CN104724886B - A kind of semi-coke wastewater decarburization removing total nitrogen processes technique - Google Patents
A kind of semi-coke wastewater decarburization removing total nitrogen processes technique Download PDFInfo
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Abstract
nullThe invention discloses a kind of semi-coke wastewater decarburization removing total nitrogen and process technique，Including pretreatment system、Biochemical treatment system、Advanced treatment system，Pretreatment system includes oil interceptor and two-stage air-flotation process，Biochemical treatment system includes multi-functional denitrification tank、First Aerobic Pond、Second sedimentation basin、Anoxic pond、Second Aerobic Pond、3rd sedimentation basin，Multi-functional denitrification tank、First Aerobic Pond、Anoxic pond and the second Aerobic Pond add HSBEMBM environmental improvement microorganism formulation respectively，The mixed liquor of the first Aerobic Pond is partly refluxed to multi-functional denitrification tank，Advanced treatment system includes photocatalytic ozonation reaction tower，Biochemical treatment system also includes a sludge absorption bed reaction tank，First Aerobic Pond has several refluxing openings in its flow direction，Photocatalytic ozonation reaction tower top is provided with discharge，Collect and cause in described first order cavitation air flotation pond after the residual ozone that the water surface overflows.Being processed can be reached good treatment effect to semi-coke wastewater by the system of this technique, applicability is strong and easy to operate simultaneously.
Description
Technical field
The present invention relates to industrial waste water treatment, particularly relate to science and engineering at a kind of semi-coke wastewater decarburization removing total nitrogen
Skill.
Background technology
Semi-coke is also known as semicoke, and it is that in passing through with jet coal, dross coal and weakly caking coal etc., low temperature distillation (600 ~ 800 DEG C) is hot
Solution obtain compared with the solid carbonaceous product of low volatile, its waste water quality composition is similar to coking chemical waste water.Destructive distillation temperature in coke production
During degree is about 1000 DEG C, and semi-coke produces, pyrolysis temperature is low.Therefore containing a large amount of not by high-temperature oxydation low point in semi-coke wastewater
Sub-pollutant, its concentration exceeds about 10 times than coking chemical waste water.Semi-coke wastewater mainly contains high-enriched organics and inorganic
Thing, organic pollution mainly contains coal tar oily substance, and wherein the content of phenols is very high, also monocyclic and polycyclic aromatic series
Compound, and heterocyclic compound etc. nitrogenous, sulphur, oxygen；Based on inorganic pollution is mainly with ammonium salt, also contain sulfide, sulphur cyanogen
The harmful substance such as compound, cyanide；Wherein COD is up to 30000-40000mg/L, and ammonia nitrogen is up to 2500-3000mg/L；If without
Process directly discharge and severe contamination will be caused to water environment.At present, semi-coke wastewater has become as the difficult degradation generally acknowledged both at home and abroad
One of waste water.
Existing semi-coke scale wastewater treatment system many employings Physical, chemical method and bioanalysis: its main process side
Method has absorption method, flue gas treatment method, activated sludge process, burning method, catalysis oxidation-biochemical process, ammonia still process dephenolize-SBR method and breast
Shape liquid-film method etc., the problem that they exist: cost of investment is high, processing cost high, applicability is strong, difficult treatment or produce secondary
The problems such as pollution, as absorption method processing cost is high, absorption regeneration difficulty, inapplicable high concentration wastewater treatment, flue gas method requires
In waste water, ammonia content must balance with ammonia amount needed for flue gas, uses restricted；It is big that burning method processes investment, water quality treatment
Asking high, applicability is not strong；Catalytic oxidation to be carried out under high-temperature and high-pressure conditions, and processing cost is high, scale of investment and running cost
With greatly；Ammonia still process dephenolize-SBR method needs to use organic solvent dephenolize, can produce secondary pollution, and first carry out impact after phenol removal
NH_3-N treating efficiency, adds the difficulty of subsequent treatment, and these all may make water outlet can not reach " coking chemistry industrial pollutants
Discharge standard " the direct discharge standard of table 2 in GB16171-2012.
Content of the invention
The problem being proposed to overcome above processing method to exist of the present invention, proposes a kind of place for semi-coke wastewater
The process technique of the decarburization removing total nitrogen that effect is good, applicability is strong for reason, reliable and stable and easy to operate, process operating cost is relatively low.
To achieve these goals, the technical solution used in the present invention is:
A kind of semi-coke wastewater decarburization removing total nitrogen processes technique, including pretreatment system, biochemical treatment system, advanced treating system
System, pretreatment system includes oil interceptor and two-stage air-flotation process, and biochemical treatment system includes multi-functional denitrification tank, first aerobic
Pond, the second sedimentation basin, anoxic pond, the second Aerobic Pond, the 3rd sedimentation basin, multi-functional denitrification tank, the first Aerobic Pond, anoxic pond and
Two Aerobic Ponds add HSBEMBM environmental improvement microorganism formulation respectively, and the mixed liquor of the first Aerobic Pond is partly refluxed to multi-functional
Denitrification tank, advanced treatment system includes photocatalytic ozonation unit, it is characterised in that:
Biochemical treatment system also includes a sludge absorption bed reactor and the first sedimentation basin, after preprocessed system is processed
Waste water enter sludge absorption bed reactor, by the first sedimentation basin mud-water separation, then enter back into multi-functional denitrification tank, first
Aerobic Pond and subsequent biochemical unit carry out biochemical reaction；Then multi-functional denitrification tank, the first Aerobic Pond and subsequent biochemical are entered back into
Unit carries out biochemical treatment；Throwing in this sludge absorption bed reactor has excess sludge produced by biochemical treatment system, throws simultaneously
Added with sorbing material and biology enzyme inducible factor；In described sludge absorption bed reaction tank, mixture concentration controls at 4000-
5000mg/L；
First Aerobic Pond has several refluxing openings in its flow direction, all connect with reflux line, wherein end
Refluxing opening maintains a normally open；When in the nitroso nitrogen concentration on remaining refluxing opening position with multi-functional denitrification tank, ammonia nitrogen concentration ratio reaches
During to 1:1.6～2.5, open the reflux pump at this refluxing opening, make mixed liquor be back to multi-functional denitrification tank from there simultaneously；
Photocatalytic ozonation reaction tower top is provided with discharge, collects described in causing after the residual ozone that the water surface overflows
First order cavitation air flotation pond in.
Multi-functional denitrification tank, is called for short HLA pond, under anoxic conditions, is converted nitrate, nitroso nitrogen by denitrifying bacteria
For nitrogen, or by anaerobic ammonia oxidizing bacteria by the process that nitroso nitrogen and mineralized nitrogen are nitrogen, thus reach the function of denitrogenation；With
When bacterium colony group in remaining heterotroph microorganism organic matter is converted into the material of intermediate state, little molecule or CO2Deng playing decarburization
Effect, therefore named multi-functional denitrification tank.
HSBEMBM environmental improvement microorganism formulation is commercially available conventional bacterial classification, is that current effect is best, and business is most widely used general
One of microorganism fungus kind.
First described waste water pre-process through oil interceptor and two-stage air supporting, and pretreatment water outlet is reacted through PASAB(sludge absorption bed
Device) reactor absorption degradation, then through " HLA+O-A/O " biochemical treatment, bio-chemical effluent flows through RBAF, photocatalysis and ozone oxygen successively
Change, BAF, more medium filter, the advanced treatment system of UF/RO membranous system, make the effluent quality after process up to standard
Discharge or reuse.
Described preprocessing process is that semi-coke wastewater initially enters oil interceptor, removes overwhelming majority heavy oil and part light oil, goes out
Water enters to connect after regulating reservoir homogeneous is processed and enters two grades of cavitation air flotation process, by scattered gas impeller, " microbubble " is divided uniformly
It is distributed in sewage, adds demulsifier simultaneously, remove overwhelming majority oil emulsion and oil slick and most of undissolved suspended material,
As added quaternary amine multipolymer, dosage about 20mg/L, significantly reduce (tradition PAC throwing than dosages such as traditional medicament PAC
Add more than 100mg/L)；Other scum silica frost generation amount is only the 1/3 of PAC；Cavitation air flotation pond air supporting section liquid level in the first order simultaneously
Residual ozone has been accessed in top so that it is being passed through in water body with the form of microbubble, recycling ozone, ozone oxidation ability is very
By force, it is generally recognized that ozone by direct reaction (ozone directly reacts with the organic matter in oxygen molecule form and water body) and
Connect reaction (to produce the intermediate products such as the very strong hydroxyl radical free radical of oxidisability after ozone decomposes in water body under the conditions of Jian Xing, occur
Indirect oxidation reacts) two kinds of approach react with many organic matters or functional group, such as C=C, C ≡ C, aromatic, heterocycle
Compound, N=N, C=N ,-OH ,-SH ,-NH2,-CHO etc.；Also apolar substance can be changed into polar substances, macromolecule is had
Machine thing is changed into low molecule organic matter, and organic for hydrophily micelle is changed into the inorganic matter that hydrophobicity easily condenses filtration, thus,
The air supporting section in first order cavitation air flotation pond introduces residual ozone, not only recycling ozone, and improves air supporting section and remove
Oil effect, the removal amount simultaneously adding harmful substance, the process load alleviating biochemical section, the operating cost reducing system
(avoid the processing cost of rear end residual ozone when system is run, raising system pre-processes efficiency, reduce biochemical system and deep
Degree processing system processing cost etc.) etc. advantage, therefore, pretreatment stage petroleum-type, total oil removing rate respectively reach 93.3% and
What 90%(did not utilized residual ozone reaches 85.3% and 76%)；Have preferable removal effect to COD simultaneously, clearance reach 20% with
Upper (the pretreatment stage COD clearance of unreferenced residual ozone is 11%), also has certain going to volatile phenol, ammonia nitrogen and total nitrogen
Except effect.Pretreatment outlet delivering a child unit.
In described biochemical treatment unit, described PASAB reactor entitled sludge absorption bed reactor, with the first sedimentation basin structure
Becoming biochemical leading portion pretreatment, the mud in pond is residual active sludge, realizes waste water and excess sludge in PASAB reactor
(excess sludge in the second sedimentation basin or the 3rd sedimentation basin) be sufficiently mixed absorption, simultaneously pass through proof dry powder feeding device, add
The sorbing material such as zeolite powder, activated carbon, plays carrier, strengthens flocculation and the effect of absorption, and need according to water quality index suitable
Amount adds biology enzyme inducible factor, for example: Ca2+、Mo2+Deng；Promote particular organisms degrading enzymatic activity in bacterium, improve absorption simultaneously
The ability of degraded poisonous and harmful substance.Therefore PASAB reactor passes through carrier and adsorption capacity and the utilization of excess sludge are surplus
Microorganism in remaining mud can remove the harmful substances such as most COD, ammonia nitrogen, volatile phenol, aromatic hydrocarbon, adsorbs saturated afterwards
Mud and sorbing material enter the first sedimentation basin and realize mud-water separation, thus realize effective point to Recalcitrant chemicals in water inlet
Leaving away and removing, the hydraulic detention time of PASAB reactor controls in 35-60min, according to water quality and system disposition spoil disposal,
First clarifier sludge is directly discharged into sludge concentration tank.
HLA and the first Aerobic Pond add HSBEMBM environmental improvement microorganism formulation respectively, and HLA mainly undertakes hydrolysis acidification
Function, also takes on denitrification and Anammox function simultaneously, and the first Aerobic Pond undertakes the function of main decarburization and short distance nitration,
Multiple refluxing opening is set in the gallery of the first Aerobic Pond, as used on " S " type gallery at the first Aerobic Pond, on whole gallery
Multiple refluxing opening is installed, as gallery the 1/3rd, the 2/3rd, end all install back head piece, according to influent quality and whole system
Ruuning situation adjusts backwash deployment and capacity of returns, i.e. the nitroso nitrogen concentration in the first Aerobic Pond gallery refluxing opening position with
HLA pond ammonia nitrogen concentration ratio can reach 40%-60%, and the pump opening this refluxing opening carries out mixed-liquor return so that it is can be in short distance
Nitration denitrification or anaerobic ammonium oxidation process, the effective denitrification effect improving system, thus multiple refluxing opening is installed so as
Implementation process adjusts in time different backwash deployment and capacity of returns realizes the function of efficient denitrification (short distance nitration of regulator control system is anti-
Nitrification, Anammox function) while remove COD, improve the nitric efficiency of system and anti-buffer capacity, thus after reducing
End A(anoxic pond)/O(the second Aerobic Pond) load of system；By the mud-water separation of the second sedimentation basin, water outlet enter anoxic pond with
Second Aerobic Pond constitutes traditional A/O system, further removal of carbon and nitrogen, it is ensured that the qualified discharge of the final outflow water of system；Lead to again
Crossing the 3rd sedimentation basin and carrying out mud-water separation, bio-chemical effluent accesses advanced treatment system.
In 2/3 gallery position of the first Aerobic Pond with end refluxes and its capacity of returns ratio respectively 60% and 40% simultaneously, right
Decarburization and denitrogenation have preferably removal effect.The COD of biochemical stage water outlet simultaneously is down to below 120mg/L, ammonia nitrogen ＜ 0.5mg/L,
Total nitrogen ＜ 20mg/L, volatile phenol ＜ 0.2mg/L, petroleum-type ＜ 1mg/L, colourity is down to less than 140 times.And only end backflow, go out
Water total nitrogen is interior near 40-60mg/L, adds advanced treating load, and final outflow water total nitrogen may be caused not up to standard
(in GB16171-2012, table 2 directly discharges).
Described advanced treatment system includes RBAF, photocatalytic ozonation, BAF (BAF), multi-medium filtering
Device, the advanced treatment system of UF/RO membranous system, be finally reached the function of reuse.Described inner circulating aerating biological filtering tank
(RBAF) it is to be arranged and water inlet aeration mode by adjusting the filter material layer in filter tank, it is achieved interior circulation in filter tank for the water inlet, from
And improving decomposition and the separating effect of BAF, the organic matter for bio-chemical effluent is effectively removed.Described photocatalytic ozonation
Undertaking decomposing organic matter is can biochemical small-molecule substance and removal part COD, the function removing cyanide and decolouring, waste water
Entering from lower end, ozone (ozone generator generation) enters water body from lower end by microporous aeration disc simultaneously, in photocatalysis and ozone
Reacting in oxidation reaction tower, waste water flows out from upper end, and remaining ozone overflows the water surface, is drained to first by top duct
Level cavitation air flotation pond air supporting section ullage, as one of air supporting section source of the gas, it is harmful that recycling residual ozone removes part
Material, saves resource and cost.Photocatalytic ozonation water outlet again through BAF, more medium filter, UF/RO film at
Reasons etc., effluent quality reaches the direct discharge standard of table 3 in " coking chemistry emission of industrial pollutants standard " GB16171-2012.
Brief description
Fig. 1 is present example process chart.
Fig. 2 is the first Aerobic Pond mixed-liquor return schematic diagram.
Fig. 3 is photocatalytic ozonation reaction unit schematic diagram.
Detailed description of the invention
Below according to the process chart of Fig. 1 specific implementation process is described:
In Fig. 1, A is semi-coke wastewater；B is residual ozone；C is excess sludge；D is sludge reflux；E is mixed-liquor return,
F is water outlet or reuse.Semi-coke wastewater in this engineering from certain semi-coke factory after ammonia still process, dephenolize, oil removing pre-treatment
Waste water, is made up of with oily waste water two parts (with the inflow of 4:6) phenol wastewater, and water quality index is as shown in table 1, by Fig. 1's
Technical flow design inflow is 1m3The plant running of/h, processing procedure is as follows:
1) pretreatment system:
Semi-coke wastewater enters oil interceptor, removes overwhelming majority heavy oil and part light oil, enters regulating reservoir homogeneous and processes laggard
Entering two grades of cavitation air flotation process, every grade adds quaternary amine multipolymer about 10mg/L, removes overwhelming majority oil emulsion and oil slick, with
When remove most of undissolved suspended material, and utilize residual ozone as gas in first order cavitation air flotation pond air supporting section
One of source, recycling ozone, oxidation processes moieties, reduce the harmful substances such as the COD in waste water, ammonia nitrogen, volatile phenol,
Air supporting water outlet accesses biochemical system.The effect of water outlet after just pre-processing in table 2 below introduces ozone to air supporting section and utilizes air-source
Illustrate (under conditions of other control parameters are the same), the pretreatment water outlet petroleum-type of recycling residual ozone, always oil
Clearance respectively reach 93.3% and 90%(do not utilize residual ozone reach 85.3% and 76%)；COD is had simultaneously and preferably go
Except effect, clearance reaches more than 20% (the pretreatment stage COD clearance of unreferenced residual ozone is 11%), to volatile phenol,
Ammonia nitrogen and total nitrogen also have certain removal effect.
2) biochemical system:
Pretreatment water outlet enters PASAB reactor, is sufficiently mixed with excess sludge, simultaneously according to actual conditions, adds load
Body and biology enzyme inducible factor, choosing mixture concentration is that the mixed liquor that interior control is different in 5000mg/L(PASAB reactor is dense
Degree, its effluent quality situation is as shown in table 3), hydraulic retention 60min, enter the first sedimentation basin afterwards and realize mud-water separation, water outlet
Enter HLA+ the first Aerobic Pond, the gallery of the first Aerobic Pond arranges multiple refluxing opening the 11st, the 12nd, 13, uses " S " type gallery
On (being equally divided into 1/3 gallery the 31st, 2/3 gallery 32 and end 33), return in 2/3 gallery position of the first Aerobic Pond and end simultaneously
Stream and its reflux ratio 60% and 40%(table 4 show the water quality feelings of the whole bio-chemical effluent in the different reflux ratio of gallery the 2/3rd, end
Condition), then carry out mud-water separation through the second sedimentation basin, the rear entrance further denitrification and decarburization of A/O system, the water outlet total nitrogen of safeguards system
Qualified discharge.Drawing in this process of the test, biochemical stage water outlet COD is down to below 120mg/L, ammonia nitrogen ＜ 0.5mg/L,
Total nitrogen ＜ 20mg/L, volatile phenol ＜ 0.2mg/L, petroleum-type ＜ 1mg/L, colourity is down to less than 140 times；And only end backflow, go out
Water total nitrogen is interior near 40-60mg/L, adds advanced treating load, it is also possible to cause final outflow water total nitrogen not up to standard
(in GB16171-2012, table 2 directly discharges).During whole biochemical treatment, the second clarifier sludge is back to HLA pond, the
Three clarifier sludge are back to anoxic pond；Simultaneously also according to water quality and system disposition spoil disposal, it is anti-that excess sludge enters PASAB
Answer device or sludge concentration tank.
3) advanced treating:
Described advanced treatment system includes RBAF, photocatalysis and ozone reaction tower, BAF (BAF), multimedium mistake
Filter, the advanced treatment system of UF/RO membranous system, be finally reached the function of reuse.Described inner circulating aerating biological filtering tank
(RBAF) it is to be arranged and water inlet aeration mode by adjusting the filter material layer in filter tank, it is achieved interior circulation in filter tank for the water inlet, from
And improving decomposition and the separating effect of BAF, the organic matter for bio-chemical effluent is effectively removed.Described photocatalytic ozonation
Undertaking decomposing organic matter is can biochemical small-molecule substance and removal part COD, the function removing cyanide and decolouring, waste water
Entering from lower end 51, ozone (ozone generator generation) enters water body from lower end 52 by microporous aeration disc 23 simultaneously, urges at light
Being reacted by the irradiation of ultraviolet source 22 in changing ozone oxidation reaction tower, waste water flows out from upper end 53, and remaining ozone overflows
Go out the water surface, be drained to first order cavitation air flotation pond air supporting section ullage by top duct 24, as one of air supporting section source of the gas,
Recycling residual ozone removes part harmful substance, saves resource and cost.Photocatalytic ozonation water outlet is again through aeration
Biofilter, more medium filter, UF/RO film process, effluent quality reaches " coking chemistry emission of industrial pollutants standard "
The direct discharge standard of table 3 in GB16171-2012.Degree of depth effluent quality is as shown in table 5:
Claims (1)
1. semi-coke wastewater decarburization removing total nitrogen processes a technique, including pretreatment system, biochemical treatment system, advanced treating system
System, pretreatment system includes oil interceptor and two-stage air-flotation process, and biochemical treatment system includes multi-functional denitrification tank, first aerobic
Pond, the second sedimentation basin, anoxic pond, the second Aerobic Pond, the 3rd sedimentation basin, multi-functional denitrification tank, the first Aerobic Pond, anoxic pond,
Two Aerobic Ponds add HSBEMBM environmental improvement microorganism formulation respectively, and the mixed liquor of the first Aerobic Pond is partly refluxed to multi-functional
Denitrification tank, advanced treatment system includes photocatalytic ozonation unit, it is characterised in that:
Biochemical treatment system also includes a sludge absorption bed reactor and the first sedimentation basin, giving up after the process of preprocessed system
Water enters sludge absorption bed reactor, by the first sedimentation basin mud-water separation, then enters back into multi-functional denitrification tank, first aerobic
Pond and subsequent biochemical unit carry out biochemical reaction；This sludge absorption bed reactor is thrown and has the produced residue of biochemical treatment system
Mud, has added sorbing material and biology enzyme inducible factor simultaneously；Mixture concentration control in described sludge absorption bed reactor
At 4000-5000mg/L；
First Aerobic Pond has several refluxing openings in its flow direction, all connects with reflux line, wherein the backflow of end
Mouth maintains a normally open；When in the nitroso nitrogen concentration on remaining refluxing opening position and multi-functional denitrification tank, ammonia nitrogen concentration ratio reaches 1:
When 1.6～2.5, open the reflux pump at this refluxing opening, make mixed liquor be back to multi-functional denitrification tank from there simultaneously；Light
O3 catalytic oxidation reaction tower top is provided with discharge, collects and causes first order cavitation air flotation after the residual ozone that the water surface overflows
In pond so that it is be passed through in water body with the form of micro-bubble.
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| CN112125478A (en) * | 2020-09-25 | 2020-12-25 | 中蓝连海设计研究院有限公司 | Biochemical treatment-ozone oxidation coupled sewage treatment method and application thereof |
| CN113149346B (en) * | 2021-04-01 | 2023-02-07 | 北京能泰高科环保技术有限公司 | Method for recycling semi-coke wastewater |
| CN115304216A (en) * | 2022-08-03 | 2022-11-08 | 上海扉悦环保科技有限公司 | Semi-coke wastewater treatment process |
| CN116813155B (en) * | 2023-08-31 | 2023-12-22 | 金科环境股份有限公司 | System and method for treating silicon wafer cutting fluid wastewater and application |
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Denomination of invention: Decarbonization and total nitrogen removal treating process for semi-coking wastewater Effective date of registration: 20181212 Granted publication date: 20161109 Pledgee: China Everbright Bank Limited by Share Ltd Hangzhou branch Pledgor: Zhejiang Hanlan Environment Technology Co., Ltd. Registration number: 2018330000458 |
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Date of cancellation: 20200401 Granted publication date: 20161109 Pledgee: China Everbright Bank Limited by Share Ltd Hangzhou branch Pledgor: ZHEJIANG HI-LEGEND ENVIRONMENT TECHNOLOGY Co.,Ltd. Registration number: 2018330000458 |