CN102874927A - 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 contain the coal chemical industrial waste water process field of high concentration organic contaminant and ammonia nitrogen.
Background technology
Coal chemical industrial waste water is the Coal Chemical Industry production process, at the waste water of coal high-temperature coking, gas purification, coke chemicals recovery and treating process generation.Various, the complicated component of pollutant kind in the coal chemical industrial waste water, such as organic pollutants such as phenols, benzene homologues, nitrogen heterocyclic ring aromatic hydrocarbons, polycyclic aromatic hydrocarbonss, the ammonia nitrogen of the poisonous inorganic pollutant such as sulfide, thiocyanide, prussiate and high density.Biological process is the treatment technology that adopts at present extensively, wherein with traditional biological denitrification process (A/O technique) and improve technique (such as A
2/ O, A
2/ O
2Etc. technique) use 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 carries out oil removal treatment by oil trap first; Passing into the acidication tower decomposes the organism of difficult degradation again; And then through anaerobic-aerobic fluidized-bed coupling biochemical system processing degradation of organic substances matter; Pass at last coagulative precipitation tank and carry out precipitation process, mud effluxes, 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) is difficult to account for by the organism that the traditional biological method is removed the 10-20% of total organic matter in the coal chemical industrial waste water, wherein mostly is baroque phenols, heterogeneous ring compound, Polycyclic aromatic hydrocarbons and Derivatives.Traditional activated sludge process carries out in the biology aerobic degradation process, and this class mass degradation speed is very slow or can not degrade; On the other hand, aerobic degradation causes the COD of processed waste water generally higher, at 300-500mg/L 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.
(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, the different biological function of performance, be unfavorable for forming functional flora, and suppress the activity of nitrobacteria, cause that treatment process organic matter removal efficient is low, operation stability is poor, processing cost is higher.In this case, heterotrophic bacterium dominant growth and the 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 the 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 it is terminal that nitration reaction only occurs in the aerobic reaction pond, and the nitrobacteria poor growth, the generation cycle is long, resistance to poison is poor, affects the bioprocess technology operation stability and improves processing cost.
(3) coal chemical industrial waste water contains the ammonia nitrogen of high density, and the 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 (climbing steel coalification factory Waste Water Treatment Optimizing Reconstruction, Zhou Mei, industrial safety and environmental protection, the 7th phase of the 35th 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 efficient of hardly degraded organic substance lower; In addition, although it separately carries out decarburization and nitration reaction, and nitration reaction was divided into for 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 the coking wastewater processing system, Li Yaxin, Zhao Yi, Yue Xiuping, Yang Huaiwang, Du Jincheng, Yao Runsheng, Ma Jianan, Treatment of Industrial Water, the 1st phase of the 28th volume, in January, 2008) employing biomembrance process A
2/ O
2The method 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 nitrifier to the processing of ammonia nitrogen.But it adopts a step nitrated, and 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 be 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 purpose of the present invention is to provide a kind of coal chemical industrial waste water biological treatment novel method, hardly degraded organic substance by the exploitation biological denitrification is removed ability and short distance nitration-denitrification biological denitrogenation new technology coupling integration, realization fast, efficiently, cheaply wastewater treatment.
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 the coal chemical industrial waste water through physico-chemical pretreatment enter successively anaerobic reactor, anoxic reacter, one-level aerobic reactor, secondary aerobic reactor and three grades of aerobic reactors, then discharging, 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 the 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 the 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 the one-level aerobic reactor, add alkali and/or phosphorus source; Preferably, described alkali is carbonate, is particularly preferably yellow soda ash; 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 the 50-100g/L, pH value is controlled between 7.0～7.5.
Preferably, the 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, the anoxic reacter dissolved oxygen concentration is below the 0.8mg/L, more preferably below the 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 the anaerobic reactor is at least 5 hours, more preferably 6-15 hour, is particularly preferably 7-10 hour.
Preferably, the hydraulic detention time in the anoxic reacter is at least 10 hours, more preferably 13-40 hour, is particularly preferably 15-30 hour.
Preferably, the hydraulic detention time in the one-level aerobic reactor is at least 10 hours, more preferably 13-40 hour, is particularly preferably 15-30 hour.
Preferably, the hydraulic detention time in the secondary aerobic reactor is at least 7 hours, 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, more preferably 8-20 hour, is particularly preferably 10-15 hour.
The present invention is by higher nitrification liquid reflux ratio (2:1-8:1) and add nitrate radical and/or nitrite anions, makes anoxic reacter that higher N/C value be arranged; Adopt present method to process coal chemical industrial waste water, water outlet can reach national sewage comprehensive discharge primary standard (GB9878-1996).
One of purpose of the present invention also is 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 secondary and/or the three grades of aerobic reactor effluent recyclings pipeline to anoxic reacter.
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, need not to be installed into water pump except anaerobic reactor.
One of purpose of the present invention also is 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 reinforcement sedimentation device 3, sludge refluxing apparatus 4, mud transmission mechanism 5 and collection mud device 6, strengthen sedimentation device 3 and be positioned at 2 tops, mud-water separation district, strengthen sedimentation device 3 bottoms the slope is set, be beneficial to the mud gravity reflux, top, slope and middle part arrange sludge refluxing apparatus 4, action edge under the pressure when depositing as mud, collection mud device 6 is installed in the 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, and 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, the bio-reaction zone 1 of anaerobic reactor and/or anoxic reacter is installed submersible agitator.
Preferably, the micro-hole aerator oxygenation is installed in the bottom of aerobic reactor.
One of purpose of the present invention also is to provide the purposes of a kind 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 all are described biological respinse-mud-water separation integrated bioreactor.
(as shown in Figure 2) illustrates the operational process of described biological respinse-mud-water separation integrated bioreactor as an example of aerobic reactor example: after coal chemical industrial waste water enters bio-reaction zone 1, under the aeration effect, fully mix with active sludge, and under microbial process, obtain oxygenolysis, muddy water mixed solution evenly enters mud-water separation district 2 by inlet channel, then carries out mud-water separation at reinforcement sedimentation device 3.Clear water outflow system after the separation, the active sludge of precipitation by the descending aeration zone that is back to of gravity, are brought to rapidly the middle and upper part of aeration zone along the slope by up aeration gas flow, mix with waste water.When causing that when mud appearance alluvial gravity reflux is smooth, can open sludge refluxing apparatus 4, accelerate sludge is descending, when the alluvial especially severe, can open mud transmission mechanism 5, impels mud to reflux to the aeration zone.Unnecessary mud can intermittently pass through the perforated sludge discharge pipe spoil disposal, then sends system by sludge pump.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 the inside reactor self-circulation, be conducive to cultivate the function bacterial classification and improve contaminant degradation efficient, can greatly improve sludge age and sludge concentration, sludge age can keep greater than 60 days, sludge concentration can be kept greater than 8mg/L, be conducive to cultivate the function bacterial classification, guarantee coal chemical industrial waste water bioremediation practical function of the present invention.Can cultivate dominant microflora in the anoxic stage and remove hardly degraded organic substance by denitrification; At aerobic stage heterotrophic bacterium and nitrobacteria are spatially isolated respectively and to cultivate, tame exclusive bacterial classification, and then optimization process effect, the processing cost that reduces.
The anaerobic acidification of employing " biological respinse-mud-water separation integrated bioreactor "-intensified anti-nitrated/oxidation of coal-short distance nitration-complete nitrification technique (A
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, impact to treatment system is very large, each stage of the method for the invention is all adopted new-type bioreactor, can realize the internal recycle of active sludge in reactor, sludge concentration can reach more than the 8mg/L, sludge age keeps being longer than 60 days, can keep the flora structural stability of active sludge and keep higher sludge concentration.
(2) the method for the invention has higher Persistent organic pollutants to remove efficient: contain the high-concentration hardly-degradable organism in the coal chemical industrial waste water, 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 the 2:1 by the mode of adjusting process parameter and interpolation nitrate radical and/or nitrite anions, and the enhanced biological denitrification is to the removal ability of hardly degraded organic substance; On the other hand, the employing of novel reactor can realize that oxidation operation finishes at reactor independently, greatly prolongs sludge age, improves sludge concentration, can cultivate efficient functional flora, optimizes the removal efficient of hardly degraded organic substance.
(3) but the method for the invention steady removal ammonia nitrogen: coal chemical industrial waste water contains high concentration organic contaminant and ammonia nitrogen, the traditional biological denitrogenation method is finished oxidation of coal and nitration reaction at single reactor, nitration reaction efficient 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 that oxidation of coal and nitration reaction finish in different reactor, can keep than high sludge concentration and makes nitrobacteria keep high reactivity; In addition, adopt the two-stage aerobic reactor to remove stage by stage ammonia nitrogen, realize respectively short distance and complete nitrification at secondary and three grades of aerobic reactors, volumetric loading is high, strong shock resistance.
(4) the method for the invention has lower processing cost: coal chemical industrial waste water contains hardly degraded organic substance and the ammonia nitrogen of high density, and traditional biology aerobic process electric power, reagent consumption amount are large, and the 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 removes the ammonia nitrogen of most of high density by short distance nitration, can reduce 30% power consumption and 20% reagent consumption, significantly reduces processing cost.
(5) anaerobic acidification of employing " biological respinse-mud-water separation integrated bioreactor "-intensified anti-nitrated/oxidation of coal-short distance nitration-complete nitrification technique (A
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.
Description of drawings
Fig. 1 is anaerobic acidification of the present invention-enhanced biological denitrification/oxidation of coal-short distance nitration-complete nitrification (A
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 of the present invention-mud-water separation integrated biological reactor.
Reference numeral is as follows:
1-bio-reaction zone; 2-mud-water separation district; 3-reinforcement sedimentation device;
4-sludge refluxing apparatus; 5-mud transmission mechanism.
Embodiment
The anaerobic acidification of employing " biological respinse-mud-water separation integrated bioreactor "-intensified anti-nitrated/oxidation of coal-short distance nitration-complete nitrification technique (A
2/ O
3) process coal chemical industrial waste water, embodiment is as follows:
Through the bottom water distribution system that pretreated coal chemical industrial waste water enters anaerobic reactor, the nitrification liquid (from secondary or three grades of aerobic reactors, reflux ratio 2:1-8:1) that refluxes simultaneously also is 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.Carrying out anaerobic acidification in anaerobic reactor processes, macromole hardly degraded organic substance in the 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 the anaerobic reactor hydraulic detention time is about at least 5 hours.The organic pollutant of denitrifying bacterium in the anoxic reacter in the coal chemical industrial waste water be as carbon source, take backflow supernatant liquor Central Asia nitrate or nitrate as electron acceptor(EA), breathes and vital movement, and it is reduced into nitrogen (N
2) overflow, remove hardly degraded organic substance when realizing biological denitrificaion.In present method, by keeping higher nitrification liquid reflux ratio and adding certain nitrate or nitroso-group nitrogen, make into the N/C value of water to maintain more than 2.5, majority of organic pollutants can be removed by the biological denitrification reaction.The basicity that anti-nitration reaction produces can compensate the basicity of follow-up nitration reaction about 50%, and the 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 the one-level aerobic reactor, replenishes simultaneously certain basicity (Na
2CO
3) and phosphorus source (Na
2HPO
3).The micro-hole aerator oxygenation is adopted in each aerobic reactor bottom, by dissolved oxygen concentration (DO) and the pH value in the automation system control reactor.Heterotrophic bacterium is removed in the coal chemical industrial waste water remaining organic pollutant after the anoxic denitrification reaction by biology aerobic reaction in the one-level aerobic reactor, realize gross decarburization, because the one-level aerobic reactor has longer sludge age and than 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, in the stage by stage oxidation of secondary and three grades of aerobic reactor realization ammonia nitrogens.Control suitable processing parameter, in the secondary aerobic reactor with the ammonia nitrogen oxidation control in nitrosification, realize short distance nitration, namely the ammonia nitrogen major part is oxidized to nitroso-group nitrogen.Three grades of aerobic reactors are removed ammonia nitrogen remaining behind the one-level aerobic reactor, and are nitrate with 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, and to strengthen the organic pollutant of removing in the coal chemical industrial waste water be a new way that is worth trial by improving in the waste water N/C value, 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 in traditional aerobe treating processes, is difficult for being degraded, greatly reduce simultaneously the material such as long-chain acids, ketone, lipid of generation, significantly reduce Process for Effluent COD.
Short distance nitration-denitrification process
Short distance nitration-denitrification process is that the ammonia nitrogen oxidising process is controlled at the nitrite anions stage, and it is applied to coal chemical industrial waste water biological treatment, has following advantage: the nitrated stage can reduce oxygen requirement about 30% and 25% alkali consumption, reduces approximately 20% processing cost; Floor space is little, and reactor volume can reduce about 30%-40%; Has higher denitrification rate (NO
2 -Denitrification rate is usually than NO
3 -High by about 63%); Sludge yield reduces (nitrifying process can produce about mud 33%-35% less, can produce less mud about 55% in the denitrification process).
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 the anoxic reacter N/C of system value, dissolved oxygen concentration, pH value, temperature, add alkali number, phosphorus amount the 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 is incited somebody to action the BOD in waste water theoretically by the biological denitrification process decomposing organic pollutant
5/ TKN〉2.86 o'clock, oxidation state nitrogen can be satisfied the demand, BOD
5Clearance can reach more than 80%.The organic pollutant that contains high density in the 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, namely needs higher N/C value, and it is 2.5-3.5 that present method is kept N/C.
(2) dissolved oxygen concentration.
Heterotrophic bacterium is removed the organic pollutant in the coal chemical industrial waste water under aerobic condition, 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.The control dissolved oxygen is with the important means of ammonia nitrogen oxidation control in the nitroso-group nitrogen stage, and Dissolved Oxygen concentration Control can efficiently be removed ammonia nitrogen by short distance nitration at 1-3mg/L in present method secondary aerobic reactor; At three grades of aerobic reactors, about 3-5mg/L, make nitroso-group nitrogen effectively be converted into fast nitrate by the control dissolved oxygen concentration, realize complete nitrification.Denitrifying bacteria is that nitrogen is overflowed with nitroso-group nitrogen and partial nitro nitrogen transformation in the anoxic reacter, is to carry out under the condition of anoxic, and dissolved oxygen in anoxic tank is controlled at below the 0.8mg/L.
(3) temperature.
Nitrobacteria is very sensitive to the variation of temperature, and the only growth temperature of nitrobacteria is between 27-32 ℃, is lower than 27 ℃ or be higher than 32 ℃ of decreased growths, and the growth of nitrobacteria and rate of nitrification below 15 ℃ significantly slow down.Denitrifying bacterium is responsive not as nitrobacteria to the variation of temperature.The suitable growth temperature of denitrifying bacterium is between 30-35 ℃, is lower than 15 ℃ of denitrification rates and 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 ℃; Strengthen the anoxic reacter denitrification, 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 the pH value is the 6-9 scope, 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 that wherein contains can disturb or destroy the normal physiological activity of bacterium such as fugitive constituent, ammonia nitrogen, heavy metal ion, complex anion, prussiate and some toxic organic compounds, and then affects the normal operation of method.As when phenol concentration greater than 5.6mg/L, ammonia nitrogen concentration during greater than 200mg/L, nitration reaction can be suppressed.Free ammonia (FA) has in various degree restraining effect to nitrobacteria, nitrite bacteria.FA concentration is during greater than 5mg/L, although that nitroso-group nitrogen accounts for the nitrate ratio is high, along with the rising of FA concentration, nitrite bacteria also can be in holddown gradually.
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 of the present invention-mud-water separation integrated bioreactor, comprises bio-reaction zone 1 and mud-water separation district 2; Wherein, mud-water separation district 2 comprises reinforcement sedimentation device 3, sludge refluxing apparatus 4, mud transmission mechanism 5 and collection mud device 6, strengthen sedimentation device 3 and be positioned at 2 tops, mud-water separation district, strengthen sedimentation device 3 bottoms the slope is set, be beneficial to the mud gravity reflux, top, slope and middle part arrange sludge refluxing apparatus 4, action edge under the pressure when depositing as mud, collection mud device 6 is installed in the 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, and 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, the top water outlet, the bio-reaction zone 1 of anaerobic reactor and anoxic reacter is installed submersible agitator, the micro-hole aerator oxygenation is installed in the bottom of one-level, secondary and three grades of aerobic reactors, by dissolved oxygen concentration (DO) and the pH value in the automation system control reactor.
Enter the bottom of anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.Carry out anaerobic acidification and process in anaerobic reactor, the anaerobic reactor hydraulic detention time is 7 hours.The anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid that refluxes simultaneously is (from secondary and three grades of aerobic reactors, reflux ratio 6:1) also is back to this water distribution system, the anoxic reacter dissolved oxygen concentration is 0.5mg/L, the 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 the one-level aerobic reactor, replenishes simultaneously certain Na
2CO
3And Na
2HPO
3One-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).
Enter the bottom of anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.Carry out anaerobic acidification and process in anaerobic reactor, the anaerobic reactor hydraulic detention time is 5 hours.The anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid that refluxes simultaneously is (from secondary and three grades of aerobic reactors, reflux ratio 2:1) also is back to this water distribution system, the anoxic reacter dissolved oxygen concentration is 0.8mg/L, the 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 the one-level aerobic reactor, replenishes simultaneously certain Na
2CO
3And Na
2HPO
3One-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).
Enter the bottom of anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.Carry out anaerobic acidification and process in anaerobic reactor, the anaerobic reactor hydraulic detention time is 15 hours.The anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid that refluxes simultaneously is (from secondary and three grades of aerobic reactors, reflux ratio 8:1) also is back to this water distribution system, the anoxic reacter dissolved oxygen concentration is 0.6mg/L, the 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 the one-level aerobic reactor, replenishes simultaneously certain Na
2CO
3And Na
2HPO
3One-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
Enter the bottom of anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.Carry out anaerobic acidification and process in anaerobic reactor, the anaerobic reactor hydraulic detention time is 6 hours.The anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid that refluxes simultaneously is (from secondary and three grades of aerobic reactors, reflux ratio 7:1) also is back to this water distribution system, the anoxic reacter dissolved oxygen concentration is 0.7mg/L, the 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 the one-level aerobic reactor, replenishes simultaneously certain Na
2CO
3And Na
2HPO
3One-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).
Enter the bottom of anaerobic reactor through pretreated coal chemical industrial waste water, each stage reactor water outlet absolute altitude successively decreases successively.Carry out anaerobic acidification and process in anaerobic reactor, the anaerobic reactor hydraulic detention time is 13 hours.The anaerobic reactor water outlet enters anoxic reacter bottom water distribution system, the nitrification liquid that refluxes simultaneously is (from secondary and three grades of aerobic reactors, reflux ratio 2.5:1) also is back to this water distribution system, the anoxic reacter dissolved oxygen concentration is 0.6mg/L, the 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 the one-level aerobic reactor, replenishes simultaneously certain Na
2CO
3And Na
2HPO
3One-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, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. 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 discharging, 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.
2. the method for claim 1 is characterized in that, secondary and/or three grades of aerobic reactor effluent recyclings are to anoxic reacter;
Preferably, described reflux ratio is 2:1-8:1, is particularly preferably 3:1-6:1;
Preferably, in anoxic reacter, add nitrate radical and/or nitrite anions;
Preferably, in the one-level aerobic reactor, add alkali and/or phosphorus source;
Preferably, described alkali is carbonate, is particularly preferably yellow soda ash;
Preferably, described phosphorus source is hydrophosphate, is particularly preferably Sodium phosphate dibasic.
3. method as claimed in claim 1 or 2 is characterized in that, the hypoxia response actuator temperature is 20-38 ℃, is preferably 23-36 ℃, is particularly preferably 25-35 ℃;
Preferably, the anoxic reacter dissolved oxygen concentration is below the 0.8mg/L, more preferably below the 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.
4. such as each described method of claim 1-3, it is characterized in that, one-level aerobic reactor dissolved oxygen concentration is 1-5mg/L, is particularly preferably 1-4mg/L;
Preferably, secondary aerobic reactor dissolved oxygen concentration is 2-3mg/L;
Preferably, secondary aerobic reaction actuator temperature is 30-37 ℃, is particularly preferably 30-35 ℃;
Preferably, the pH of secondary aerobic reactor is 7.5-8.7, is particularly preferably 7.5-8.5;
Preferably, three grades of aerobic reactor dissolved oxygen concentrations are 4mg/L;
Preferably, three grades of aerobic reaction actuator temperatures are 24-30 ℃, are particularly preferably 25-30 ℃;
Preferably, the pH of three grades of aerobic reactors is 6.8-7.5, is particularly preferably 7.0-7.5.
5. such as each described method of claim 1-4, it is characterized in that, the hydraulic detention time in the anaerobic reactor is at least 5 hours, more preferably 6-15 hour, is particularly preferably 7-10 hour;
Preferably, the hydraulic detention time in the anoxic reacter is at least 10 hours, more preferably 13-40 hour, is particularly preferably 15-30 hour;
Preferably, the hydraulic detention time in the one-level aerobic reactor is at least 10 hours, more preferably 13-40 hour, is particularly preferably 15-30 hour;
Preferably, the hydraulic detention time in the secondary aerobic reactor is at least 7 hours, 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, more preferably 8-20 hour, is particularly preferably 10-15 hour.
6. coal chemical industrial waste water biological treatment system comprises successively according to the flow direction of waste water: physico-chemical pretreatment system, anaerobic reactor, anoxic reacter, one-level aerobic reactor, secondary aerobic reactor and three grades of aerobic reactors.
7. coal chemical industrial waste water biological treatment system as claimed in claim 6 is characterized in that, described coal chemical industrial waste water biological treatment system also comprises secondary and/or the three grades of aerobic reactor effluent recyclings pipeline to anoxic reacter;
Preferably, each stage reactor water outlet absolute altitude according to wastewater streams to successively decreasing successively.
8. 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 reinforcement sedimentation device (3), sludge refluxing apparatus (4), mud transmission mechanism (5) and collection mud device (6), strengthen sedimentation device (3) and be positioned at top, mud-water separation district (2), strengthen sedimentation device (3) bottom the slope is set, top, slope and middle part arrange sludge refluxing apparatus (4), collection mud device (6) is installed in the bottom, slope, mud transmission mechanism (5) is installed with bio-reaction zone (1) bottom connecting place in bottom, mud-water separation district (2), and mud transmission mechanism (5) is positioned at collection mud device (6) top.
9. reactor as claimed in claim 8 is characterized in that, described slope and horizontal plane angle are 30-80 °, is particularly preferably 40-70 °;
Preferably, described reactor bottom water inlet, top water outlet;
Preferably, the bio-reaction zone of anaerobic reactor and/or anoxic reacter (1) is installed submersible agitator;
Preferably, the micro-hole aerator oxygenation is installed in the bottom of aerobic reactor.
10. the purposes of biological respinse-mud-water separation integrated bioreactor as claimed in claim 8 or 9 is characterized in that, described reactor is used for claim 6 or 7 described coal chemical industrial waste water biological treatment systems.
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