pool is divided into upper and lower two layers, and upper layer is filled with the polypropylene that filling rate is 50~70%
Polyhedron empty ball filler, lower layer are filled with the polyethylene 3 D elastic filler that filling rate is 30~50%.
Preferably, the pH in hydrolysis acidification pool is 6.5~7.5 in step (2), water temperature is 18~25 DEG C, hydraulic retention
Time is 8~72h.
Preferably, hydraulic detention time is 10~72h in intermittent anoxic/aerobic MBR reaction tank in step (3).
Preferably, in step (3), in intermittent anoxic/aerobic MBR reaction tank in anoxic and aerobic alternate run mode
The number of alternate run is 6~20 times.
Preferably, the membrane module that the intermittent anoxic/aerobic MBR reaction tank uses is hollow for PVDF in step (3)
Fiber film component, water flux are 10~18L/ (m2·h)。
Compared with prior art, the invention has the following advantages:
(1) present invention is directed to high total nitrogen, the antibiotics production waste water of high salinity uses coagulation air-float+hydrolysis acidification
The treatment process of+intermittent anoxic/aerobic MBR, can not only realize the efficient denitrification of total nitrogen and ammonia nitrogen under hypersaline environment, and
And the aniline in antibiotics pharmacy waste water can be efficiently removed, guarantee that stable effluent quality is up to standard.
(2) present invention process process is simple, and operation control is easy, energy saving.
Specific embodiment
The invention will be further described combined with specific embodiments below, and what is be exemplified below is only specific implementation of the invention
Example, but protection scope of the present invention is not limited only to this.
Embodiment 1
Handled waste water is the useless of the pharmaceutical factory of certain production antibiotic such as Levofloxacin and Moxifloxacin in the present embodiment
Water, the Determination of Total Nitrogen in Waste Water are mainly derived from n,N-Dimethylformamide (abbreviation DMF), COD 7000mg/L, TN 800mg/L,
Ammonia nitrogen is 100mg/L, and aniline 37mg/L, dissolvability solid amount (abbreviation TDS) is 10000mg/L, and waste water salt content is
1.4%.
Specific processing step is as follows:
(1) waste water is passed through in coagulation floatation, the dosing coagulant into coagulation floatation, carries out coagulation air-float and locates in advance
Reason；
Wherein, pH is 7.5 in coagulation floatation, and water temperature is 25 DEG C, and hydraulic detention time 2h, coagulant is polyaluminium
Aluminium, adding concentration is 30mg/L；
(2) water outlet of step (1) is passed through hydrolysis acidification pool, acidification is hydrolyzed；
Wherein, hydrolysis acidification pool is divided into upper and lower two layers, and upper layer is filled with the polypropylene polyhedron empty ball that filling rate is 50%
Filler, lower layer are filled with the polyethylene 3 D elastic filler that filling rate is 50%, and pH is 7.0 in pond, and water temperature is 20 DEG C, and waterpower is stopped
Staying the time is 48h,；
(3) water outlet of step (2) is passed through in intermittent anoxic/aerobic MBR reaction tank, advanced treating is carried out, after processing
Water outlet direct emission；
Wherein, hydraulic detention time is that for 24 hours, hypoxic exposure 90min is aerobic in intermittent anoxic/aerobic MBR reaction tank
Time is 120min, and anoxic/aerobic cycle-index is 6 times；The dissolved oxygen of aerobic stage is 2-4mg/L, the dissolution of anoxic phases
Oxygen is 0.1-0.3mg/L, and sludge concentration is 5000mg/L in reactor；Membrane material used is pvdf membrane, membrane flux 15L/
m2·h。
As a result:
In water outlet, COD≤200mg/L, ammonia nitrogen≤5mg/L, TN≤40mg/L, aniline≤1mg/L, stable effluent quality.
Comparative example 1
This comparative example handles and the identical waste water of embodiment 1, except step (3) are different from embodiment 1 in processing step
Outside, remaining step is identical with embodiment 1.
Step (3): being first passed through anoxic pond for the water outlet of step (2), then is passed through aerobic MBR reaction tank, successively carries out depth
Processing, water outlet direct emission that treated；
Wherein, dissolved oxygen is 0.1-0.3mg/L, hydraulic detention time 9h, sludge concentration 5000mg/L in anoxic pond；
Dissolved oxygen is 2-4mg/L in aerobic MBR reaction tank, and hydraulic detention time 14h, sludge concentration 5000mg/L, aerobic MBR are anti-
The membrane material for answering pond inner membrane member to use is pvdf membrane, membrane flux 15L/m2·h.(above-mentioned parameter value is the comparative example step
(3) the optimal parameter value for the treatment of effect)
As a result:
In water outlet, COD≤200~500mg/L, ammonia nitrogen≤10mg/L, TN be 500~700mg/L, 5~10mg/L of aniline,
Stable effluent quality.
Comparative example 2
This comparative example handles and the identical waste water of embodiment 1, except step (3) are different from embodiment 1 in processing step
Outside, remaining step is identical with embodiment 1.
Step (3): the water outlet of step (2) is passed through aerobic MBR reaction tank, carries out advanced treating, treated, and water outlet is straight
Run in and puts；
Wherein, dissolved oxygen is 2-4mg/L in aerobic MBR reaction tank, and hydraulic detention time is for 24 hours that sludge concentration is
5000mg/L, the membrane material that aerobic MBR reaction tank inner membrane member uses is pvdf membrane, membrane flux 15L/m2·h.(above-mentioned ginseng
Numerical value is the optimal parameter value of comparative example step (3) treatment effect)
As a result:
In water outlet, COD be 1500~2000mg/L, ammonia nitrogen≤10mg/L, TN700~800mg/L, aniline be 10~
15mg/L, stable effluent quality.
Comparative example 3~4
The processing of comparative example 3~4 and the identical waste water of embodiment 1, the filler used except step (2) in processing step for
Single filler, i.e., only with polypropylene polyhedron empty ball filler (comparative example 3) and only with the (comparison of polyethylene 3 D elastic filler
Example 4).
Test result is as follows:
Influence (%) of the different fillers of table 1 to pollutants removal rate in hydrolysis acidification pool
As shown in Table 1, it is handled using composite filling, the COD for entering MBR sections can be effectively prevent excessively high, avoided different
It supports type bacterium and nitrobacteria generates competition, while guaranteeing carbon source required for denitrification.Meanwhile using composite filling to can
DMF is effectively decomposed, reduces DMF to the inhibiting effect of later period nitrobacteria.Single type filler can be compared using composite filling,
Institute's enriched biological amount is more, and is capable of providing microbe species more abundant, improves reactor capacity of resisting impact load.
Influence (%) of the different fillers of table 2 to pollutant entirety removal effect
As shown in Table 2, it is handled using composite filling, is capable of the biodegradability of significantly more efficient promotion organic matter, it is small
Molecular organic can be made full use of in MBR anoxic phases by denitrifying bacteria, while realizing high efficiency denitrogenation, make COD
Obtain fully degraded.
Comparative example 5
This comparative example handles and the identical waste water of embodiment 1, except step (3) are different from embodiment 1 in processing step
Outside, remaining step is identical with embodiment 1.
Step (3): the water outlet of step (2) is passed through in intermittent anoxic/aerobic MBR reaction tank, carries out advanced treating, place
Water outlet direct emission after reason；
Wherein, hydraulic detention time is that for 24 hours, hypoxic exposure 30min is aerobic in intermittent anoxic/aerobic MBR reaction tank
Time is 40min, and anoxic/aerobic cycle-index is 6 times；The dissolved oxygen of aerobic stage is 2-4mg/L, the dissolved oxygen of anoxic phases
For 0.1-0.3mg/L, sludge concentration is 5000mg/L in reactor；Membrane material used is pvdf membrane, membrane flux 15L/m2·
h。
As a result:
It is discharged COD≤200mg/L, ammonia nitrogen is 5~10mg/L, and TN is 100~150mg/L, and aniline is 5~10mg/L,
Middle COD treatment effect is identical as 1 treatment effect of embodiment, and the removal effect of ammonia nitrogen, total nitrogen and aniline is poor compared with embodiment 1.
Comparative example 6
This comparative example handles and the identical waste water of embodiment 1, except step (3) are different from embodiment 1 in processing step
Outside, remaining step is identical with embodiment 1.
Step (3): the water outlet of step (2) is passed through in intermittent anoxic/aerobic MBR reaction tank, carries out advanced treating, place
Water outlet direct emission after reason；
Wherein, hydraulic detention time is for 24 hours in intermittent anoxic/aerobic MBR reaction tank, and hypoxic exposure 150min is good
The oxygen time is 200min, and anoxic/aerobic cycle-index is 6 times；The dissolved oxygen of aerobic stage be 2-4mg/L, anoxic phases it is molten
Solution oxygen is 0.1-0.3mg/L, and sludge concentration is 5000mg/L in reactor；Membrane material used is pvdf membrane, membrane flux 15L/
m2·h.Aniline
As a result:
It is discharged COD≤200mg/L, ammonia nitrogen is≤5mg/L, and TN is 100~170mg/L, and aniline is 3~5mg/L, wherein
COD, NH_3-N treating effect are identical as 1 treatment effect of embodiment, and the removal effect of total nitrogen and aniline is poor compared with embodiment 1.
Claims (8)
1. a kind of processing method of the antibiotics pharmacy waste water of high total nitrogen, high salinity, which is characterized in that including following step
It is rapid:
(1) antibiotics pharmacy waste water is passed through in coagulation floatation, the dosing coagulant into coagulation floatation, carries out coagulation gas
Floating pretreatment；
(2) water outlet of step (1) is passed through in the hydrolysis acidification pool of built-in filler, acidification is hydrolyzed；
(3) water outlet of step (2) is passed through in intermittent anoxic/aerobic MBR reaction tank, carries out advanced treating, treated goes out
Water direct emission；
Sludge concentration is 3000~8000mg/L in the intermittent anoxic/aerobic MBR reaction tank, and pH is between 6.5~8.5；
Using anoxic and aerobic alternate run mode, in anoxic phases, runing time is 60~120min, and control antibiotics pharmacy is useless
Content of oxygen dissolved in water < 0.5mg/L；In aerobic stage, runing time is 90~180min, controls antibiotics pharmacy waste water
Middle dissolved oxygen content is 2~4mg/L.
2. the processing method of the antibiotics pharmacy waste water of high total nitrogen as described in claim 1, high salinity, feature exist
In in step (1), the coagulant is aluminium polychloride, and the dosage of the aluminium polychloride is 10~60mg/L.
3. the processing method of the antibiotics pharmacy waste water of high total nitrogen as claimed in claim 2, high salinity, feature exist
In in step (1), it is 7.0~8.0 that coagulation vapour, which floats the pH in pond, and water temperature is 20~30 DEG C, and hydraulic detention time is 0.5~2h.
4. the processing method of the antibiotics pharmacy waste water of high total nitrogen as described in claim 1, high salinity, feature exist
In in step (2), the hydrolysis acidification pool is divided into upper and lower two layers, and it is more that upper layer is filled with the polypropylene that filling rate is 50~70%
Face hollow sphere filler, lower layer are filled with the polyethylene 3 D elastic filler that filling rate is 30~50%.
5. the processing method of the antibiotics pharmacy waste water of high total nitrogen as claimed in claim 4, high salinity, feature exist
In in step (2), the pH in hydrolysis acidification pool is 6.5~7.5, and water temperature is 18~25 DEG C, and hydraulic detention time is 8~72h.
6. the processing method of the antibiotics pharmacy waste water of high total nitrogen as described in claim 1, high salinity, feature exist
In in step (3), hydraulic detention time is 10~72h in intermittent anoxic/aerobic MBR reaction tank.
7. the processing method of the antibiotics pharmacy waste water of high total nitrogen as described in claim 1, high salinity, feature exist
In, in step (3), in intermittent anoxic/aerobic MBR reaction tank in anoxic and aerobic alternate run mode alternate run number
It is 6~20 times.
8. the processing method of the antibiotics pharmacy waste water of high total nitrogen as described in claim 1, high salinity, feature exist
In in step (3), the membrane module that the intermittent anoxic/aerobic MBR reaction tank uses is PVDF hollow fiber film assembly, water
Flux is 10~18L/ (m2·h)。
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| CN113213715A (en) * | 2021-06-16 | 2021-08-06 | 中国科学院生态环境研究中心 | Combined treatment method for fermentation antibiotic production wastewater |
| CN113480107A (en) * | 2021-08-03 | 2021-10-08 | 苏州青和环境科技有限公司 | Zero-emission process for treating high-salinity high-organic wastewater based on wet catalytic oxidation technology |
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Application publication date: 20190614 |