CN103641277A - Acrylonitrile waste water treatment method - Google Patents
Acrylonitrile waste water treatment method Download PDFInfo
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- CN103641277A CN103641277A CN201310681566.0A CN201310681566A CN103641277A CN 103641277 A CN103641277 A CN 103641277A CN 201310681566 A CN201310681566 A CN 201310681566A CN 103641277 A CN103641277 A CN 103641277A
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Abstract
The invention relates to an acrylonitrile waste water treatment method, which is mainly used for solving the problems of low efficiency of removing COD (Chemical Oxygen Demand) and TN (Total Nitrogen), yielding water of non-compliance, long process flow and high operation cost of acrylonitrile waste water treatment in the prior art. The acrylonitrile waste water treatment method provided by the invention comprises the following steps: (1) firstly feeding the acrylonitrile waste water into a short-cut nitrification and denitrification tank; (2) dividing the efflux of the short-cut nitrification and denitrification tank into two branches, and feeding one branch into an anaerobic tank, returning the mixed liquid of the anaerobic tank to the short-cut nitrification and denitrification tank, and feeding the other branch into the sedimentation tank; (3) returning one part of sludge at the bottom of the sedimentation tank to the short-cut nitrification and denitrification tank, and discharging one part as sludge, and feeding the supernatant into an advanced oxidation pond; (4) feeding the efflux of the advanced oxidation pond into a biological aerated filter to obtain the waste water for discharge which is up to the A-level standard of Integrated Wastewater Discharge Standard GB8978-1996; the technical scheme can be used for well solving the problems; therefore, the acrylonitrile waste water treatment method can be applied to industrial treatment of the acrylonitrile waste water.
Description
Technical field
The present invention relates to a kind for the treatment of process of acrylic nitrile waste water.
Background technology
Vinyl cyanide is mainly used in the productions such as acrylic fibers, paracril, adiponitrile, acrylamide, ABS resin, also can be used for the production of hexanolactam, polyhydric alcohol polymer, it has broad application prospects in fields such as synthon, synthetic rubber, plastics, the demand strong growth to vinyl cyanide of China and even the whole world, production device for acrylic nitrile will constantly start.The production method of vinyl cyanide has four kinds of cyanoethanol method, acetylene method, propylene ammmoxidation process and propane ammoxidation methods, what domestic and international application was maximum at present is propylene ammmoxidation process, take propylene, ammonia and air as main raw material, under the effect of certain reaction conditions and catalyzer, generate vinyl cyanide and water, by product is mainly acetonitrile and prussic acid.Reaction product, after the series of measures such as absorption, extraction and stripping are separated, still contain the organism such as vinyl cyanide, prussic acid, acetonitrile, pyridine, vinylformic acid, propenal, anti-maleic nitrile and cyanalcohol, and reacts residual ammonia in factory effluent.The key character of acrylic nitrile waste water is that high chemical oxygen demand (hereinafter to be referred as COD), high total nitrogen (hereinafter to be referred as TN) and high prussiate are (hereinafter to be referred as CN
-); Toxicity is high, and intractability is large.
For this class acrylic nitrile waste water, early stage more employing burning method, simpler because burning method is processed, incineration temperature is 850～1100 ℃, the most thorough to the destruction of pollutent; But burn the high-temp waste gas producing, be directly discharged in atmosphere, have serious energy consumption waste and problem of environmental pollution.Conventional method is first to adopt the physics such as multiple-effect evaporation, hydrogen peroxide oxidation, wet oxidation or Fenton reagent or chemical process to carry out pre-treatment to acrylic nitrile waste water, removes vinyl cyanide and prussiate, reduce its to the toxicity of microorganism after, then take biological process to process.
Acrylic nitrile waste water is after pre-treatment, and COD and TN are still very high, and (COD is up to 3500mg/L, and TN is up to 550mg/L, TN is mainly organonitrogen and ammonia nitrogen), adopt existing biological method to process and have difficulty, efficiency is lower, need to utilize service water or low concentration wastewater dilution aftertreatment.As: after Shanghai acrylonitrile installation water reuse service water is diluted to COD < 1000mg/L, adopt Wastewater Treated by Activated Sludge Process, water outlet COD is 300～500mg/L, ammonia nitrogen < 150mg/L; Anqing acrylonitrile installation waste water and Nitrilon waste water adopt A/O method to process after being mixed to the about 700mg/L of COD, water outlet COD < 170mg/L; It is 650-800mg/L that grand celebration acrylonitrile installation waste water and Nitrilon waste water are mixed to COD, after TN is 60-70mg/L, adopts pure oxygen aeration+contact oxidation method to process, water outlet COD and NH
3-N is substantially up to standard; Jilin acrylonitrile installation water reuse low concentration wastewater is diluted to after COD < 1800mg/L, adopts SBR method to process, and water outlet COD is 800～900mg/L, NH
3-N < 300mg/L, can not be up to standard; After transformation, adopt biological multiplication method to process, water outlet COD < 300mg/L, NH
3-N < 50mg/L, still below standard.Therefore, although acrylic nitrile waste water has been carried out diluting (2～5 times), the COD of water outlet and NH
3-N does not all reach the requirement of < < integrated wastewater discharge standard > > (GB8978-1996) primary standard, directly outer row.In addition, owing to not stipulating the index of TN in GB8978-1996, although above user has adopted the treatment process with denitrification functions, all do not examine water outlet TN.
Pay attention to day by day along with China's environmental pollution problem, improved the pollution exhaust criteria of all kinds of manufacturing enterprises, especially country and provincial standard have been put into effect total nitrogen discharge index successively, if < < urban wastewater treatment firm pollutant emission standard > > (GB18918-2002) regulation one-level/secondary total nitrogen index is 15/20mg/L, < < Shanghai City integrated wastewater discharge standard > > (DB31/199-2009) regulation one-level/secondary total nitrogen index is 25/35mg/L, the integrated wastewater discharge standard > > of < < Liaoning Province (DB21/1627-2008) total nitrogen index is 15mg/L.Due to biological process, removing COD and TN is most economical, method the most thoroughly, so, the bioremediation of development of new, or to take biological treatment be main combination treatment method, improves COD clearance and the nitric efficiency of acrylic nitrile waste water, significant.In recent years, disclose successively several biologic treating techniques for acrylic nitrile waste water, but have that treatment scheme is long, processing efficiency is lower or the problem such as running cost is higher.
Chinese patent CN102190408B(201110096473.2) adopt preaeration reaction tank-hydrolysis acidification pool-oxygen compatibility pool-mono-section Aerobic Pond-bis-section Aerobic Pond-second pond combination process to 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 that 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 CN202016935U(201120121780.7) disclose a kind of nitrile wastewater denitrification treatment apparatus that contains, adopting anaerobic pond-settling tank-oxygen compatibility pool-Aerobic Pond combination process to process COD is 3000～5000mg/L, and 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 is in oxygen compatibility pool, to add a large amount of carbon sources (methyl alcohol etc.), and to meet the required carbon-nitrogen ratio of 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 (being A/O method).While adopting A/O method to remove TN, require the carbon-nitrogen ratio in sewage to be greater than 4, just can reach higher nitric efficiency.
Chinese patent CN202529945U(201120523601.2) adopt alkaline hydrolysis-aerobic biochemical-Fenton advanced oxidation-acidication-aerobic biochemical combination process to 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 examine; 2., after mixing with polymerization waste water 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.
Chinese patent CN102718362(201210205190.1) a kind of bioremediation of Wastewater from Acrylonitrile Production, the flow process adopting is: homogeneous equalizing tank-hypoxia response district-aerobic reactor zone-nitration reaction district-second pond, in anoxic, aerobic and nitration reaction district, filler is all installed, Bing nitration reaction district front end adds carbon source.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 adding is easy to by aerobic degradation, and the hypoxia response district that carries out denitrification denitrogenation can not get supplementing of carbon source.In addition, the residence time of each reaction zone is all wrong at last according to COD load gauge.The object that should process according to each district calculates respectively: hypoxia response district adopts nitric nitrogen load to calculate, and aerobic reactor zone adopts COD load to calculate, and nitration reaction district adopts ammonia nitrogen loading to calculate.
Chinese patent CN102399044A(201110371133.6) in a kind of integrated processing method of Wastewater from Acrylonitrile Production, biological treatment part has adopted two sections of conventional A/O techniques, to the clearance of COD and ammonia nitrogen, be 85% and 90%, the COD that enters ultrafiltration and reverse osmosis is up to 132 and 118mg/L, ultrafiltration and reverse osmosis membrane are posed a big pressure, and cleaning and the frequency of maintenance of system are higher.
Chinese patent CN103159374A(201110424220.3) a kind for the treatment of process to the organic waste water containing vinyl cyanide material, adopts (1) materialization to process; (2) anoxic/aerobic (A/O) biochemical treatment; (3) waste water that comprises vinyl cyanide material of deep oxidation treatment combination flow processing CODcr≤1000mg/L, the final COD149mg/L that processes water outlet, BOD19mg/L, colourity < 20, pH6～9, reach sewage second-level emission request substantially.The applicable influent concentration of this technology is lower, and removal efficiency is low, and effluent quality does not reach the requirement of GB8978-1996 primary standard.
Chinese patent CN103086576A(201310064394.2) in a kind of vinyl cyanide, acrylic fiber production process comprehensive effluent disposal technology, acrylic nitrile waste water is 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 processes.Its advantage is COD and the 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 is to overcome prior art to process acrylic nitrile waste water and have that removal efficiency is lower, water outlet is not up to standard, and the problem that technical process is long, running cost is high, provides a kind of new acrylic nitrile waste water treatment process.The method is for the processing of the fine waste water of propylene, has COD and TN removal efficiency is high, water outlet is up to standard, flow process is simple, running cost is low feature.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind for the treatment of process of acrylic nitrile waste water, comprises the following steps:
(1) by COD, be that 1500～3500 mg/litre, TN are 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 with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge, carries out the anti-nitration reaction of the nitrated and nitric nitrogen of organic matter degradation, ammonia nitrogen;
(2) effluent in described short-cut nitrification and denitrification pond is divided into two-way, and a road enters anoxic pond, mixes with adding the hydrocarbon polymer of anoxic pond, and the mixed solution of formation returns to short-cut nitrification and denitrification pond as anoxic pond phegma, and another road enters settling tank;
(3) part for the mud of described settling tank bottom is returned to short-cut nitrification and denitrification pond as described settling tank returned sluge, and a part is as mud discharging, and the supernatant liquor on settling tank top enters advanced oxidation pond, contacts with oxygenant with catalyzer;
(4) effluent in advanced oxidation pond enters after BAF contacts with porous filter-material, obtains COD≤60 mg/litre, TN≤50 mg/litre, NH
3the discharge of wastewater up to standard of-N≤10 mg/litre, the mud that BAF produces is as mud discharging.
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 is accurately controlled at 0.3～0.5 mg/litre, and pH is controlled at 7.5～8.0, and temperature is 10～35 ℃, and sludge concentration is 4000～8000 mg/litre; The part that is entered anoxic pond by short-cut nitrification and denitrification pond utilizes pump to promote, and controls and promotes 2～5 times that flow is flooding quantity; The part that is entered settling tank by short-cut nitrification and denitrification pond is run by gravity, without controlling flow; Short-cut nitrification and denitrification pond adopts at least one in airlift, submersible agitator, pump to realize the internal recycle of mixed solution in pond, inner circulating reflux flow quantity is flooding quantity 10～30 times.
In technique scheme, preferably, described in add the hydrocarbon polymer of anoxic pond to be selected from least one in methyl alcohol, ethanol; The carbon-nitrogen ratio of controlling mixed solution in anoxic pond is that (3～5): 1, DO is less than 0.3 mg/litre, and pH is 7.0～7.8, and temperature is 15～35 ℃, and sludge concentration is 4000～8000mg/L; Submersible agitator is installed in anoxic pond, and the mixed liquor flows by gravity of anoxic pond is back to short-cut nitrification and denitrification pond.
In technique scheme, preferably, the hydraulic load of described settling tank is 0.5～1.0m
3/ m
2.h, settling tank bottom sludge reflux to the flow in short-cut nitrification and denitrification pond is flooding quantity 50～100%.
In technique scheme, preferably, described catalyzer is heterogeneous catalyst, and more preferably, 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 effluent in described advanced oxidation pond enters after BAF contacts with porous filter-material, discharged wastewater met the national standard, and the mud of back flush discharge is discharge after dehydration; Described porous filter-material is selected from least one in porous ceramic grain or porous porcelain grain, and filtrate height is 3.0～4.5m, and the volumetric loading of BAF is 0.2～0.5kgCOD/m
3.d.
In technique scheme, preferably, there is inner circulating reflux liquid in described anoxic pond, by submersible agitator, realizes, and agitator power is every cubic metre of anoxic pond volume 4～8W.
In technique scheme, preferably, the standard of described discharge of wastewater is < < integrated wastewater discharge standard > > GB8978-1996 primary standard.
In the inventive method, first acrylic nitrile waste water enters short-cut nitrification and denitrification pond, with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge short mix.The effect of internal recycle: the one, the water inlet of diluting high-concentration, reduces the toxicity of acrylic nitrile waste water to microorganism; The 2nd, the nitric nitrogen that Ammonia Nitrification is generated is back to the inlet segment that carbon source is more sufficient, improves denitrification rate.The effect of anoxic pond mixed-liquor return is utilized the remaining hydrocarbon polymer of denitrification or is degraded in short-cut nitrification and denitrification pond.The effect of settling tank sludge reflux is to reclaim active sludge, maintains sludge concentration higher in biological reaction tank, improves the clearance of pollutent.Controlling DO in pond is 0.3～0.5mg/L, and pH is 7.5～8.0, reaches short-cut nitrification and denitrification and reacts required top condition, and denitrification flora can utilize NO
2-as electron acceptor(EA), carry out denitrification, nitrosification microorganism is by NH
4 +-N is converted into NO
2 --N, directly carries out anti-nitration reaction by denitrifying microorganism, immediately by NO
2 --N is reduced to N
2discharge.
The effluent in short-cut nitrification and denitrification pond is divided into two-way, and a road enters anoxic pond, and another road enters settling tank.The effect of anoxic pond is intensified anti-nitrated, raising nitric efficiency, by following measures, realizes: control the interior mixed solution of anoxic pond in the required optimum regime of denitrification, DO is less than 0.3mg/L, and pH value is 7.0～7.8, and temperature is 15～35 ℃; Add the hydrocarbon polymer of lower molecular weight, the carbon source of the required abundance of denitrification is provided; The mixed solution that enters anoxic pond utilizes pump to promote, and avoids air-lift unit that the DO of anoxic pond is raise, and is unfavorable for denitrification.Compare with the preposition anoxic pond of conventional A/O technique, more easily control DO value and pH value, external carbon hydrogen compound is more easily utilized by denitrifying bacteria, therefore has higher denitrification efficiency.The flow that enters anoxic pond determines according to DO value in short-cut nitrification and denitrification pond end nitrate and anoxic pond, get flooding quantity 2～5 times.After complete denitrification, the mixed solution run by gravity of anoxic pond is back to short-cut nitrification and denitrification pond, by adding excessive hydrocarbon polymer, is utilized or degrade in short-cut nitrification and denitrification pond.The effect of settling tank is mud-water separation, prevents that mud from entering advanced oxidation pond on the one hand, increases oxidant consumption amount; Recyclable active sludge, maintains sludge concentration higher in biological reaction tank on the other hand, improves the clearance of pollutent.The supernatant liquor of settling tank drains into advanced oxidation pond and further processes, and the mud of bottom promotes, is back to short-cut nitrification and denitrification pond front end by pump or airlift, a small amount of mud discharging.
The effect in advanced oxidation pond is to remove part hardly degraded organic substance, or makes it resolve into small organic molecule; Adopt ozone as oxygenant, can avoid adopting Fenton oxidation style 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; In pond, filling heterogeneous catalyst, improves ozone oxidation speed, eliminates the selectivity of ozone to hardly degraded organic substance.In the water outlet in advanced oxidation pond, still contain a small amount of ozone, ozone can kill the microorganism of BAF, so its water outlet must enter BAF after 1～2h ozone is cleared up again.Due to porous filtrate being housed in BAF, microorganic adhesion, at filter material surface, can make sewage, air and microorganism fully contact, and has COD, the NH of removal
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 seldom, is discharged with back flushing draining, discharge after concentrated and dehydration.
Adopt disposal methods acrylic nitrile waste water of the present invention, the water outlet COD≤60mg/L after processing, NH
3-N≤5mg/L, reaches or is better than < < integrated wastewater discharge standard > > GB8978-1996 primary standard; TN≤50mg/L, meets TN emission request.In the present invention owing to having adopted short-cut nitrification and denitrification technique, in same pond, complete organic matter degradation, nitrification and denitrification process, than traditional A/O technique, reduce by approximately 25% oxygen requirement, approximately 40% carbon source, reaction times shortens approximately 63%, has reached the object of saving energy consumption and improving removal efficiency.In the present invention, owing to having increased external anoxic pond, strengthen denitrification effect, improved TN clearance.In the present invention, owing to having adopted catalytic ozonation technique, applicable to the removal of various refractory organics, improve the biodegradability of sewage, do not increase the saltiness of sewage, be conducive to effluent reuse.In the present invention, owing to having adopted BAF as second stage aerobic treatment facility, easily soon, it integrates bio-oxidation and holds back suspended solids, has saved post precipitation pond for biofilm, biological startup.Method of the present invention be take and removed organism and total nitrogen is most economical, the simplest bioremediation is as basis, is aided with high-level oxidation technology, has the advantages that removal efficiency is high, flow process is simple, running cost is low, has obtained 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-settling tank, 4-advanced oxidation pond, 5-BAF, 6-waste water feed line, 7-anoxic pond inner circulating reflux, 8-oxygenant pipeline, the outer draining of 9-, the outer comb line of 10-BAF mud, 11-mud is arranged main pipe line outward, the outer comb line of 12-settling tank mud, 13-settling tank bottom mud pipeline, 14-short-cut nitrification and denitrification pond inner circulating reflux, 15-settling tank return sludge line, 16-hydrocarbon polymer adds pipeline.
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 3000mg/L, NH
3-N is 40mg/L, and TN is 495mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is flooding quantity 25 times; Controlling DO in pond is 0.4mg/L, and pH is 7.8, and temperature is 20 ℃, and sludge concentration is 6000mg/L.
The effluent in short-cut nitrification and denitrification pond is divided into two-way: a route pump promotes and enters anoxic pond, it promotes 3.5 times that flow is flooding quantity, in pond, add methyl alcohol, dosage is that 3:1 calculates by carbon-nitrogen ratio, and the DO of anoxic pond is 0.1mg/L, and pH is 7.5, temperature is 25 ℃, sludge concentration is 6000mg/L, establishes submersible agitator to realize the internal recycle of mixed solution in anoxic pond, and agitator power is every cubic metre of anoxic pond volume 4W; Another road run by gravity enters settling tank, and the hydraulic load of settling tank is 0.75m
3/ m
2.h, return sludge ratio is 80%, and the supernatant liquor of settling tank enters advanced oxidation pond, and wherein COD is 125mg/L, NH
3-N is 5.5mg/L, and TN is 39mg/L.
Advanced oxidation is equipped with catalyzer in pond, and catalyzer is activated alumina loaded copper oxide, and cupric oxide charge capacity is 15%(weight), ozone dosage is 50mg/L, and dwell time of sewage is 2h, and the COD of water outlet is 85mg/L, NH
3-N and TN are constant.
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 0.5kgCOD/m
3.d, final outflow water water quality: COD is 53.4mg/L, NH
3-N is 3.5mg/L, and TN is 39mg/L, reaches < < integrated wastewater discharge standard > > GB8978-1996 primary standard.
[embodiment 2]
Certain acrylic nitrile waste water water quality: COD is 3500mg/L, NH
3-N is 45mg/L, and TN is 520mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is flooding quantity 30 times; Controlling DO in pond is 0.5mg/L, and pH is 8.1, and temperature is 30 ℃, and sludge concentration is 8000mg/L.
The effluent in short-cut nitrification and denitrification pond is divided into two-way: a route pump promotes and enters anoxic pond, its flow is 2.8 times of flooding quantity, in pond, add methyl alcohol, dosage is that 4:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.3mg/L, and pH is 7.8, and temperature is 35 ℃, sludge concentration is 8000mg/L, and in anoxic pond, agitator power is every cubic metre of anoxic pond volume 6W; Another road run by gravity enters settling tank, and the hydraulic load of settling tank is 0.50m
3/ m
2.h, return sludge ratio is 100%, and the supernatant liquor of settling tank enters advanced oxidation pond, and wherein COD is 147mg/L, NH
3-N is 6.7mg/L, and TN is 48mg/L.
Activated carbon supported manganese dioxide-catalyst is housed in advanced oxidation pond, and manganese dioxide load amount is 5%(weight), ozone dosage is 80mg/L, and dwell time of sewage is 2h, and the COD of water outlet is 90mg/L, NH
3-N and TN are constant.
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 4.5m, and volumetric loading is 0.3kgCOD/m
3.d, final outflow water water quality: COD is 56.5mg/L, NH
3-N is 3.8mg/L, and TN is 48mg/L.
[embodiment 3]
The water quality of mixing of certain acrylic nitrile waste water and other waste water: COD is 1500mg/L, NH
3-N is 33mg/L, and TN is 220mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is flooding quantity 10 times; Controlling DO in pond is 0.3mg/L, and pH is 7.5, and temperature is 25 ℃, and sludge concentration is 4000mg/L.
The effluent in short-cut nitrification and denitrification pond is divided into two-way: a route pump promotes and enters anoxic pond, its flow is 5 times of flooding quantity, in pond, add ethanol, dosage is that 5:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.2mg/L, and pH is 7.3, and temperature is 30 ℃, sludge concentration is 4000mg/L, and in anoxic pond, agitator power is every cubic metre of anoxic pond volume 4W; Another road run by gravity enters settling tank, and the hydraulic load of settling tank is 1.00m
3/ m
2.h, return sludge ratio is 50%, and the supernatant liquor of settling tank enters advanced oxidation pond, and wherein COD is 119mg/L, NH
3-N is 5.3mg/L, and TN is 28.6mg/L.
Activated alumina load manganese dioxide-catalyst is housed in advanced oxidation pond, and manganese dioxide load amount is 5%(weight), ozone dosage is 40mg/L, and dwell time of sewage is 2h, and the COD of water outlet is 80mg/L, NH
3-N and TN are constant.
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 0.25kgCOD/m
3.d, final outflow water water quality: COD is 45mg/L, NH
3-N is 0.8mg/L, and TN is 28.6mg/L.
Claims (9)
1. a treatment process for acrylic nitrile waste water, comprises the following steps:
(1) by COD, be that 1500～3500 mg/litre, TN are 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 with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge, carries out the anti-nitration reaction of the nitrated and nitric nitrogen of organic matter degradation, ammonia nitrogen;
(2) effluent in described short-cut nitrification and denitrification pond is divided into two-way, and a road enters anoxic pond, mixes with adding the hydrocarbon polymer of anoxic pond, and the mixed solution of formation returns to short-cut nitrification and denitrification pond as anoxic pond phegma, and another road enters settling tank;
(3) part for the mud of described settling tank bottom is returned to short-cut nitrification and denitrification pond as described settling tank returned sluge, and a part is as mud discharging, and the supernatant liquor on settling tank top enters advanced oxidation pond, contacts with oxygenant with catalyzer;
(4) effluent in advanced oxidation pond enters after BAF contacts with porous filter-material, obtains COD≤60 mg/litre, TN≤50 mg/litre, NH
3the discharge of wastewater up to standard of-N≤10 mg/litre, the mud that BAF produces is as mud discharging.
2. the treatment process of acrylic nitrile waste water according to claim 1, 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 is accurately controlled at 0.3～0.5 mg/litre, and pH is controlled at 7.5～8.0, and temperature is 10～35 ℃, and sludge concentration is 4000～8000 mg/litre; The part that is entered anoxic pond by short-cut nitrification and denitrification pond utilizes pump to promote, and controls and promotes 2～5 times that flow is flooding quantity; The part that is entered settling tank by short-cut nitrification and denitrification pond is run by gravity, without controlling flow; Short-cut nitrification and denitrification pond adopts at least one in airlift, submersible agitator, pump to realize the internal recycle of mixed solution in pond, inner circulating reflux flow quantity is flooding quantity 10～30 times.
3. the treatment process of acrylic nitrile waste water according to claim 1, adds the hydrocarbon polymer of anoxic pond to be selected from least one in methyl alcohol, ethanol described in it is characterized in that; The carbon-nitrogen ratio of controlling mixed solution in anoxic pond is that (3～5): 1, DO is less than 0.3 mg/litre, and pH is 7.0～7.8, and temperature is 15～35 ℃, and sludge concentration is 4000～8000mg/L; Submersible agitator is installed in anoxic pond, and the mixed liquor flows by gravity of anoxic pond is back to short-cut nitrification and denitrification pond.
4. the treatment process of acrylic nitrile waste water according to claim 1, the hydraulic load that it is characterized in that described settling tank is 0.5～1.0m
3/ m
2.h, settling tank bottom sludge reflux to the flow in short-cut nitrification and denitrification pond is flooding quantity 50～100%.
5. the treatment process of acrylic nitrile waste water according to claim 1, 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.
6. the treatment process of acrylic nitrile waste water according to claim 1, the effluent that it is characterized in that described advanced oxidation pond enters after BAF contacts with porous filter-material, discharged wastewater met the national standard, the mud of back flush discharge is discharge after dehydration; Described porous filter-material is selected from least one in porous ceramic grain or porous porcelain grain, and filtrate height is 3.0～4.5m, and the volumetric loading of BAF is 0.2～0.5kgCOD/m
3.d.
7. the treatment process of acrylic nitrile waste water according to claim 1, is characterized in that described anoxic pond exists inner circulating reflux liquid, by submersible agitator, realizes, and agitator power is every cubic metre of anoxic pond volume 4～8W.
8. the treatment process of acrylic nitrile waste water according to claim 1, the standard that it is characterized in that described discharge of wastewater is < < integrated wastewater discharge standard > > GB8978-1996 primary standard.
9. the treatment process of acrylic nitrile waste water according to claim 5, 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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