CN102874927B - Biological treatment method, biological treatment system and bioreactor of coal chemical wastewater - Google Patents
Biological treatment method, biological treatment system and bioreactor of coal chemical wastewater Download PDFInfo
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Abstract
The invention relates to a biological treatment method of coal chemical wastewater, which adopts a biological reaction-muddy water separation integrated bioreactor. The method comprises the following steps of: sequentially feeding materialized and pre-treated coal chemical wastewater into an anaerobic bioreactor, an anoxic bioreactor, a first-stage aerobiotic bioreactor, a second-stage aerobiotic bioreactor and a third-stage aerobiotic bioreactor, selecting each aerobiotic bioreactor to discharge water and inflow into the anoxic bioreactor; and carrying out anaerobic acidification treatment by the anaerobic reactor, reinforcing a biological denitrification reaction in the anoxic reactor to remove non-gradable organic matters, completely decarbonizing by the first-stage aerobiotic bioreactor, and realizing the short-course nitratlon reaction and the whole-course nitratlon reaction by the second-stage aerobiotic bioreactor and the third-stage aerobiotic bioreactor, wherein the sludge concentration in the reactor can be guaranteed to be greater than 8mg/L due to the biological reaction-muddy water separation integrated bioreactor, the sludge age is greater than 60 days, the specific strains can be preferably cultured, and the function realization of a novel method can be guaranteed. The coal chemical wastewater is treated by the method, so that the discharged water can reach the requirement of the national wastewater comprehensive discharge standard.
Description
Technical field
The present invention relates to field of waste water treatment, particularly, the present invention relates to the coal chemical industrial waste water process field containing high concentration organic contaminant and ammonia nitrogen.
Background technology
Coal chemical industrial waste water is Coal Chemical Industry production process, the waste water producing in coal high-temperature coking, gas purification, coke chemicals recovery and treating process.Various, the complicated component of pollutant kind in coal chemical industrial waste water, as the organic pollutants such as phenols, benzene homologues, nitrogen heterocyclic ring aromatic hydrocarbons, polycyclic aromatic hydrocarbons, the ammonia nitrogen of the poisonous inorganic pollutants such as sulfide, thiocyanide, prussiate and high density.Biological process is the treatment technology adopting at present extensively, wherein with traditional biological denitrification process (A/O technique) and improve technique (as A
2/ O, A
2/ O
2etc. technique) application is at most.
For example, CN 102659287A discloses the integrated processes that a kind of coal chemical industrial waste water is processed, and it relates to coal chemical industry wastewater treating method.This invention realizes as follows: coal chemical industrial waste water first carries out oil removal treatment by oil trap; Passing into acidication tower decomposes the organism of difficult degradation again; And then process degradation of organic substances matter through anaerobic-aerobic fluidized-bed coupling biochemical system; Finally pass into coagulative precipitation tank and carry out precipitation process, mud is arranged outward, and water outlet flows into clean water basin.
These treatment process water outlets COD is difficult to reach national sewage comprehensive emission standard requirement (GB9878-1996, i.e. COD<100mg/L), and processing cost is very high.Major cause is:
(1) organism that is difficult in coal chemical industrial waste water to remove by traditional biological method accounts for the 10-20% of total organic matter, mostly wherein is baroque phenols, heterogeneous ring compound, Polycyclic aromatic hydrocarbons and Derivatives.Traditional activated sludge process carries out in biology aerobic degradation process, and this class mass degradation speed is very slow or can not degrade; On the other hand, aerobic degradation, along with the open loop of polycyclic aromatic hydrocarbons structure may produce the more difficult materials that are biodegradable such as long-chain acids, ketone, lipid, causes the COD of processed waste water generally higher, at 300-500mg/L.
(2) on the other hand, traditional biological technique often adopts single aerobic reaction pond to remove organism and ammonia nitrogen, be that aerobic heterotrophic bacterium and nitrobacteria grow simultaneously, and bioprocess technology adopts very high return sludge ratio (>150%), make active sludge periodically-varied growth conditions, bring into play different biological functions, be unfavorable for forming functional flora, and suppress the activity of nitrobacteria, cause that treatment process organic matter removal efficiency is low, operation stability is poor, processing cost is higher.In this case, heterotrophic bacterium dominant growth and nitrobacteria activity is suppressed, the preferential degradation of organic substances of active sludge; The functional flora poor growth of the hardly degraded organic substance that degrading waste water toxic is very strong and external environment that need to be stable, culture cycle is longer.The organism of high density can suppress the activity of nitrobacteria, and nitration reaction only occurs in aerobic reaction pond end, and nitrobacteria poor growth, the generation cycle is long, resistance to poison is poor, affects bioprocess technology operation stability and improves processing cost.
(3) coal chemical industrial waste water is containing the ammonia nitrogen of high density, and traditional biological denitrification process is longer, needs to consume a large amount of power and medicament, causes cost for wastewater treatment very high.
Zhou Mei (Pan Gang coal plant Waste Water Treatment Optimizing Reconstruction, Zhou Mei, industrial safety and environmental protection, the 35th the 7th phase of volume in 2009, in July, 2009) adopts A/O
2+ Biological Contact Oxidation Process is processed waste water.This invention does not adopt anaerobic reaction that hardly degraded organic substance is converted into easy degradation of small molecular organism at hypoxia response, causes hypoxia response pressure larger, causes the removal efficiency of hardly degraded organic substance lower; In addition, although it separately carries out decarburization and nitration reaction, and nitration reaction is divided into two steps, but its two steps nitration reaction condition is identical, i.e. short distance nitration reaction and complete nitrification reaction are carried out simultaneously, cause oxygen requirement and alkali consumption higher, processing cost is high, and treatment rate is lower.
(the biomembrance process A such as Li Yaxin
2/ O
2aerobic reactor operational characteristic in coking wastewater processing system, Li Yaxin, Zhao Yi, Yue Xiuping, Yang Huaiwang, Du Jincheng, Yao Runsheng, Ma Jianan, Treatment of Industrial Water, the 28th the 1st phase of volume, in January, 2008) employing biomembrance process A
2/ O
2method Treatment of Wastewater in Coking, it adopts two step aerobic reactions, i.e. and decarburization and nitration reaction are separately carried out, and are conducive to the processing of nitrifier to ammonia nitrogen.But it adopts a step nitrated, short distance nitration reaction and complete nitrification reaction are carried out simultaneously, and in order to reduce water outlet Nitrite content, reduce water outlet toxicity, certainly will take complete nitrification as main, therefore, oxygen requirement and alkali consumption are higher, and processing cost is high, and treatment rate is lower.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of coal chemical industrial waste water biological treatment novel method, hardly degraded organic substance by exploitation biological denitrification is removed ability and short distance nitration-denitrification biological denitrogenation new technology coupling integration, realization fast, efficiently, wastewater treatment cheaply.
Described coal chemical industrial waste water bioremediation is anaerobic-anoxic/oxidation of coal-short distance nitration-complete nitrification (A
2/ O
3) method, comprise: make to enter successively anaerobic reactor, anoxic reacter, one-level aerobic reactor, secondary aerobic reactor and three grades of aerobic reactors through the coal chemical industrial waste water of physico-chemical pretreatment, then discharge, wherein, anoxic reacter N/C value is 2.5-3.5, one-level aerobic reactor dissolved oxygen concentration is 1-6mg/L, secondary aerobic reactor dissolved oxygen concentration is 1-3mg/L, temperature is 30-38 ℃, pH is 7.5-9, three grades of aerobic reactor dissolved oxygen concentrations are 3-5mg/L, and temperature is 22-30 ℃, and pH is 6.5-7.5.
Described anoxic process is enhanced biological denitrification process.
Described physico-chemical pretreatment is the conventional physical chemistry pretreatment process in affiliated field, such as: oil removal, coagulating sedimentation etc.
Preferably, secondary and/or three grades of aerobic reactor effluent recyclings are to anoxic reacter; Described reflux ratio is nitrification liquid reflux ratio, is preferably 2:1-8:1, is particularly preferably 3:1-6:1.
Preferably, in anoxic reacter, add nitrate radical and/or nitrite anions.
Preferably, in one-level aerobic reactor, add alkali and/or phosphorus source; Preferably, described alkali is carbonate, is particularly preferably sodium carbonate; Preferably, described phosphorus source is hydrophosphate, is particularly preferably Sodium phosphate dibasic.
Field normal condition under the processing condition of described anaerobic reaction can adopt, for example: temperature is controlled between 32-35 ℃, hydraulic detention time is that 24-36 hour, sludge concentration are controlled between 50-100g/L, pH value is controlled between 7.0～7.5.
Preferably, hypoxia response actuator temperature is 20-38 ℃, such as 20.1 ℃, 20.2 ℃, 20.5 ℃, 21 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 35.8 ℃, 35.9 ℃, 36.1 ℃, 36.5 ℃, 37 ℃, 37.5 ℃, 37.8 ℃, 37.9 ℃ etc., be preferably 23-36 ℃, be particularly preferably 25-35 ℃.
Preferably, anoxic reacter dissolved oxygen concentration is below 0.8mg/L, more preferably, below 0.6mg/L, is particularly preferably 0.5mg/L.
Preferably, anoxic reacter N/C value is 2.9-3.2, is particularly preferably 3.
Preferably, anoxic reacter pH value is 7.7-9.3, and more preferably 7.9-9.1, is particularly preferably 8-9.
One-level aerobic reactor dissolved oxygen concentration can be preferably 1-5mg/L for 1.1mg/L, 1.2mg/L, 1.3mg/L, 1.5mg/L, 2mg/L, 3mg/L, 3.9mg/L, 4.1mg/L, 4.5mg/L, 4.8mg/L, 4.9mg/L etc., is particularly preferably 1-4mg/L.
Secondary aerobic reactor dissolved oxygen concentration can, for 1.1mg/L, 1.2mg/L, 1.3mg/L, 1.5mg/L, 1.8mg/L, 1.9mg/L, 2.1mg/L, 2.2mg/L, 2.5mg/L, 2.8mg/L, 2.9mg/L etc., be preferably 2-3mg/L.
Secondary aerobic reaction actuator temperature can be 30.1 ℃, 30.2 ℃, 30.3 ℃, 30.5 ℃, 31 ℃, 32 ℃, 34 ℃, 36 ℃, 36.5 ℃, 36.9 ℃, 37.1 ℃, 37.5 ℃, 37.8 ℃, 37.9 ℃ etc., be preferably 30-37 ℃, be particularly preferably 30-35 ℃.
The pH of secondary aerobic reactor can be 7.51,7.52,7.53,7.55,7.6,7.7,7.9,8.0,8.1,8.2,8.3,8.4,8.45,8.49,8.51,8.55,8.59,8.61,8.69,8.71,8.75,8.8,8.9,8.95,8.98,8.99 etc., be preferably 7.5-8.7, be particularly preferably 7.5-8.5.
Three grades of aerobic reactor dissolved oxygen concentrations can, for 3.1mg/L, 3.2mg/L, 3.3mg/L, 3.5mg/L, 3.8mg/L, 3.9mg/L, 4.1mg/L, 4.2mg/L, 4.5mg/L, 4.8mg/L, 4.9mg/L etc., be preferably 4mg/L.
Three grades of aerobic reaction actuator temperatures can be 22.1 ℃, 22.2 ℃, 22.5 ℃, 23 ℃, 23.5 ℃, 23.8 ℃, 23.9 ℃, 24.1 ℃, 24.5 ℃, 24.9 ℃, 25.1 ℃, 25.5 ℃, 26 ℃, 28 ℃, 29.5 ℃, 29.8 ℃, 29.9 ℃ etc., be preferably 24-30 ℃, be particularly preferably 25-30 ℃.
The pH of three grades of aerobic reactors can be 6.51,6.52,6.55,6.6,6.7,6.75,6.79,6.81,6.85,6.9,6.95,6.99,7.1,7.2,7.3,7.4,7.45,7.48,7.49 etc., be preferably 6.8-7.5, be particularly preferably 7.0-7.5.
Preferably, the hydraulic detention time in anaerobic reactor is at least 5 hours, and more preferably 6-15 hour, is particularly preferably 7-10 hour.
Preferably, the hydraulic detention time in anoxic reacter is at least 10 hours, and more preferably 13-40 hour, is particularly preferably 15-30 hour.
Preferably, the hydraulic detention time in one-level aerobic reactor is at least 10 hours, and more preferably 13-40 hour, is particularly preferably 15-30 hour.
Preferably, the hydraulic detention time in secondary aerobic reactor is at least 7 hours, and more preferably 8-30 hour, is particularly preferably 10-20 hour.
Preferably, the hydraulic detention time in three grades of aerobic reactors is at least 6 hours, and more preferably 8-20 hour, is particularly preferably 10-15 hour.
The present invention, by higher nitrification liquid reflux ratio (2:1-8:1) and additional nitrate radical and/or nitrite anions, makes anoxic reacter have higher N/C value; Adopt present method to process coal chemical industrial waste water, water outlet can reach national sewage comprehensive discharge primary standard (GB9878-1996).
One of object of the present invention is also to provide a kind of coal chemical industrial waste water biological treatment system.As shown in Figure 1, described coal chemical industrial waste water biological treatment system comprises successively according to the flow direction of waste water: physico-chemical pretreatment system, anaerobism (A
1) reactor, anoxic (A
2) reactor, the aerobic (O of one-level
1) reactor, the aerobic (O of secondary
2) reactor and three grades of aerobic (O
3) reactor.Each reactor detects each processing parameter by online dissolved oxygen (DO), redox potential (ORP) and pH electrode.Each reactor connects by the known mode in affiliated field.
Preferably, described coal chemical industrial waste water biological treatment system also comprises the pipeline to anoxic reacter by secondary and/or three grades of aerobic reactor effluent recyclings.
Preferably, each stage reactor water outlet absolute altitude to successively decreasing successively, makes coal chemical industrial waste water realize gravity flow at each stage reactor according to wastewater streams, except anaerobic reactor without being installed into water pump.
One of object of the present invention is also to provide a kind of novel " biological respinse-mud-water separation integrated bioreactor ".Described biological respinse-mud-water separation integrated bioreactor comprises bio-reaction zone 1 and mud-water separation district 2, wherein, mud-water separation district 2 comprises strengthening sedimentation device 3, sludge refluxing apparatus 4, mud transmission mechanism 5 and collection mud device 6, strengthening sedimentation device 3 is positioned at 2 tops, mud-water separation district, strengthening sedimentation device 3 bottoms arrange slope, be beneficial to mud gravity reflux, top, slope and middle part arrange sludge refluxing apparatus 4, action edge under pressure while depositing as mud, collection mud device 6 is installed in bottom, slope, 2 bottoms, mud-water separation district and bio-reaction zone 1 bottom connecting place are installed mud transmission mechanism 5, mud is advanced to bio-reaction zone 1 from mud-water separation district 2, mud transmission mechanism 5 is positioned at collection mud device 6 tops.
Preferably, described slope and horizontal plane angle are 30-80 °, are particularly preferably 40-70 °.
Preferably, described reactor bottom water inlet, top water outlet.
Preferably, submersible agitator is installed in the bio-reaction zone 1 of anaerobic reactor and/or anoxic reacter.
Preferably, micro-hole aerator oxygenation is installed in the bottom of aerobic reactor.
One of object of the present invention is also to provide a kind of purposes of described biological respinse-mud-water separation integrated bioreactor.Described biological respinse-mud-water separation integrated bioreactor can be used for described coal chemical industrial waste water biological treatment system, particularly preferably, all reactors of described coal chemical industrial waste water biological treatment system are all described biological respinse-mud-water separation integrated bioreactor.
The aerobic reactor of take illustrates the operational process of described biological respinse-mud-water separation integrated bioreactor as example (as shown in Figure 2): coal chemical industrial waste water enters behind bio-reaction zone 1, under aeration effect, fully mix with active sludge, and obtain oxygenolysis under microbial process, muddy water mixed solution evenly enters mud-water separation district 2 by inlet channel, then at strengthening sedimentation device 3, carries out mud-water separation.Clear water outflow system after separation, the active sludge of precipitation by the descending aeration zone that is back to of gravity, is brought to rapidly the middle and upper part of aeration zone along slope by up aeration gas flow, mix with waste water.While causing that when mud appearance alluvial gravity reflux is smooth, can open sludge refluxing apparatus 4, accelerate sludge is descending, when alluvial especially severe, can open mud transmission mechanism 5, impels mud to reflux to aeration zone.Unnecessary mud can intermittently pass through perforated sludge discharge pipe spoil disposal, then by sludge pump, sends system.Wherein, the long-width ratio of bio-reaction zone 1 is 1:1～2:1.
Described biological respinse-mud-water separation integrated bioreactor can make active sludge in inside reactor self-circulation, be conducive to cultivate function bacterial classification and improve contaminant degradation efficiency, can greatly improve sludge age and sludge concentration, sludge age can keep being greater than 60 days, sludge concentration can maintain and be greater than 8mg/L, be conducive to cultivate function bacterial classification, guarantee coal chemical industrial waste water bioremediation practical function of the present invention.In the anoxic stage, can cultivate dominant microflora and remove hardly degraded organic substance by denitrification; At aerobic stage, heterotrophic bacterium and nitrobacteria are spatially isolated respectively and cultivated, tame exclusive bacterial classification, and then optimization process effect, the processing cost that reduces.
Adopt anaerobic acidification-intensified anti-nitrated/oxidation of coal-short distance nitration-complete nitrification technique (A of " biological respinse-mud-water separation integrated bioreactor "
2/ O
3) process coal chemical industrial waste water, water outlet can reach national sewage comprehensive discharge primary standard (GB9878-1996).
N/C value of the present invention is NO
3 --N and NO
2 --N/COD, i.e. ([NO
3 --N]+[NO
2 --N])/COD.
Compared with prior art, advantage of the present invention is:
(1) the method for the invention has higher antipollution thing load impact ability: the variation water quality of coal chemical industrial waste water is larger, especially ammonia nitrogen, the influent ammonium concentration of coal chemical industrial waste water generally fluctuates between 50-500mg/L, very large to the impact for the treatment of system, each stage of the method for the invention all adopts new-type bioreactor, can realize the internal recycle of active sludge in reactor, more than sludge concentration can reach 8mg/L, sludge age keeps being longer than 60 days, can maintain the flora structural stability of active sludge and keep higher sludge concentration.
(2) the method for the invention has higher Persistent organic pollutants removal efficiency: in coal chemical industrial waste water, contain high-concentration hardly-degradable organism, traditional biological method is lower to the clearance of these materials, causes effluent COD concentration higher; The method of the invention improves waste water N/C value for more than 2:1, the removal ability of enhanced biological denitrification to hardly degraded organic substance by the mode of adjusting process parameter and interpolation nitrate radical and/or nitrite anions; On the other hand, the employing of novel reactor can realize oxidation operation and complete at reactor independently, greatly extends sludge age, improves sludge concentration, can cultivate efficient functional flora, optimizes the removal efficiency of hardly degraded organic substance.
(3) the method for the invention can steady removal ammonia nitrogen: coal chemical industrial waste water is containing high concentration organic contaminant and ammonia nitrogen, traditional biological denitrogenation method completes oxidation of coal and nitration reaction at single reactor, nitration reaction efficiency is low and operation is very unstable, and is vulnerable to the impact of operating load and causes system crash; The method of the invention realizes oxidation of coal and nitration reaction completes in different reactor, can maintain compared with high sludge concentration and make nitrobacteria keep high reactivity; In addition, adopt two-stage aerobic reactor to remove stage by stage ammonia nitrogen, at secondary and three grades of aerobic reactors, realize respectively short distance and complete nitrification, volumetric loading is high, strong shock resistance.
(4) the method for the invention has lower processing cost: coal chemical industrial waste water is containing hardly degraded organic substance and the ammonia nitrogen of high density, and traditional biology aerobic process electric power, reagent consumption amount are large, and biological treatment cost is very high; The method of the invention is removed most of hardly degraded organic substance by the anti-nitration reaction of strengthening anoxic reacter, and by short distance nitration, removes the ammonia nitrogen of most of high density, can reduce 30% power consumption and 20% reagent consumption, significantly reduces processing cost.
(5) adopt anaerobic acidification-intensified anti-nitrated/oxidation of coal-short distance nitration-complete nitrification technique (A of " biological respinse-mud-water separation integrated bioreactor "
2/ O
3) processing coal chemical industrial waste water, COD and ammonia nitrogen removal frank can reach respectively more than 95% and 97%, and water outlet can reach the requirement of national sewage comprehensive discharge primary standard.
Accompanying drawing explanation
Fig. 1 is anaerobic acidification-enhanced biological denitrification/oxidation of coal-short distance nitration-complete nitrification (A of the present invention
2/ O
3) schema of an embodiment of coal chemical industrial waste water bioremediation.
Fig. 2 is the schematic diagram of an embodiment of biological respinse-mud-water separation integrated biological reactor of the present invention.
Reference numeral is as follows:
1-bio-reaction zone; 2-mud-water separation district; 3-strengthening sedimentation device;
4-sludge refluxing apparatus; 5-mud transmission mechanism.
Embodiment
Adopt anaerobic acidification-intensified anti-nitrated/oxidation of coal-short distance nitration-complete nitrification technique (A of " biological respinse-mud-water separation integrated bioreactor "
2/ O
3) process coal chemical industrial waste water, embodiment is as follows:
The bottom water distribution system that enters anaerobic reactor through pretreated coal chemical industrial waste water, the nitrification liquid (from secondary or three grades of aerobic reactors, reflux ratio 2:1-8:1) simultaneously refluxing is also back to this water distribution system.Each stage reactor water outlet absolute altitude successively decreases successively, makes coal chemical industrial waste water realize gravity flow at each stage reactor.In anaerobic reactor, carry out anaerobic acidification processing, macromole hardly degraded organic substance in coal chemical industrial waste water is converted into easy degradation of small molecular organism to a certain extent, can improve coal chemical industrial waste water can be biological and play the effect of regulating water quality, and anaerobic reactor hydraulic detention time is about at least 5 hours.The organic pollutant that denitrifying bacterium in anoxic reacter be take in coal chemical industrial waste water is carbon source, and reflux supernatant liquor Central Asia nitrate or the nitrate of take is electron acceptor(EA), breathes and vital movement, is reduced into nitrogen (N
2) overflow, when realizing biological denitrificaion, remove hardly degraded organic substance.In present method, by maintaining higher nitrification liquid reflux ratio and adding certain nitrate or nitroso-group nitrogen, make to maintain more than 2.5 into the N/C value of water, make majority of organic pollutants in coal chemical industrial waste water react removal by biological denitrification.The basicity that anti-nitration reaction produces can compensate the basicity of follow-up nitration reaction 50% left and right, and removal process do not need aeration, therefore can greatly reduce processing cost.The hydraulic detention time of anoxic reacter is about at least 10 hours.
The water outlet gravity flow of anoxic reacter enters one-level aerobic reactor, supplements certain basicity (Na simultaneously
2cO
3) and phosphorus source (Na
2hPO
3).Each aerobic reactor bottom adopts micro-hole aerator oxygenation, by automation system, controls dissolved oxygen concentration (DO) and the pH value in reactor.In one-level aerobic reactor, heterotrophic bacterium is reacted and is removed in coal chemical industrial waste water remaining organic pollutant after anoxic denitrification reaction by biology aerobic, realize gross decarburization, because one-level aerobic reactor has longer sludge age and compared with high sludge concentration, and anoxic reacter steady running can largely reduce organic loading, one-level aerobic reactor water outlet gravity flow enters secondary and three grades of aerobic reactors successively, realizes the oxidation stage by stage of ammonia nitrogen at secondary and three grades of aerobic reactors.Control suitable processing parameter, in secondary aerobic reactor by ammonia nitrogen oxidation control in nitrosification, realize short distance nitration, ammonia nitrogen major part is oxidized to nitroso-group nitrogen.Three grades of aerobic reactors are removed ammonia nitrogen remaining after one-level aerobic reactor, and are nitrate by the nitroso-group nitrogen transformation in the water outlet of secondary aerobic reactor, realize complete nitrification.
Denitrification
Traditional denitrification is mainly used in removing nitrate, by improving the organic pollutant that in waste water, the strengthening of N/C value is removed in coal chemical industrial waste water, is a new way that is worth trial, take phenol as example, its reaction formula as the formula (1):
Anaerobic environment is rich in polycyclic aromatic hydrocarbons ring-opening enzyme system, the method of the invention denitrification section not only has the function of biological denitrificaion, and can remove the organism that is difficult for being degraded in traditional aerobe treating processes, the material such as long-chain acids, ketone, lipid that simultaneously greatly reduces generation, significantly reduces Process for Effluent COD.
Short distance nitration-denitrification process
Short distance nitration-denitrification process is that ammonia nitrogen oxidising process is controlled to the nitrite anions stage, and it is applied to coal chemical industrial waste water biological treatment, and tool has the following advantages: the nitrated stage can reduce the oxygen requirement of 30% left and right and 25% alkali consumption, reduces approximately 20% processing cost; Floor space is little, and reactor volume can reduce 30%-40% left and right; There is higher denitrification rate (NO
2 -denitrification rate is conventionally than NO
3 -high 63% left and right); Sludge yield reduces (nitrifying process can produce mud 33%-35% left and right less, in denitrification process, can produce less mud 55% left and right).
The method of the invention operation control condition:
Adopt anaerobic acidification-enhanced biological denitrification/oxidation of coal-short distance nitration-complete nitrification (A
2/ O
3) coal chemical industrial waste water biological denitrification method and system anoxic reacter N/C value, dissolved oxygen concentration, pH value, temperature, add alkali number, phosphorus amount control quality relevant, not only affect method to pollutant removal, and be related to the height of processing cost, therefore, on-line monitoring and analytical test are important rings of controlling run.
(1) anoxic reacter N/C value.
Denitrifying bacterium, by biological denitrification process decomposing organic pollutant, is incited somebody to action the BOD in waste water theoretically
5during/TKN>2.86, oxidation state nitrogen can be satisfied the demand, BOD
5clearance can reach more than 80%.The organic pollutant that contains high density in coal chemical industrial waste water, especially contains hardly degraded organic substance, thereby the TKN concentration that intensified anti-nitrated reaction process need to be higher, needs higher N/C value, and it is 2.5-3.5 that present method maintains N/C.
(2) dissolved oxygen concentration.
Heterotrophic bacterium is removed the organic pollutant in coal chemical industrial waste water under aerobic condition, and one-level aerobic reactor dissolved oxygen concentration maintains 1-6mg/L.Nitrite bacteria, nitrobacteria are aerobic bacterias, must have under the environment of dissolved oxygen, make ammonia nitrogen be oxidized to nitroso-group nitrogen and nitrate.Controlling dissolved oxygen is the important means in the nitroso-group nitrogen stage by ammonia nitrogen oxidation control, and in present method secondary aerobic reactor, Dissolved Oxygen concentration Control, at 1-3mg/L, can efficiently be removed ammonia nitrogen by short distance nitration; At three grades of aerobic reactors, by controlling dissolved oxygen concentration in 3-5mg/L left and right, make nitroso-group nitrogen effectively be converted into fast nitrate, realize complete nitrification.In anoxic reacter, denitrifying bacteria is that nitrogen is overflowed by nitroso-group nitrogen and partial nitro nitrogen transformation, is to carry out under the condition of anoxic, and dissolved oxygen in anoxic tank is controlled at below 0.8mg/L.
(3) temperature.
Nitrobacteria is very sensitive to the variation of temperature, and the most suitable growth temperature of nitrobacteria is between 27-32 ℃, and lower than 27 ℃ or higher than 32 ℃ of decreased growths, growth and the rate of nitrification of 15 ℃ of following nitrobacterias significantly slow down.It is responsive that denitrifying bacterium is not so good as nitrobacteria to the variation of temperature.The suitable growth temperature of denitrifying bacterium is between 30-35 ℃, lower than 15 ℃ of denitrification rates, significantly slows down.The effect of present method secondary aerobic denitrification performance short distance nitration, temperature is controlled at 30-38 ℃; Three grades of aerobic reactors are realized complete nitrification, and temperature is controlled at 22-30 ℃; The denitrification of strengthening anoxic reacter, temperature is controlled at 20-38 ℃.
(4) pH value.
Nitrite bacteria and nitrobacteria are very responsive to the variation of pH value, and the suitable pH value of nitrite bacteria is 7.0-8.5, and the suitable pH value of nitrobacteria is 6.5-7.5.Secondary aerobic reactor pH value is controlled at 7.5-9, and three grades of aerobic reactor pH values are controlled at 6.5-7.5.Denitrifying bacterium is responsive not as nitrobacteria to the variation of pH value, in pH value, is within the scope of 6-9, all can carry out normal physiological metabolism, and anoxic reacter pH value is controlled at 7.7-9.3.
(5) impact of toxic substance
Coal chemical industrial waste water forms complicated, and the pollutent wherein containing, as fugitive constituent, ammonia nitrogen, heavy metal ion, complex anion, prussiate and some toxic organic compounds can disturb or destroy the normal physiological activity of bacterium, and then affects the normal operation of method.While being greater than 200mg/L as being greater than 5.6mg/L, ammonia nitrogen concentration when phenol concentration, nitration reaction can be suppressed.Free ammonia (FA) has restraining effect in various degree to nitrobacteria, nitrite bacteria.When FA concentration is greater than 5mg/L, although nitroso-group nitrogen accounts for nitrate ratio height, along with FA concentration rises, nitrite bacteria also can be gradually in holddown.
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Each reactor of following examples is biological respinse-mud-water separation integrated bioreactor of the present invention, comprises bio-reaction zone 1 and mud-water separation district 2, wherein, mud-water separation district 2 comprises strengthening sedimentation device 3, sludge refluxing apparatus 4, mud transmission mechanism 5 and collection mud device 6, strengthening sedimentation device 3 is positioned at 2 tops, mud-water separation district, strengthening sedimentation device 3 bottoms arrange slope, be beneficial to mud gravity reflux, top, slope and middle part arrange sludge refluxing apparatus 4, action edge under pressure while depositing as mud, collection mud device 6 is installed in bottom, slope, 2 bottoms, mud-water separation district and bio-reaction zone 1 bottom connecting place are installed mud transmission mechanism 5, mud is advanced to bio-reaction zone 1 from mud-water separation district 2, mud transmission mechanism 5 is positioned at collection mud device 6 tops, described slope and horizontal plane angle are 30-80 °, described reactor bottom water inlet, top water outlet, submersible agitator is installed in the bio-reaction zone 1 of anaerobic reactor and anoxic reacter, micro-hole aerator oxygenation is installed in the bottom of one-level, secondary and three grades of aerobic reactors, by automation system, controls dissolved oxygen concentration (DO) and the pH value in reactor.
Embodiment 1
The bottom that enters anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.In anaerobic reactor, carry out anaerobic acidification processing, anaerobic reactor hydraulic detention time is 7 hours.Anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid simultaneously refluxing is (from secondary and three grades of aerobic reactors, reflux ratio 6:1) be also back to this water distribution system, anoxic reacter dissolved oxygen concentration is 0.5mg/L, N/C value is 3, temperature is 25 ℃, and pH is 9, and hydraulic detention time is about 15 hours.The water outlet gravity flow of anoxic reacter enters one-level aerobic reactor, supplements certain Na simultaneously
2cO
3and Na
2hPO
3.One-level aerobic reactor dissolved oxygen concentration is 4mg/L, and temperature is 28 ℃, and pH is 7, and hydraulic detention time is about 30 hours.One-level aerobic reactor water outlet gravity flow enters secondary and three grades of aerobic reactors successively, secondary aerobic reactor dissolved oxygen concentration is 2mg/L, temperature is 35 ℃, pH is 8.0, hydraulic detention time is about 15 hours, and three grades of aerobic reactor dissolved oxygen concentrations are 4mg/L, and temperature is 28 ℃, pH is 7.2, and hydraulic detention time is about 15 hours.Reflux in secondary aerobic reactor and three grades of aerobic reactor water parts, reflux ratio is 6:1, three grades of all the other water outlet COD of aerobic reactor and ammonia nitrogen removal frank reach respectively 98% and 99%, and water outlet can reach national sewage comprehensive discharge primary standard requirement (GB9878-1996).
Embodiment 2
The bottom that enters anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.In anaerobic reactor, carry out anaerobic acidification processing, anaerobic reactor hydraulic detention time is 5 hours.Anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid simultaneously refluxing is (from secondary and three grades of aerobic reactors, reflux ratio 2:1) be also back to this water distribution system, anoxic reacter dissolved oxygen concentration is 0.8mg/L, N/C value is 2.5, temperature is 38 ℃, and pH is 7.7, and hydraulic detention time is about 40 hours.The water outlet gravity flow of anoxic reacter enters one-level aerobic reactor, supplements certain Na simultaneously
2cO
3and Na
2hPO
3.One-level aerobic reactor dissolved oxygen concentration is 6mg/L, and temperature is 28 ℃, and pH is 7, and hydraulic detention time is about 40 hours.One-level aerobic reactor water outlet gravity flow enters secondary and three grades of aerobic reactors successively, secondary aerobic reactor dissolved oxygen concentration is 3mg/L, temperature is 30 ℃, pH is 9, hydraulic detention time is about 7 hours, and three grades of aerobic reactor dissolved oxygen concentrations are 5mg/L, and temperature is 22 ℃, pH is 7.5, and hydraulic detention time is about 20 hours.Reflux in secondary aerobic reactor and three grades of aerobic reactor water parts, reflux ratio is 2:1, three grades of all the other water outlet COD of aerobic reactor and ammonia nitrogen removal frank reach respectively 96% and 97%, and water outlet can reach national sewage comprehensive discharge primary standard requirement (GB9878-1996).
Embodiment 3
The bottom that enters anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.In anaerobic reactor, carry out anaerobic acidification processing, anaerobic reactor hydraulic detention time is 15 hours.Anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid simultaneously refluxing is (from secondary and three grades of aerobic reactors, reflux ratio 8:1) be also back to this water distribution system, anoxic reacter dissolved oxygen concentration is 0.6mg/L, N/C value is 3.5, temperature is 20 ℃, and pH is 9.3, and hydraulic detention time is about 10 hours.The water outlet gravity flow of anoxic reacter enters one-level aerobic reactor, supplements certain Na simultaneously
2cO
3and Na
2hPO
3.One-level aerobic reactor dissolved oxygen concentration is 1mg/L, and temperature is 28 ℃, and pH is 7, and hydraulic detention time is about 10 hours.One-level aerobic reactor water outlet gravity flow enters secondary and three grades of aerobic reactors successively, secondary aerobic reactor dissolved oxygen concentration is 1mg/L, temperature is 38 ℃, pH is 7.5, hydraulic detention time is about 30 hours, and three grades of aerobic reactor dissolved oxygen concentrations are 3mg/L, and temperature is 30 ℃, pH is 6.5, and hydraulic detention time is about 6 hours.Reflux in secondary aerobic reactor and three grades of aerobic reactor water parts, reflux ratio is 8:1, three grades of all the other water outlet COD of aerobic reactor and ammonia nitrogen removal frank reach respectively 95% and 98%, and water outlet can reach national sewage comprehensive discharge primary standard requirement (GB9878-1996).
Embodiment 4
The bottom that enters anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.In anaerobic reactor, carry out anaerobic acidification processing, anaerobic reactor hydraulic detention time is 6 hours.Anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid simultaneously refluxing is (from secondary and three grades of aerobic reactors, reflux ratio 7:1) be also back to this water distribution system, anoxic reacter dissolved oxygen concentration is 0.7mg/L, N/C value is 3.3, temperature is 22 ℃, and pH is 7.8, and hydraulic detention time is about 13 hours.The water outlet gravity flow of anoxic reacter enters one-level aerobic reactor, supplements certain Na simultaneously
2cO
3and Na
2hPO
3.One-level aerobic reactor dissolved oxygen concentration is 2mg/L, and temperature is 28 ℃, and pH is 7, and hydraulic detention time is about 12 hours.One-level aerobic reactor water outlet gravity flow enters secondary and three grades of aerobic reactors successively, secondary aerobic reactor dissolved oxygen concentration is 1.5mg/L, temperature is 36 ℃, pH is 7.6, hydraulic detention time is about 8 hours, and three grades of aerobic reactor dissolved oxygen concentrations are 3.5mg/L, and temperature is 23 ℃, pH is 7.2, and hydraulic detention time is about 8 hours.Reflux in secondary aerobic reactor and three grades of aerobic reactor water parts, reflux ratio is 7:1, three grades of all the other water outlet COD of aerobic reactor and ammonia nitrogen removal frank reach respectively 96% and 98%, and water outlet can reach national sewage comprehensive discharge primary standard requirement (GB9878-1996).
Embodiment 5
The bottom that enters anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.In anaerobic reactor, carry out anaerobic acidification processing, anaerobic reactor hydraulic detention time is 13 hours.Anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid simultaneously refluxing is (from secondary and three grades of aerobic reactors, reflux ratio 2.5:1) be also back to this water distribution system, anoxic reacter dissolved oxygen concentration is 0.6mg/L, N/C value is 2.7, temperature is 37 ℃, and pH is 9.2, and hydraulic detention time is about 14 hours.The water outlet gravity flow of anoxic reacter enters one-level aerobic reactor, supplements certain Na simultaneously
2cO
3and Na
2hPO
3.One-level aerobic reactor dissolved oxygen concentration is 1.4mg/L, and temperature is 28 ℃, and pH is 7, and hydraulic detention time is about 35 hours.One-level aerobic reactor water outlet gravity flow enters secondary and three grades of aerobic reactors successively, secondary aerobic reactor dissolved oxygen concentration is 1.2mg/L, temperature is 37 ℃, pH is 8.8, hydraulic detention time is about 25 hours, and three grades of aerobic reactor dissolved oxygen concentrations are 4.5mg/L, and temperature is 24 ℃, pH is 6.6, and hydraulic detention time is about 17 hours.Reflux in secondary aerobic reactor and three grades of aerobic reactor water parts, reflux ratio is 2.5:1, three grades of all the other water outlet COD of aerobic reactor and ammonia nitrogen removal frank reach respectively 97% and 99%, and water outlet can reach national sewage comprehensive discharge primary standard requirement (GB9878-1996).
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (45)
1. a coal chemical industrial waste water bioremediation, comprise: the coal chemical industrial waste water through physico-chemical pretreatment enters anaerobic reactor, anoxic reacter, one-level aerobic reactor, secondary aerobic reactor and three grades of aerobic reactors successively, then discharge, wherein, anoxic reacter N/C value is 2.5-3.5, one-level aerobic reactor dissolved oxygen concentration is 1-6mg/L, secondary aerobic reactor dissolved oxygen concentration is 1-3mg/L, temperature is 30-38 ℃, pH is 7.5-9, three grades of aerobic reactor dissolved oxygen concentrations are 3-5mg/L, and temperature is 22-30 ℃, and pH is 6.5-7.5;
In anoxic reacter, add nitrate radical and/or nitrite anions;
Secondary and/or three grades of aerobic reactor effluent recyclings are to anoxic reacter, and described reflux ratio is 2:1-8:1.
2. the method for claim 1, is characterized in that, described reflux ratio is 3:1-6:1.
3. the method for claim 1, is characterized in that, adds alkali and/or phosphorus source in one-level aerobic reactor.
4. method as claimed in claim 3, is characterized in that, described alkali is carbonate.
5. method as claimed in claim 4, is characterized in that, described alkali is sodium carbonate.
6. method as claimed in claim 3, is characterized in that, described phosphorus source is hydrophosphate.
7. method as claimed in claim 6, is characterized in that, described phosphorus source is Sodium phosphate dibasic.
8. method as claimed in claim 1 or 2, is characterized in that, hypoxia response actuator temperature is 20-38 ℃.
9. method as claimed in claim 8, is characterized in that, described hypoxia response actuator temperature is 23-36 ℃.
10. method as claimed in claim 8, is characterized in that, described hypoxia response actuator temperature is 25-35 ℃.
11. methods as claimed in claim 1 or 2, is characterized in that, anoxic reacter dissolved oxygen concentration is below 0.8mg/L.
12. methods as claimed in claim 11, is characterized in that, anoxic reacter dissolved oxygen concentration is below 0.6mg/L.
13. methods as claimed in claim 12, is characterized in that, anoxic reacter dissolved oxygen concentration is 0.5mg/L.
14. methods as claimed in claim 1 or 2, is characterized in that, anoxic reacter N/C value is 2.9-3.2.
15. methods as claimed in claim 14, is characterized in that, anoxic reacter N/C value is 3.
16. methods as claimed in claim 1 or 2, is characterized in that, anoxic reacter pH value is 7.7-9.3.
17. methods as claimed in claim 16, is characterized in that, anoxic reacter pH value is 7.9-9.1.
18. methods as claimed in claim 17, is characterized in that, anoxic reacter pH value is 8-9.
19. methods as described in claim 1-3 any one, is characterized in that, one-level aerobic reactor dissolved oxygen concentration is 1-5mg/L.
20. methods as claimed in claim 19, is characterized in that, one-level aerobic reactor dissolved oxygen concentration is 1-4mg/L.
21. methods as described in claim 1-3 any one, is characterized in that, secondary aerobic reactor dissolved oxygen concentration is 2-3mg/L.
22. methods as described in claim 1-3 any one, is characterized in that, secondary aerobic reaction actuator temperature is 30-37 ℃.
23. methods as claimed in claim 22, is characterized in that, secondary aerobic reaction actuator temperature is 30-35 ℃.
24. methods as described in claim 1-3 any one, is characterized in that, the pH of secondary aerobic reactor is 7.5-8.7.
25. methods as claimed in claim 24, is characterized in that, the pH of secondary aerobic reactor is 7.5-8.5.
26. methods as described in claim 1-3 any one, is characterized in that, three grades of aerobic reactor dissolved oxygen concentrations are 4mg/L.
27. methods as described in claim 1-3 any one, is characterized in that, three grades of aerobic reaction actuator temperatures are 24-30 ℃.
28. methods as claimed in claim 27, is characterized in that, three grades of aerobic reaction actuator temperatures are 25-30 ℃.
29. methods as described in claim 1-3 any one, is characterized in that, the pH of three grades of aerobic reactors is 6.8-7.5.
30. methods as claimed in claim 29, is characterized in that, the pH of three grades of aerobic reactors is 7.0-7.5.
31. methods as described in claim 1-4 any one, is characterized in that, the hydraulic detention time in anaerobic reactor is at least 5 hours.
32. methods as claimed in claim 31, is characterized in that, the hydraulic detention time in anaerobic reactor is 6-15 hour.
33. methods as claimed in claim 32, is characterized in that, the hydraulic detention time in anaerobic reactor is 7-10 hour.
34. methods as described in claim 1-4 any one, is characterized in that, the hydraulic detention time in anoxic reacter is at least 10 hours.
35. methods as claimed in claim 34, is characterized in that, the hydraulic detention time in anoxic reacter is 13-40 hour.
36. methods as claimed in claim 35, is characterized in that, the hydraulic detention time in anoxic reacter is 15-30 hour.
37. methods as described in claim 1-4 any one, is characterized in that, the hydraulic detention time in one-level aerobic reactor is at least 10 hours.
38. methods as claimed in claim 37, is characterized in that, the hydraulic detention time in one-level aerobic reactor is 13-40 hour.
39. methods as claimed in claim 38, is characterized in that, the hydraulic detention time in one-level aerobic reactor is 15-30 hour.
40. methods as described in claim 1-4 any one, is characterized in that, the hydraulic detention time in secondary aerobic reactor is at least 7 hours.
41. methods as claimed in claim 40, is characterized in that, the hydraulic detention time in secondary aerobic reactor is 8-30 hour.
42. methods as claimed in claim 41, is characterized in that, the hydraulic detention time in secondary aerobic reactor is 10-20 hour.
43. methods as described in claim 1-4 any one, is characterized in that, the hydraulic detention time in three grades of aerobic reactors is at least 6 hours.
44. methods as claimed in claim 43, is characterized in that, the hydraulic detention time in three grades of aerobic reactors is 8-20 hour.
45. methods as claimed in claim 44, is characterized in that, the hydraulic detention time in three grades of aerobic reactors is 10-15 hour.
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| CN103288299B (en) * | 2013-05-26 | 2016-02-10 | 哈尔滨理工大学 | The biochemical processing method of coal chemical industrial waste water |
| CN103508625B (en) * | 2013-07-16 | 2016-05-11 | 中石化宁波工程有限公司 | A kind for the treatment of facility of removing fluoride and calcium ion in coal chemical industry sewage |
| CN104496114B (en) * | 2014-12-15 | 2016-04-06 | 呼伦贝尔东北阜丰生物科技有限公司 | A kind of environment-protective process processing coal chemical industry sewage |
| CN107720939A (en) * | 2017-12-04 | 2018-02-23 | 江西省科学院能源研究所 | Aeration lifting multi-stage aerobic bioreactor and operating method |
| CN110240262A (en) * | 2019-06-05 | 2019-09-17 | 华东理工大学 | A method of not only retaining ammonia nitrogen in livestock and poultry cultivation biological wastewater treatment process but also had removed antibiotic |
| CN110550739B (en) * | 2019-09-29 | 2022-04-01 | 上海师范大学 | Aerobic and anaerobic VBBR (viable but anaerobic) series coupling device and sewage treatment method |
| CN110642476A (en) * | 2019-10-30 | 2020-01-03 | 重庆郅治环保科技有限公司 | Multistage A/O sewage treatment system |
| CN111268796A (en) * | 2019-12-17 | 2020-06-12 | 北控水务(中国)投资有限公司 | System and method for treating low C/N ratio domestic sewage by anaerobic/anoxic filler and staged water inlet three-stage AO |
| CN111072146A (en) * | 2019-12-23 | 2020-04-28 | 深圳市深投环保科技有限公司 | Treatment system and treatment method for high-COD high-ammonia nitrogen wastewater |
| CN111170573A (en) * | 2020-01-16 | 2020-05-19 | 河海大学 | Method for treating sewage containing organic waste liquid |
| CN113321306A (en) * | 2021-07-01 | 2021-08-31 | 上海环境卫生工程设计院有限公司 | Biochemical advanced treatment method for domestic waste leachate |
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