CN103663875B - Method for improving denitrification rate of acrylonitrile waste water - Google Patents
Method for improving denitrification rate of acrylonitrile waste water Download PDFInfo
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Abstract
The method relates to a method for improving the denitrification rate of acrylonitrile waste water, and mainly solves the problems that the removal efficiency is relatively low and the effluent COD (Chemical Oxygen Demand) or TN (Total Nitrogen) cannot reach the standard during the acrylonitrile waste water treatment in the prior art. The method for improving the denitrification rate of the acrylonitrile waste water adopted by the invention comprises the following steps: (1) the acrylonitrile waste water enters a partial nitrification denitrification tank; (2) substances flowing out from the partial nitrification denitrification tank enters an oxygen-poor tank; (3) substances flowing out from the oxygen-poor tank enters a primary settling pond, substances flowing out from the upper part of the oxygen-poor tank enters an aerobiotic tank, and at least one part of bottom sludge of the oxygen-poor tank is discharged; (4) upper part substances flowing out from the aerobiotic tank enters a secondary settling pond, upper clean liquid of the aerobiotic tank enters an advanced oxidation tank, and the bottom sludge of the aerobiotic tank is discharged; (5) substances flowing out from the advanced oxidation tank enters a biological aerated filter to contact with the porous filter material and air, the waste water up-to-standard release technical scheme solve the problem in the prior art well, and the method can be applied to the industrial treatment of the acrylonitrile waste water.
Description
Technical field
The present invention relates to a kind of method improving denitrification rate of acrylonitrile waste water.
Background technology
The key character of acrylic nitrile waste water is high chemical oxygen demand (hereinafter referred to as COD), high total nitrogen (hereinafter referred to as TN), and containing the toxic ingredient such as vinyl cyanide and prussiate, intractability is larger.
Because the sewage drainage standard of China only has NH to trade effluent
3-N Con trolling index, does not all list the Con trolling index of TN in always.So, select often only to consider the nitrated of ammonia nitrogen during acrylic nitrile waste water treatment process, or, even if selected the treatment process with denitrification functions, but in the value of design variable, also think little of the Denitrification rate (i.e. nitric efficiency) of nitric nitrogen, during actual motion, all do not examine water outlet TN.As: adopt Wastewater Treated by Activated Sludge Process after Shanghai acrylonitrile installation water reuse service water is diluted to COD < 1000mg/L, water outlet COD is 300 ~ 500mg/L, ammonia nitrogen < 150mg/L; Anqing acrylonitrile installation waste water and Nitrilon waste water are mixed to after COD is about 700mg/L and adopt the process of A/O method, water outlet COD < 170mg/L; It is 650-800mg/L, TN is after 60-70mg/L that grand celebration acrylonitrile installation waste water and Nitrilon waste water are mixed to COD, adopts pure oxygen aeration+contact oxidation method process, water outlet COD and NH
3-N is substantially up to standard; After Jilin acrylonitrile installation water reuse low concentration wastewater is diluted to COD < 1800mg/L, adopt the process of SBR method, water outlet COD is 800 ~ 900mg/L, NH
3-N < 300mg/L; Biological multiplication method process is adopted, water outlet COD < 300mg/L, NH after transformation
3-N < 50mg/L.Therefore (i) acrylic nitrile waste water intractability is very large, although carried out diluting (2 ~ 5 times) to acrylic nitrile waste water, COD and NH of water outlet
3-N is still difficult to the requirement reaching " integrated wastewater discharge standard " GB8978-1996 primary standard, can not arrange directly outward.(ii) water outlet TN index all do not examined by existing acrylic nitrile waste water treatment unit.
But nitrogen and phosphorus are the principal elements causing body eutrophication, as TN > 0.02mg/L, TP > 0.01mg/L, water body is just identified as exists eutrophication.TN in water body is from daily life activity and trade effluent.Along with day by day increasing the weight of of China's Inland Water eutrophication problem, country and provincial standard have put into effect total nitrogen emission standard successively, if " urban wastewater treatment firm pollutant emission standard " GB 18918-2002 regulation one-level/secondary total nitrogen index is 15/20mg/L, " Shanghai City integrated wastewater discharge standard " DB 31/199-2009 regulation one-level/secondary total nitrogen index is 25/35mg/L, and " Liaoning Province's integrated wastewater discharge standard " DB 21/1627-2008 total nitrogen index is 15mg/L.Existing " integrated wastewater discharge standard " is implemented more than 15 years, between these 15 years, the industrial and agricultural production level of China there occurs great variety, environmental quality and environmental capacity also there occurs great variety, be badly in need of revision " integrated wastewater discharge standard ", increase the Con trolling index of the serious broken ring environments such as TN.Removing COD and TN due to biological process is most economical, method the most thoroughly, so, the bioremediation of development of new or based on the combination treatment method of biological treatment, the COD clearance of raising acrylic nitrile waste water and nitric efficiency, significant.In recent years, several biologic treating technique for acrylic nitrile waste water is disclosed successively, but still have that processing efficiency is lower, water outlet can not the problem such as up to standard or running cost is higher.
Chinese patent CN 102190408B (201110096473.2) adopts preaeration reaction tank-hydrolysis acidification pool-oxygen compatibility pool-mono-section Aerobic Pond-bis-section Aerobic Pond-second pond combination process process vinyl cyanide, acrylic fiber production process comprehensive wastewater, COD is 4500 ~ 6100mg/L, when TN is 380 ~ 523mg/L, water outlet COD is 450 ~ 638mg/L, and total nitrogen is 38 ~ 56mg/L.COD clearance is 86% ~ 92%, TN clearance is 85% ~ 93%.The advantage of this technology is that TN clearance is higher, but water outlet COD is higher, still needs further biochemical treatment.
Chinese patent CN 202016935U (201120121780.7) discloses a kind of containing nitrile wastewater denitrification treatment apparatus, adopting anaerobic pond-settling tank-oxygen compatibility pool-Aerobic Pond combination process process COD to be 3000 ~ 5000mg/L, TN is 600 ~ 800mg/L, CN
-be 10 ~ 20mg/L containing nitrile waste water, water outlet COD < 62.8mg/L, NH
3-N < 3.66mg/L, TN < 32.5mg/L.The advantage of this technology is COD, NH
3the clearance of-N and TN is all higher, and water outlet reaches GB8978-1996 first discharge standard substantially.Shortcoming needs in oxygen compatibility pool, add a large amount of carbon source (methyl alcohol etc.), and to meet the carbon-nitrogen ratio needed for nitric nitrogen denitrification, running cost is very high.Because anaerobic pond is 50% ~ 70% to the clearance of COD, but to TN and NH
3-N does not have removal effect substantially, and TN can only remove at oxygen compatibility pool-Aerobic Pond (i.e. A/O method).When adopting A/O method to remove TN, require that the carbon-nitrogen ratio in sewage is greater than 4, just can reach higher nitric efficiency.
Chinese patent CN 202529945U (201120523601.2) adopts alkaline hydrolysis-aerobic biochemical-Fenton advanced oxidation-acidication-aerobic biochemical combination process process vinyl cyanide and acrylic fibers device waste water, in this technology, 1. mainly for the removal of COD, to NH
3-N and TN examines; 2., after mixing with polymeric wastewater and filature wastewater, the COD of waste water is less than 1000mg/L; 3. advanced oxidation need be removed COD and reaches 350mg/L, and running cost is higher.
The bioremediation of a kind of Wastewater from Acrylonitrile Production of Chinese patent CN 102718362 (201210205190.1), the flow process adopted is: homogeneous equalizing tank-hypoxia response district-aerobic reactor zone-nitration reaction district-second pond, in anoxic, aerobic and nitration reaction district, all filler is installed, and adds carbon source in front end, nitration reaction district.It is not right that the subject matter of the method is that carbon source adds position, and nitration reaction district is also aerobic reaction, and the carbon source added is easy to by aerobic degradation, and the hypoxia response district carrying out denitrification denitrogenation can not get supplementing of carbon source.In addition, the residence time of each reaction zone is all wrong according to COD carry calculation.The object that should process according to each district calculates respectively: hypoxia response district adopts nitric nitrogen carry calculation, and aerobic reactor zone adopts COD carry calculation, and nitration reaction district adopts ammonia nitrogen loading to calculate.
In the integrated processing method of Chinese patent CN 102399044A (201110371133.6) a kind of Wastewater from Acrylonitrile Production, biological treatment part have employed two sections of conventional A/O techniques, be 85% and 90% to the clearance of COD and ammonia nitrogen, enter the COD of ultrafiltration and reverse osmosis up to 132 and 118mg/L, pose a big pressure to ultrafiltration and reverse osmosis membrane, cleaning and the frequency of maintenance of system are higher.
A kind for the treatment of process to the organic waste water containing vinyl cyanide material of Chinese patent CN 103159374A (201110424220.3), adopts (1) materializing strategy; (2) anoxic/aerobic (A/O) biochemical treatment; (3) waste water comprising vinyl cyanide material of deep oxidation treatment combination flow processing CODcr≤1000mg/L, the COD 149mg/L of final process water outlet, BOD 19mg/L, colourity < 20, pH6 ~ 9, reach sewage second-level emission request substantially.The influent concentration that this technology is suitable for is lower, and removal efficiency is low, and effluent quality does not reach the requirement of GB8978-1996 primary standard.
In Chinese patent CN 103086576A (201310064394.2) a kind of vinyl cyanide, acrylic fiber production process comprehensive effluent disposal technology, acrylic nitrile waste water with after pretreated lower concentration Nitrilon waste water mixes, adopt one-stage hydrolysis acidifying-anoxic pond-one-level aerobic-second pond-secondary acidication-secondary is aerobic-nitrification tank-second pond combination process process.Its advantage is COD and NH of water outlet
3-N reaches GB8978-1996 first discharge standard, and TN is less than 30mg/L.But its influent concentration is low, be only 1/4 ~ 1/5 of acrylic nitrile waste water, treatment scheme is long, and construction investment and running cost are all higher.
Summary of the invention
Technical problem to be solved by this invention overcomes prior art process acrylic nitrile waste water to there is the problem that removal efficiency is lower, water outlet COD or TN is not up to standard, provides a kind of method of raising acrylic nitrile waste water nitric efficiency newly.The method is used in the process of the fine waste water of propylene, have the advantages that removal efficiency is high, water outlet TN reaches " urban wastewater treatment firm pollutant emission standard " GB 18918-2002 primary standard, all the other indexs reach " integrated wastewater discharge standard " GB8978-1996 primary standard, flow process is simple, running cost is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method improving denitrification rate of acrylonitrile waste water, comprises the steps: that COD is 1500 ~ 3500 mg/litre by (1), TN is 200 ~ 550 mg/litre, NH
3-N is that first the acrylic nitrile waste water of 20 ~ 80 mg/litre enters short-cut nitrification and denitrification pond, mixes, carries out the nitration reaction of organic matter degradation and ammonia nitrogen under air effect, complete the anti-nitration reaction of most of nitric nitrogen simultaneously with inner circulating reflux liquid;
(2) effluent in described short-cut nitrification and denitrification pond enters anoxic pond, mixes with inner circulating reflux liquid and the carbon source adding anoxic pond, completes the anti-nitration reaction of residue nitric nitrogen;
(3) effluent of described anoxic pond enters first stage precipitation tank and carries out mud-water separation, and top effluent enters Aerobic Pond, and base sludge is at least partially as mud discharging;
(4) contact with air with filler after the top effluent of described first stage precipitation tank enters Aerobic Pond, remove anoxic pond and add excessive carbon source; Then enter second-level settling pond and carry out mud-water separation, supernatant liquor enters advanced oxidation pond, and base sludge discharges;
(5) supernatant liquor of described second-level settling pond in advanced oxidation pond with catalyzer and oxidising agent, make the larger molecular organics of difficult degradation in acrylic nitrile waste water resolve into small organic molecule, improve the biodegradability of sewage;
(6) effluent in described advanced oxidation pond enters BAF, contacts with air with porous filter-material, reduces COD and NH further
3-N, obtains COD≤60 mg/litre, NH
3the discharge of wastewater up to standard of-N≤5 mg/litre, TN≤15 mg/litre, the mud discharging that BAF produces.
In technique scheme, preferably, described short-cut nitrification and denitrification pond adopts DO instrument and interlock of fan; In short-cut nitrification and denitrification pond, DO accurately controls in 0.3 ~ 0.5 mg/litre, and pH controls 7.5 ~ 8.0, and temperature is 10 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000 mg/litre; Short-cut nitrification and denitrification pond adopts airlift to realize the internal recycle of mixed solution in pond, and inner circulating reflux flow quantity is 10 ~ 30 times of flooding quantity;
In technique scheme, preferably, the described carbon source adding anoxic pond is methyl alcohol, the dosage of methyl alcohol is according to entering the carbon-nitrogen ratio of anoxic pond mixed solution for (3 ~ 5): 1 controls, and control anoxic pond DO and be less than 0.3 mg/litre, pH is 7.0 ~ 7.8, and temperature is 15 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000mg/L; Install submersible agitator in anoxic pond, realize the internal recycle of anoxic pond, agitator power is every cubic metre of anoxic pond volume 4 ~ 8W;
In technique scheme, preferably, the hydraulic load of described first stage precipitation tank is 0.5 ~ 1.0m
3/ m
2h, a first stage precipitation tank base sludge part is back to short-cut nitrification and denitrification pond, and return flow is 50 ~ 100% of flooding quantity.
In technique scheme, preferably, described Aerobic Pond is biological contact oxidation pond, and filler is fixing semi soft packing, and volumetric loading is 0.4 ~ 1.0kgCOD/m
3d.
In technique scheme, preferably, the hydraulic load of described second-level settling pond is 1.0 ~ 1.5m
3/ m
2h.
In technique scheme, preferably, described catalyzer is heterogeneous catalyst; More preferably, described heterogeneous catalyst is the oxide compound of activated carbon supported copper or manganese, or at least one in the oxide compound of activated alumina supported copper or manganese.Oxygenant is ozone, and ozone dosage is 40 ~ 80 mg/litre; In advanced oxidation pond, dwell time of sewage is 1 ~ 2h.
In technique scheme, preferably, the porous filter-material of described BAF is selected from the one in porous ceramic grain or porous porcelain grain, and filtrate height is 3 ~ 4.5m, and volumetric loading is 0.2 ~ 0.5kgCOD/m
3d.
In technique scheme, preferably, the standard of described discharge of wastewater is " integrated wastewater discharge standard " GB8978-1996 primary standard and " urban wastewater treatment firm pollutant emission standard " GB 18918-2002 primary standard.
In the inventive method, first acrylic nitrile waste water enters short-cut nitrification and denitrification pond, with inner circulating reflux liquid and settling tank returned sluge short mix.The effect of internal recycle: one is the water inlet of diluting high-concentration, reduces acrylic nitrile waste water to the toxicity of microorganism; Two is that the nitric nitrogen that Ammonia Nitrification generates is back to the more sufficient inlet segment of carbon source, improves denitrification rate.Active sludge is reclaimed in the effect of clarifier sludge backflow, maintains sludge concentration higher in biological reaction tank, improves the clearance of pollutent; And recyclable part adds excessive carbon source.In control pond, DO is 0.3 ~ 0.5mg/L, pH is 7.5 ~ 8.0, and reach the top condition needed for short-cut nitrification and denitrification reaction, denitrification flora can utilize NO
2 -carry out denitrification as electron acceptor(EA), namely nitrosification microorganism is by NH
4 +-N is converted into NO
2 --N, directly carries out anti-nitration reaction, by NO by denitrifying microorganism immediately
2 --N is reduced to N
2release, realizes denitrogenation object.
The effluent in short-cut nitrification and denitrification pond enters anoxic pond, and the effect of anoxic pond is intensified anti-nitrated, raising nitric efficiency.Control the optimum regime of mixed solution needed for denitrification in anoxic pond, namely DO is less than 0.3mg/L, and pH value is 7.0 ~ 7.8, and temperature is 15 ~ 35 DEG C; Add sufficient carbon source, lot of experiments and facts have proved, when selecting methyl alcohol as carbon source, denitrification rate and transformation efficiency all can reach the highest; Under this condition, denitrification process can carry out very thorough, and the nitric nitrogen of water outlet in theory can close to 0.Compared with preposition anoxic pond in conventional A/O technique, be located at short-cut nitrification and denitrification pond anoxic pond below more easily control DO value and pH value, additional carbon more easily utilize by denitrifying bacteria, therefore have higher denitrification efficiency.Because short-cut nitrification and denitrification pond has completed the denitrification denitrogenation of most of nitric nitrogen, the nitrate nitrogen content entering anoxic pond is lower, compared with, rear-mounted denitrification technique aerobic with the prime of routine, the carbon source amount needed for the method greatly reduces, thus reaches the object of saving processing cost.Because the biochemical degradation performance of methyl alcohol is fine, adopt common semi soft packing biological contact oxidation pond can obtain good effect.
The effect of settling tank is mud-water separation, and the partial sludge of first stage precipitation tank is back to short-cut nitrification and denitrification pond, recyclable active sludge, maintains sludge concentration higher in biological reaction tank, improves the clearance of pollutent; The mud of second-level settling pond all discharges.
The effect in advanced oxidation pond is that the larger molecular organics of difficult degradation in acrylic nitrile waste water is resolved into small organic molecule, or directly removes; Adopt ozone as oxygenant, can avoid adopting Fenton oxidation method to need first acid adding to be adjusted to acidity, add alkali again and be adjusted to alkalescence and cause equipment corrosion, increase the problems such as sewage saltiness; Load heterogeneous catalyst in pond, improve ozone oxidation speed, eliminate ozone to the selectivity of hardly degraded organic substance.Owing to still containing a small amount of ozone in the water outlet in advanced oxidation pond, ozone can kill the microorganism of BAF, so its water outlet must enter BAF again after 1 ~ 2h ozone is cleared up.Because BAF is built with porous filtrate, microorganic adhesion, at filter material surface, can make sewage, air fully contacts with microorganism, has and removes COD, NH
3the multi-functional of-N, TN and SS, is specially adapted to the advanced treatment of low concentration wastewater, makes water outlet qualified discharge; The sludge quantity that BAF produces is little, discharges with back flushing draining, discharge after precipitation and dehydration.
Adopt disposal methods acrylic nitrile waste water of the present invention, the water outlet COD≤60mg/L after process, NH
3-N≤5mg/L, reaches or is better than " integrated wastewater discharge standard " GB8978-1996 primary standard; TN≤15mg/L, reaches " urban wastewater treatment firm pollutant emission standard " GB 18918-2002 primary standard.Owing to have employed short-cut nitrification and denitrification technique in the present invention, organic matter degradation, nitrification and denitrification process is completed in same pond, reduce by the oxygen requirement of about 25% than traditional A/O technique, the carbon source of about 40%, reaction times shortens about 63%, reaches the object of saving energy consumption and improving removal efficiency.Owing to adding rearmounted anoxic pond in the present invention, enhance denitrification effect, improve TN clearance.Owing to have employed catalytic ozonation technique in the present invention, be applicable to the removal of various refractory organic, improve the biodegradability of sewage, do not need to add bronsted lowry acids and bases bronsted lowry adjust ph.Owing to have employed BAF as final stage aerobic treatment facility in the present invention, soon, it integrates bio-oxidation and retains suspended solids, saves post precipitation pond for easy biofilm, biological startup.Method of the present invention is by organics removal and total nitrogen is most economical, based on the simplest bioremediation, be aided with high-level oxidation technology, have the advantages that removal efficiency is high, flow process is simple, running cost is low, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention:
In figure, the implication of each label is: 1-short-cut nitrification and denitrification pond, 2-anoxic pond, 3-first stage precipitation tank, 4-Aerobic Pond, 5-second-level settling pond, 6-advanced oxidation pond, 7-BAF, 8-waste water feed line, 9-short-cut nitrification and denitrification pond inner circulating reflux, 10-anoxic pond carbon source adds pipeline, 11-anoxic pond inner circulating reflux, 12-first stage precipitation tank return sludge line, the outer comb line of 13-first stage precipitation tank mud, the outer comb line of 14-second-level settling pond mud, 15-oxygenant pipeline, the outer comb line of 16-BAF mud, the outer draining of 17-, 18-mud arranges main pipe line outward.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment
Embodiment
[embodiment 1]
Certain acrylic nitrile waste water water quality: COD is 3500mg/L, NH
3-N is 45mg/L, TN is 520mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is 30 times of flooding quantity; In control pond, DO is 0.5mg/L, pH is 7.8, and temperature is 30 DEG C, and sludge concentration is 8000mg/L.
The effluent in short-cut nitrification and denitrification pond enters anoxic pond, methyl alcohol is added in pond, dosage is that 5:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.3mg/L, pH is 7.8, and temperature is 35 DEG C, and sludge concentration is 8000mg/L, establish submersible agitator to realize the internal recycle of mixed solution in anoxic pond, agitator power is every cubic metre of anoxic pond volume 8W; The effluent of anoxic pond enters first stage precipitation tank, and the hydraulic load of first stage precipitation tank is 0.5m
3/ m
2h, return sludge ratio is 100%; The supernatant liquor of first stage precipitation tank enters Aerobic Pond and second-level settling pond successively, and the volumetric loading of Aerobic Pond is 0.4kgCOD/m
3d, the hydraulic load of second-level settling pond is 1.0m
3/ m
2h.
Advanced oxidation pond is built with catalyzer, and catalyzer is activated alumina loaded copper oxide, and cupric oxide charge capacity is 15% (weight), and ozone dosage is 80mg/L, and dwell time of sewage is 2h.The water outlet in advanced oxidation pond enters BAF after ozone is cleared up, and porous filter-material is porous ceramic grain, and packed height is 4m, and volumetric loading is 0.25kgCOD/m
3d.
The effluent quality of each section is in table 1.
Table 1. embodiment 1 each section of water quality
[embodiment 2]
Certain acrylic nitrile waste water water quality: COD is 2850mg/L, NH
3-N is 35mg/L, TN is 356mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is 25 times of flooding quantity; In control pond, DO is 0.4mg/L, pH is 8.0, and temperature is 20 DEG C, and sludge concentration is 6000mg/L.
The effluent in short-cut nitrification and denitrification pond enters anoxic pond, methyl alcohol is added in pond, dosage is that 4:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.2mg/L, pH is 7.5, and temperature is 25 DEG C, and sludge concentration is 6000mg/L, establish submersible agitator to realize the internal recycle of mixed solution in anoxic pond, agitator power is every cubic metre of anoxic pond volume 6W; The effluent of anoxic pond enters first stage precipitation tank, and the hydraulic load of first stage precipitation tank is 0.75m
3/ m
2h, return sludge ratio is 80%; The supernatant liquor of first stage precipitation tank enters Aerobic Pond and second-level settling pond successively, and the volumetric loading of Aerobic Pond is 0.65kgCOD/m
3d, the hydraulic load of second-level settling pond is 1.2m
3/ m
2h.
Advanced oxidation pond is built with catalyzer, and catalyzer is activated alumina load Manganse Dioxide, and manganese dioxide load amount is 5% (weight), and ozone dosage is 50mg/L, and dwell time of sewage is 1.6h.The water outlet in advanced oxidation pond enters BAF after ozone is cleared up, and porous filter-material is porous ceramic grain, and packed height is 3.5m, and volumetric loading is 0.4kgCOD/m
3d.
The effluent quality of each section is in table 2.
Table 2. embodiment 2 each sections of water quality
[embodiment 3]
Certain acrylic nitrile waste water mixes water quality with other waste water: COD is 1500mg/L, NH
3-N is 33mg/L, TN is 220mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is 10 times of flooding quantity; In control pond, DO is 0.3mg/L, pH is 7.5, and temperature is 15 DEG C, and sludge concentration is 4000mg/L.
The effluent in short-cut nitrification and denitrification pond enters anoxic pond, methyl alcohol is added in pond, dosage is that 3:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.1mg/L, pH is 7.2, and temperature is 20 DEG C, and sludge concentration is 4000mg/L, establish submersible agitator to realize the internal recycle of mixed solution in anoxic pond, agitator power is every cubic metre of anoxic pond volume 4W; The effluent of anoxic pond enters first stage precipitation tank, and the hydraulic load of first stage precipitation tank is 1.0m
3/ m
2h, return sludge ratio is 50%; The supernatant liquor of first stage precipitation tank enters Aerobic Pond and second-level settling pond successively, and the volumetric loading of Aerobic Pond is 1.0kgCOD/m
3d, the hydraulic load of second-level settling pond is 1.5m
3/ m
2h.
Advanced oxidation pond is built with catalyzer, and catalyzer is activated carbon supported cupric oxide, and cupric oxide charge capacity is 15% (weight), and ozone dosage is 30mg/L, and dwell time of sewage is 1.0h.The water outlet in advanced oxidation pond enters BAF after ozone is cleared up, and porous filter-material is porous porcelain grain, and packed height is 3.0m, and volumetric loading is 0.2kgCOD/m
3d.
The effluent quality of each section is in table 3.
Table 3. embodiment 3 each sections of water quality
Claims (10)
1. improve a method for denitrification rate of acrylonitrile waste water, comprise the following steps:
(1) be 1500 ~ 3500 mg/litre by COD, TN is 200 ~ 550 mg/litre, NH
3-N is that first the acrylic nitrile waste water of 20 ~ 80 mg/litre enters short-cut nitrification and denitrification pond, mixes, carries out the nitration reaction of organic matter degradation and ammonia nitrogen under air effect, complete the anti-nitration reaction of most of nitric nitrogen simultaneously with inner circulating reflux liquid;
(2) effluent in described short-cut nitrification and denitrification pond enters anoxic pond, mixes with inner circulating reflux liquid and the carbon source adding anoxic pond, completes the anti-nitration reaction of residue nitric nitrogen;
(3) effluent of described anoxic pond enters first stage precipitation tank and carries out mud-water separation, and top effluent enters Aerobic Pond, and base sludge is at least partially as mud discharging;
(4) contact with air with filler after the top effluent of described first stage precipitation tank enters Aerobic Pond, remove anoxic pond and add excessive carbon source; Then enter second-level settling pond and carry out mud-water separation, supernatant liquor enters advanced oxidation pond, and base sludge discharges;
(5) supernatant liquor of described second-level settling pond in advanced oxidation pond with catalyzer and oxidising agent, make the larger molecular organics of difficult degradation in acrylic nitrile waste water resolve into small organic molecule, improve the biodegradability of sewage;
(6) effluent in described advanced oxidation pond enters BAF, contacts with air with porous filter-material, reduces COD and NH further
3-N, obtains COD≤60 mg/litre, NH
3the discharge of wastewater up to standard of-N≤5 mg/litre, TN≤15 mg/litre, the mud discharging that BAF produces.
2. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, it is characterized in that described short-cut nitrification and denitrification pond adopts DO instrument and interlock of fan; In short-cut nitrification and denitrification pond, DO accurately controls in 0.3 ~ 0.5 mg/litre, and pH controls 7.5 ~ 8.0, and temperature is 10 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000 mg/litre; Short-cut nitrification and denitrification pond adopts airlift to realize the internal recycle of mixed solution in pond, and inner circulating reflux flow quantity is 10 ~ 30 times of flooding quantity;
3. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, the carbon source adding anoxic pond described in it is characterized in that is methyl alcohol, the dosage of methyl alcohol is that 3 ~ 5:1 controls according to the carbon-nitrogen ratio entering anoxic pond mixed solution, and control anoxic pond DO and be less than 0.3 mg/litre, pH is 7.0 ~ 7.8, temperature is 15 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000mg/L; Install submersible agitator in anoxic pond, realize the internal recycle of anoxic pond, agitator power is every cubic metre of anoxic pond volume 4 ~ 8W;
4. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, it is characterized in that the hydraulic load of described first stage precipitation tank is 0.5 ~ 1.0m
3/ m
2h, a first stage precipitation tank base sludge part is back to short-cut nitrification and denitrification pond, and return flow is 50 ~ 100% of flooding quantity.
5. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, it is characterized in that described Aerobic Pond is biological contact oxidation pond, filler is fixing semi soft packing, and volumetric loading is 0.4 ~ 1.0kgCOD/m
3d.
6. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, it is characterized in that the hydraulic load of described second-level settling pond is 1.0 ~ 1.5m
3/ m
2h.
7. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, it is characterized in that described catalyzer is heterogeneous catalyst; Oxygenant is ozone, and ozone dosage is 40 ~ 80 mg/litre; In advanced oxidation pond, dwell time of sewage is 1 ~ 2h.
8. improve the method for denitrification rate of acrylonitrile waste water according to claim 1; it is characterized in that the porous filter-material of described BAF is selected from least one in porous ceramic grain or porous porcelain grain; filtrate height is 3 ~ 4.5m, and volumetric loading is 0.2 ~ 0.5kgCOD/m
3d.
9. improve the method for denitrification rate of acrylonitrile waste water according to claim 1, it is characterized in that the standard of described discharge of wastewater is for " integrated wastewater discharge standard " GB8978-1996 primary standard and " urban wastewater treatment firm pollutant emission standard " GB 18918-2002 primary standard.
10. improve the method for denitrification rate of acrylonitrile waste water according to claim 7, it is characterized in that described heterogeneous catalyst is the oxide compound of activated carbon supported copper or manganese, or at least one in the oxide compound of activated alumina supported copper or manganese.
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