CN101514069B - Coking wastewater biological denitrificaion treatment process - Google Patents
Coking wastewater biological denitrificaion treatment process Download PDFInfo
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Abstract
The invention relates to a coking wastewater biological denitrificaion treatment process, belonging to the technical field of environmental protection and wastewater processing, which is characterized in that the biological denitrificaion treatment process with A/O/A/O, namely, anoxia/oxic/ anoxia/oxic as the core is adopted. The pretreated coking wastewater sequentially enters into a first-levelanoxic tank, a first-level oxic tank, a reflow sedimentation tank, a second-level anoxic tank, a second-level oxic tank, a second-level sedimentation tank, short-range nitrification and denitrification biological denitrificaion treatment are carried out on the coking wastewater in the first-level anoxic tank and the first-level oxic tank, hydrolysis acidification and fine denitrification treatment are carried out on the coking wastewater in the second-level anoxic tank, and the second-level oxic tank realizes the full nitration reaction. The process method has stable operational effect, low operational cost, high denitrification percent, water-quality indexes such as CODCr, NH3-N and the like of water from the second-level sedimentation tank can simultaneously reach a first-level discharge standard in Integrated Wastewater Discharge Standard (GB8978-1996), and can be recycled and used by other users after advanced treatment, thus realizing the zero discharge of the coking wastewater.
Description
Technical field
The invention belongs to environment protection and technical field of waste water processing; a kind of coking wastewater biological denitrificaion treatment process particularly is provided; adopting " A/O/A/O (anoxic/aerobic/anoxic/aerobic) " is the biological denitrificaion treatment process of core, is applicable to coking industry wastewater biological denitrificaion treatment system.
Background technology
Coking chemical waste water is the waste water that produces in raw coal high temperature carbonization, gas purification and Chemicals treating process, its main source has three: the one, and remained ammonia, it is the waste water that generates in the dry distillation of coal and coal gas cooling, its water yield accounts for the over half of coking chemical waste water total amount, is the main source of coking chemical waste water; The 2nd, the waste water that generates in the gas purification process divides dried up etc. as gas final cold water and crude benzol; The 3rd, in treating processes such as tar, crude benzol, reach the waste water that other occasion produces.Coking chemical waste water is the trade effluent that contains a large amount of Persistent organic pollutants, and its complicated component contains tens kinds of pollutents such as a large amount of phenol, ammonia nitrogen, cyanogen, benzene, pyridine, indoles and quinoline, and the coking chemical waste water of the discharging that exceeds standard causes serious pollution to environment.How to improve and solve the pollution problem of coking chemical waste water, become the problem that press for solution of pendulum in face of people environment.
In coking chemical waste water, can not account for COD by biochemical organism
CrAbout the 13-17% of total amount, wherein mostly be polycyclic aromatic hydrocarbons, when traditional activated sludge process was carried out a biological disposal upon, polycyclic aromatic hydrocarbons can not be degraded substantially, so the COD of processed waste water
CrAlways about 300-500mg/L.The anoxia/aerobic biological technology that adopts is handled, in anoxic pond, because the anaerobic denitrifying bacterium utilizes organism as carbon source, make organic matter degradation 40% in the waste water, thereby reduced the organic loading of Aerobic Pond, make waste water enter Aerobic Pond after, under the situation that conditions such as basicity, temperature, dissolved oxygen all are fit to, enter the nitrated stage of oxidation ammonia nitrogen very soon, make ammonia nitrogen can be oxidized to nitrite nitrogen and nitrate nitrogen.The waste water that contains nitrite nitrogen and nitrate nitrogen turns back to anoxic pond in a large number, makes it under the anoxybiotic condition, by the anaerobic denitrifying bacterium it is reduced into nitrogen (N
2) separate out, thereby reach the purpose of denitrogenation.
Nitration reaction process and reaction formula:
Under the effect of nitrifier, ammonia nitrogen progressively decomposes, oxidation, divides two stages to carry out, and at first under the effect of nitrococcus, ammonia nitrogen is converted into nitrite nitrogen, and reaction formula is:
NH
4 ++3/2O
2——NO
2 -+H
2O+2H
++ΔF1 <1>
Continue after, nitrite nitrogen (NO
2 --N) under the effect of nitrifier, further being converted into nitrate nitrogen, its reaction formula is: NO
2 -+ 1/2O
2---NO
3 -+ Δ F
2＜2 〉
Net reaction is: NH
4 ++ 2O
2---NO
3 -+ H
2O+2H
++ Δ F
Can calculate from above-listed reaction formula, the 1g ammonia nitrogen is oxidized to nitrate nitrogen and needs 4.57g oxygen, the aerobic 3.43g of nitrosation reaction wherein, and the aerobic 1.14g of nitration reaction, the hydrocarbonate basicity in the consume water also in the reaction process is about 7.14g (CaCO
3)/gNH
3-N.
Denitrification process and reaction formula:
Anti-nitration reaction is meant nitrate nitrogen (NO
3 --N) and nitrite nitrogen (NO
2 --N) under the effect of denitrifying bacteria, be reduced to nitrogen (N
2) process.
Reaction formula: 2NO
2 -+ 6H
+(electron donor)---N
2↑+2H
2O+20H
-＜3 〉
2NO
3 -+ 10H
+(electron donor)---N
2↑+4H
2O+20H
-＜4 〉
Can calculate from above-listed reaction formula, the carbonaceous organic material in the waste water can be used as the electron donor of denitrification process.Transforming the 1g nitrite nitrogen is nitrogen, needs organism (with BOD
5Expression) 1.71g when conversion 1g nitrate nitrogen is nitrogen, needs organism 2.86g, produces 3.57g basicity simultaneously (with CaCO
3Meter).
From＜3〉＜4〉formula we find out that nitrite and nitrate can both participate in denitrification reaction equally.And find out from nitrite-oxidizing to nitrate from reaction formula＜2, increase about 25% oxygen-consumption, from formula＜4〉upward we see that nitrate denitrogenation meeting consumes more carbon source.So can be than better from the nitrate denitrification effect from nitrite denitrification, the more important thing is two class nitration reactions are confined to two relatively independent spaces, can control separately spatial parameter respectively and finish reaction, make specific biological inoculum in its optimum living environment, maximum bacterial classification advantage will be obtained, its potential will obtain maximum performance, overcome the deficiency of Anoxybiotic-aerobic biologic denitrogenation processing, shortened reaction mechanism, improved nitric efficiency, that is to say that employing short-cut nitrification and denitrification bio-denitrification technology is more advanced.But in actual production,, realize very difficulty of short-cut nitrification and denitrification bio-denitrification technology fully owing to the extremely difficult control of various operational conditionss.Increase secondary anoxic/aerobic treatment again after the short-cut nitrification and denitrification biological denitrification process, can make coking chemical waste water be hydrolyzed acidifying, smart denitrogenation processing in the secondary anoxic pond, the secondary Aerobic Pond is realized complete nitration reaction.The ability of system's anti-shock loading is strengthened, and effluent quality is more stable, and denitrification percent is higher, the COD of secondary sedimentation basins water outlet
CrAnd NH
3Water-quality guideline such as-N can reach " integrated wastewater discharge standard " first discharge standard in (GB8978-1996) simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of coking wastewater biological denitrificaion treatment process, after the short-cut nitrification and denitrification biological denitrification process, increase secondary anoxic/aerobic treatment again, can make coking chemical waste water be hydrolyzed in the secondary anoxic pond acidifying, smart denitrogenation processing, the secondary Aerobic Pond is realized complete nitration reaction.The ability of system's anti-shock loading is strengthened, and effluent quality is more stable, and denitrification percent is higher, the COD of secondary sedimentation basins water outlet
CrAnd NH
3Water-quality guideline such as-N can reach " integrated wastewater discharge standard " first discharge standard in (GB8978-1996) simultaneously.
It is the biological denitrificaion treatment process of core that the present invention adopts " A/O/A/O (anoxic/aerobic/anoxic/aerobic) ", brief description of the process is as follows: enter one-level anoxic pond, one-level Aerobic Pond, reflux sedimentation tank, secondary anoxic pond, secondary Aerobic Pond, secondary sedimentation basins successively through pretreated coking chemical waste water, carrying out short distance nitration and denitrification biological denitrogenation in one-level anoxic pond and Aerobic Pond handles, be hydrolyzed in the secondary anoxic pond acidifying, smart denitrogenation processing, the secondary Aerobic Pond is realized complete nitration reaction.
The pretreated coking chemical waste water of process enters the bottom water distribution system of one-level anoxic pond, the supernatant liquor (reflux ratio 2～3: 1) also be back to this water distribution system of reflux sedimentation tank simultaneously after promoting.
One-level anoxic pond of the present invention is vertical-flow, and water distribution system adopts big resistance water distribution mode, is abound with fixedly elastic biological filler in the pond; Under the anoxic operating mode, the anaerobic denitrifying bacterium in the one-level anoxic pond is with the organic cod in the raw wastewater
CrBe carbon source, as being subjected to electric body, breathe and vital movement, it is reduced into nitrogen overflows, one-level anoxic pond name about 18～25h of the residence time with the oxygen of nitrite nitrogen in the backflow supernatant liquor and part nitric nitrogen.The water outlet of one-level anoxic pond relies on run by gravity to enter the one-level Aerobic Pond, the returned sluge of reflux sedimentation tank (reflux ratio 1～2: 1) also be back to the import of one-level Aerobic Pond
The water outlet of one-level Aerobic Pond of the present invention relies on run by gravity to enter reflux sedimentation tank, mixed solution is carried out solid-liquid separation, part supernatant liquor and underflow mud promote through pump respectively and are back to one-level anoxic pond, one-level Aerobic Pond, and the following current of another part supernatant liquor is to the secondary anoxic pond.Reflux sedimentation tank adopts the radical sedimentation basin of peripheral water-in and water-out pattern, and hydraulic load is 1～1.5m
3/ m
2H.
Secondary anoxic pond of the present invention also is vertical-flow, and water distribution system adopts big resistance water distribution mode, is abound with fixedly elastic biological filler in the pond; After coking chemical waste water entered the secondary anoxic pond, under the anoxic operating mode, the acidification reaction that further is hydrolyzed in the pond for anti-nitration reaction provides organism, carried out smart denitrogenation processing, has reduced organic content, has improved the denitrification percent of coking chemical waste water; Secondary anoxic pond name about 5～12h of the residence time.
The water outlet of secondary Aerobic Pond of the present invention relies on run by gravity to enter secondary sedimentation basins, and mixed solution is carried out solid-liquid separation, and secondary sedimentation basins underflow mud promotes through pump and is back to secondary Aerobic Pond, the COD of the supernatant liquor water outlet of secondary sedimentation basins
CrAnd NH
3-N reaches the primary standard of national waste water comprehensive discharge standard (GB9878-1996) simultaneously, can be back to other users through after the advanced treatment, realizes Zero-discharge coked wastewater.
Secondary sedimentation basins of the present invention adopts radical sedimentation basin, and effluent weir is set up traverse baffle, and hydraulic load is 0.6～1m
3/ m
2H.
The invention has the advantages that operating performance is stable, running cost is low, denitrification percent height, the COD of secondary sedimentation basins water outlet
CrAnd NH
3Water-quality guideline such as-N can reach " integrated wastewater discharge standard " first discharge standard in (GB8978-1996) simultaneously, can be back to other users through after the advanced treatment, realize Zero-discharge coked wastewater.
Description of drawings
Fig. 1 is the process flow sheet of the specific embodiment of the invention.
Embodiment
Adopting " A/O/A/O (anoxic/aerobic/anoxic/aerobic) " is the coking wastewater biological denitrificaion treatment process of core, and embodiment is as follows:
The pretreated coking chemical waste water of process enters the bottom water distribution system of one-level anoxic pond after promoting, the supernatant liquor (reflux ratio 3: 1) of reflux sedimentation tank also is back to this water distribution system simultaneously.The one-level anoxic pond is vertical-flow, and water distribution system adopts big resistance water distribution mode, is abound with fixedly elastic biological filler in the pond.Under the anoxic operating mode, the anaerobic denitrifying bacterium in the one-level anoxic pond is with the organism (COD in the raw wastewater
Cr) be carbon source,, breathe and vital movement as being subjected to electric body with the oxygen of nitrite nitrogen in the backflow supernatant liquor and part nitric nitrogen, it is reduced into nitrogen (N
2) overflow, thereby realize biological denitrificaion.The basicity that anti-nitration reaction can produce can compensate about half of basicity that follow-up nitration reaction consumes, therefore can save the Treatment of Coking Effluent cost.One-level anoxic pond name about 18h of the residence time.
The water outlet of one-level anoxic pond relies on run by gravity to enter the one-level Aerobic Pond, the returned sluge of reflux sedimentation tank (reflux ratio 2: 1) also is back to the import of one-level Aerobic Pond, plug-flow operation in the one-level Aerobic Pond after mixing, the one-level Aerobic Pond adopts the micro-hole aerator oxygenation, microorganism carries out nitration reaction under aerobic operating mode, progressively removes phenol, prussiate, thiocyanide etc. in order and the ammonia nitrogen in the coking chemical waste water is converted into nitrite nitrogen and part nitric nitrogen.Nitrifying process need add yellow soda ash, with the hydrocarbonate basicity of additional nitration reaction consumes, and adds microcosmic salt in right amount to keep the synthetic required carbon N/P ratio example relation of cell.One-level Aerobic Pond name about 36h of the residence time.
The water outlet of one-level Aerobic Pond relies on run by gravity to enter reflux sedimentation tank, and mixed solution is carried out solid-liquid separation, and a part of supernatant liquor and underflow mud promote through pump respectively and is back to one-level anoxic pond, one-level Aerobic Pond, and the following current of another part supernatant liquor is to the secondary anoxic pond.Reflux sedimentation tank adopts the radical sedimentation basin of peripheral water-in and water-out pattern, and hydraulic load is 1m
3/ m
2H.
The secondary anoxic pond also is vertical-flow, and water distribution system adopts big resistance water distribution mode, is abound with fixedly elastic biological filler in the pond.After coking chemical waste water entered the secondary anoxic pond, under the anoxic operating mode, the acidification reaction that further is hydrolyzed in the pond for anti-nitration reaction provides organism, carried out smart denitrogenation processing, has reduced organic content, has improved the denitrification percent of coking chemical waste water.Secondary anoxic pond name about 9h of the residence time.
The import that the water outlet of secondary anoxic pond relies on run by gravity to enter the secondary Aerobic Pond, the returned sluge (reflux ratio 1: 1) of secondary sedimentation basins also is back to the import of secondary Aerobic Pond simultaneously, plug-flow operation in the secondary Aerobic Pond after mixing, the secondary Aerobic Pond adopts the micro-hole aerator oxygenation, microorganism carries out nitration reaction under aerobic operating mode, as far as possible nitrite nitrogen is converted into nitric nitrogen, COD further degrades
CrNitrifying process need add yellow soda ash, with the hydrocarbonate basicity of additional nitration reaction consumes, and adds microcosmic salt in right amount to keep the synthetic required carbon N/P ratio example relation of cell.Secondary Aerobic Pond name about 18h of the residence time.
The water outlet of secondary Aerobic Pond relies on run by gravity to enter secondary sedimentation basins, and mixed solution is carried out solid-liquid separation, and secondary sedimentation basins underflow mud promotes through pump and is back to secondary Aerobic Pond, the supernatant liquor water outlet COD of secondary sedimentation basins
CrAnd NH
3-N can reach the primary standard of national waste water comprehensive discharge standard (GB9878-1996) simultaneously, can be back to other users through after the advanced treatment, realizes Zero-discharge coked wastewater.Secondary sedimentation basins adopts radical sedimentation basin, and effluent weir is set up traverse baffle, and hydraulic load is 0.8m
3/ m
2H.
Coking wastewater biological denitrificaion treatment process operation control condition
Adopt " A/O/A/O (anoxic/aerobic/anoxic/aerobic) " for the coking wastewater biological denitrificaion treatment process of core and system dissolves oxygen concn, temperature, carbon-nitrogen ratio and reflux ratio, mud age with to add the control quality of alkali number, phosphorus amount relevant, whether the water outlet after not only influence is handled is up to standard, but also be related to the height of processing cost, therefore, online detection and analytical test are important rings of control operation.
(1) dissolved oxygen (DO)
Nitrite bacteria, nitrobacteria must have under the environment of dissolved oxygen, make ammonia nitrogen be oxidized to nitrite nitrogen and nitrate nitrogen and are used for growth to obtain enough energy.The Aerobic Pond dissolved oxygen is controlled at 2.0-4.0mg/L, and back aeration tank dissolved oxygen is controlled at 2.0-5.0mg/L.
Denitrifying bacteria is reduced into nitrogen with nitrite nitrogen and nitrate nitrogen and separates out, and is to carry out under the anoxybiotic condition, and dissolved oxygen in anoxic tank is controlled at below the 0.5mg/L.
(2) temperature
Nitrobacteria is very sensitive to 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 growth of nitrobacteria and rate of nitrification below 15 ℃ significantly slow down.
Denitrifying bacterium is not so good as the nitrobacteria sensitivity to variation of temperature.The suitable growth temperature of denitrifying bacterium is between 30-35 ℃, is lower than that denitrification rate significantly slows down below 15 ℃.
(3) denitrification carbon-nitrogen ratio (BOD5/TKN) and reflux ratio (R)
Denitrifying bacterium is to carry out denitrification denitrogenation in the process of decomposing organic matter, and theoretically, when the BOD5/TKN in the waste water＞2.86, organism can be satisfied the demand.When the BOD5/TKN in the waste water was 4 left and right sides, return of waste water was 3 than R (ratio of supernatant liquor quantity of reflux and Q), and its denitrification percent is more than 70%.
(4) pH, basicity and phosphorus
Nitrite bacteria, nitrobacteria are very sensitive to the variation of pH, and the suitable pH value of nitrite bacteria is 7.0-8.5, and the pH value that nitrobacteria suits is 6.5-7.5.Reflux sedimentation tank goes out alkalinity of water and generally is controlled at more than the 250mg/L, and second pond goes out alkalinity of water and generally is controlled at 80-150mg/L, and total phosphorus generally is controlled at 0.5mg/L.
Denitrifying bacterium is not so good as the nitrobacteria sensitivity to the variation of pH, in the pH value is the scope of 6-9, all can carry out normal physiological metabolism.
(5) organic loading (F/M) and sludge age (SRT)
F/M refers to the active sludge of unit weight, will guarantee certain organic pollutant amount that treatment effect bore in the unit time, and unit is kgBOD
5/ (kgMLVSSd).Biological nitration belongs to underload technology, and F/M is generally at 0.15kgBOD
5/ (kgMLVSSd) below, it is low more to load, and nitratedly carries out fully more, nitrification efficiency is high more.Corresponding with underload, the generation cycle of nitrifier is 31 hours, and for the normal breeding that guarantees nitrifier is not run off, aerobic section is controlled SRT more than 62 hours by generation cycle operation more than two times by the control surplus sludge volume.
(6) influence of toxic substance
Some heavy metal ion, complex anion, prussiate and some organism can disturb or destroy the normal physiological activity of bacterium.Higher when the concentration of these materials in water, just can suppress normally carrying out of biological nitration.For example, when lead ion greater than 0.5mg/L, phenol greater than 5.6mg/L, NH3-N concentration during greater than 200mg/L, nitratedly all can be suppressed.Free ammonia (FA) has in various degree restraining effect to nitrobacteria, nitrite bacteria.When FA was 0.6mg/L-5mg/L, nitrobacteria was for the intensive holddown, and it is very high that nitrite nitrogen accounts for the nitric nitrogen ratio; FA is during greater than 5mg/L, though that nitrite nitrogen accounts for the nitric nitrogen ratio is higher, along with FA concentration rises, nitrite bacteria also is in holddown gradually.
Claims (1)
1. a coking wastewater biological denitrificaion treatment process belongs to environment protection and technical field of waste water processing, it is characterized in that, adopting anoxic/aerobic/anoxic/aerobic is the biological denitrificaion treatment process of core; Technical process is as follows:
Enter one-level anoxic pond, one-level Aerobic Pond, reflux sedimentation tank, secondary anoxic pond, secondary Aerobic Pond, secondary sedimentation basins successively through pretreated coking chemical waste water, carrying out short distance nitration and denitrification biological denitrogenation in one-level anoxic pond and Aerobic Pond handles, in the secondary anoxic pond, be hydrolyzed acidifying, smart denitrogenation processing, the secondary Aerobic Pond is realized complete nitration reaction;
The pretreated coking chemical waste water of process enters the bottom water distribution system of one-level anoxic pond after promoting, the supernatant liquor of reflux sedimentation tank also is back to this water distribution system simultaneously; Reflux ratio 2～3: 1; Described one-level anoxic pond is vertical-flow, and water distribution system adopts big resistance water distribution mode, is abound with fixedly elastic biological filler in the pond; Under the anoxic operating mode, the anaerobic denitrifying bacterium in the one-level anoxic pond is with the organic cod in the raw wastewater
CrBe carbon source, with the oxygen of nitrite nitrogen in the backflow supernatant liquor and part nitric nitrogen as being subjected to electric body, breathe and vital movement, it is reduced into nitrogen overflows, the one-level anoxic pond name residence time 18～25h, the water outlet of one-level anoxic pond relies on run by gravity to enter the one-level Aerobic Pond, and the returned sluge of reflux sedimentation tank also is back to the import of one-level Aerobic Pond, reflux ratio 1～2: 1;
The water outlet of described one-level Aerobic Pond relies on run by gravity to enter reflux sedimentation tank, mixed solution is carried out solid-liquid separation, part supernatant liquor and underflow mud promote through pump respectively and are back to one-level anoxic pond, one-level Aerobic Pond, and the following current of another part supernatant liquor is to the secondary anoxic pond; Reflux sedimentation tank adopts the radical sedimentation basin of peripheral water-in and water-out pattern, and hydraulic load is 1～1.5m
3/ m
2H;
Described secondary anoxic pond also is vertical-flow, and water distribution system adopts big resistance water distribution mode, is abound with fixedly elastic biological filler in the pond; After coking chemical waste water entered the secondary anoxic pond, under the anoxic operating mode, the acidification reaction that further is hydrolyzed in the pond for anti-nitration reaction provides organism, carried out smart denitrogenation processing, has reduced organic content, has improved the denitrification percent of coking chemical waste water; The secondary anoxic pond name residence time 5～12h;
The water outlet of described secondary Aerobic Pond relies on run by gravity to enter secondary sedimentation basins, and mixed solution is carried out solid-liquid separation, and secondary sedimentation basins underflow mud promotes through pump and is back to secondary Aerobic Pond, the supernatant liquor water outlet COD of secondary sedimentation basins
CrAnd NH
3-N reaches the primary standard of national waste water comprehensive discharge standard GB9878-1996 simultaneously, can be back to other users through after the advanced treatment, realizes Zero-discharge coked wastewater;
Described secondary sedimentation basins adopts radical sedimentation basin, and effluent weir is set up traverse baffle, and hydraulic load is 0.6～1m
3/ m
2H.
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| CN111410308A (en) * | 2020-03-03 | 2020-07-14 | 广东新会中集特种运输设备有限公司 | Two-stage AO integrated sewage treatment equipment |
| CN111847774B (en) * | 2020-07-10 | 2022-05-03 | 珠海九通水务股份有限公司 | Application method of mud-water separation tank |
| CN113754059A (en) * | 2021-09-24 | 2021-12-07 | 陕西华陆化工环保有限公司 | A high-efficient biological denitrogenation system for waste water treatment |
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